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

Abstract

Provided is 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. This photosensitive resin composition includes 100 parts by mass of a polyimide precursor resin, 0.5–10 parts by mass of a photopolymerization initiator, and 50–500 parts by mass of a solvent. The polyimide precursor resin includes at least one terminal structure selected from the group consisting of general formulas (1)–(3). The total value for the aliphatic hydrocarbon group concentration T of the polyimide precursor resin is 4–35 wt%.

Description

[Technical field]

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

[0002] Conventionally, polyimide resins, polybenzoxazole resins, phenolic resins, etc., which have excellent heat resistance, electrical properties, and mechanical properties, have been used as insulating materials for electronic components, and passivation films, surface protective films, interlayer insulating films, etc. for 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, exposing, developing, and curing the composition to light, and by ring-closing treatment (imidization, benzoxazole formation) or thermal crosslinking. Such photosensitive resin compositions have the characteristic of enabling a significant reduction in the process compared to conventional non-photosensitive materials, and are used in the production of semiconductor devices.

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

[0004] Therefore, flip-chip mounting has been proposed, in which a rewiring layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed thereon, and then the chip is flipped over and directly mounted on a printed circuit board. This flip-chip mounting allows accurate control of the wiring distance, and is therefore adopted for high-end devices that handle high-speed signals, and for mobile phones and the like due to its small mounting size, and demand is rapidly expanding. More recently, a semiconductor chip mounting technology called fan-out wafer-level packaging (FOWLP) has been proposed, in which a wafer that has undergone pre-processing is diced to manufacture individual chips, the individual chips are reconstructed on a support, sealed with molding resin, and a rewiring layer is formed after the support is peeled off (for example, Patent Document 1). In the fan-out wafer-level packaging, the rewiring layer is formed with a thin film thickness, which has the advantages of making the package thinner, enabling high-speed transmission, and reducing costs.

[0005] In recent years, with the remarkable increase in the amount of information communication, it is necessary to speed up communication beyond the conventional level, and it is unavoidable to move to the fifth generation communication (5G) using frequencies of 3 GHz or more, or to communication in the ultra-high frequency band of the quasi-millimeter wave band (20 GHz to 30 GHz) to millimeter wave band (30 GHz or more) where it is easy to secure a wider frequency bandwidth, and high frequency compatibility is required not only for printed circuit boards but also for semiconductor chips on which the boards are mounted. Therefore, in order to reduce transmission loss, an antenna-in-package (AiP) has been developed in which a front-end module (FEM) that transmits and receives radio waves and an antenna are integrated (for example, see Patent Document 2 below). Since the wiring length is short in AiP, it is possible to suppress the transmission loss that increases in proportion to the wiring length.

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

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

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

[0009] In recent years, the diversification of packaging technology has led to a diversification of the types of supports and the multi-layering of rewiring layers, which has led to a greater influence of the dielectric constant and dielectric dissipation factor (tan δ) of the insulating material used to form the wiring. When the dielectric constant and dielectric dissipation factor are high, the transmission loss increases due to an increase in dielectric loss. Polyimide resins have excellent insulation performance and thermomechanical properties, so they have high material reliability, but the high dielectric constant and dielectric dissipation factor are problematic due to the polar functional groups derived from the imide groups, the addition of polar functional groups for photosensitization, and the effects of additives. In addition, the frequency dependency of the dielectric dissipation factor can be a problem in some cases, and it is considered preferable for the insulating layer to have low moisture permeability.

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

[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 photopolymerization initiator; (C) 50 to 500 parts by mass of a solvent; A photosensitive resin composition comprising: The polyimide precursor resin (A) contains at least one terminal structure selected from the group consisting of the following general formulas (1) to (3): [ka] {In the formula, W is a divalent or trivalent organic group, R1 to R3 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, m1 is a group represented by an integer of 1 or 2, m2 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 repeating units 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 mass of a photosensitizer; (C) 100 to 300 parts by mass of a solvent; A photosensitive resin composition comprising: In the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350° C., 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] 3. The photosensitive resin composition according to any one of items 1 and 2, wherein the polyimide precursor resin (A) is represented by the following general formula (4): [ka] {In the formula, X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, n1 is an integer from 2 to 150, and R4 and R5 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, provided that at least one of R4 and R5 is a group represented by the following general formula (5).} [ka] {In the formula, R6, R7 and R8 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m2 is an integer of 2 to 10.} [4] 4. The photosensitive resin composition according to any one of items 1 to 3, wherein 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 polyimide precursor resin (A) represented by the general formula (4), is 15 wt% to 35 wt%. [5] 5. The photosensitive resin composition according to any one of items 1 to 4, wherein the polyimide precursor resin (A) contains a structure represented by the following general formula (6): [ka] {where, R9, R 10 are each independently an organic group having 1 to 10 carbon atoms, m3 and m4 are integers 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] 7. The photosensitive resin composition according to any one of items 1 to 6, further comprising: (E) a radically polymerizable compound. [8] (F) The photosensitive resin composition according to any one of items 1 to 7, further comprising a thermal crosslinking agent. [9] 9. The photosensitive resin composition according to any one of items 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 the main chain, 1 10. The photosensitive resin composition according to any one of items 1 to 9, wherein a terminal blocking value indicating a terminal blocking rate is 0.02 or more when the 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 mass 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 the main chain, 1A photosensitive resin composition having an end-capping value, which indicates the end-capping rate, of 0.02 or more when the peak area of ​​the amide group derived from the 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 mass 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 the main chain, 1 A photosensitive resin composition having an end-capping value, which indicates the end-capping rate, of 0.06 or more when the peak area of ​​the amide group derived from the 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 items 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 the steps of:

[14] 13. A method for producing a cured film, comprising applying the resin composition according to any one of items 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 ~1.3×10 -2 A method for producing a polyimide cured film, the range being:

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

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

[17] A method for producing a photosensitive resin composition, the 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 mass of a solvent; Including, The method includes the steps of: synthesizing the polyimide precursor resin (A); and mixing the polyimide precursor resin (A), the photopolymerization initiator (B), and a solvent (C) to obtain a photosensitive resin composition; The synthesis process includes 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 the above (i) and / or (ii); 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 (A) polyimide precursor resin 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 the above (i) and / or (ii); 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. Effect of the Invention

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

[0013] [Figure 1] This is an example of the NMR spectrum of a polyimide obtained by heat curing a polyimide precursor at 230°C. [Diagram 2] This is an example of the NMR spectrum of a polyimide obtained by heat curing a polyimide precursor at 230°C. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

[0015] <Photosensitive resin composition> The photosensitive resin composition of the present disclosure contains (A) 100 parts by mass of 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. In addition, the photosensitive resin composition of the present disclosure may further contain, in addition to the above components, (D) a silane coupling agent, (E) an ethylenically unsaturated group-containing compound, (F) a thermal crosslinking agent, (G) a filler, and other components, as desired.

[0016] [(A) Polyimide precursor]

[0017] (Condition 1) It is preferable that the polyimide precursor resin satisfies at least 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 formulas (1) to (3). [ka] {In the formula, W is a divalent or trivalent organic group, R1 to R3 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, m1 is an integer of 1 to 2, m2 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 group to the molecular weight of the repeating unit containing the structure derived from the tetracarboxylic dianhydride and the diamine compound, is 4 wt% to 35 wt%. When the polyimide precursor satisfies these conditions (1-i) and (1-ii), a negative photosensitive resin composition having low dielectric properties, low moisture permeability, and good chemical resistance and high resolution can be obtained.

[0018] (Method 1 for introducing terminal structures) To form the terminal structure of the above general formula (1) and the above general formula (2), a tetracarboxylic dianhydride having a desired tetravalent organic group X is reacted with a compound having an isocyanate group, and then an alcohol having a photopolymerizable group (e.g., an unsaturated double bond) is 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 body). 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. Saturated aliphatic alcohols may be used in combination with the above alcohols having a photopolymerizable group.

[0019] (Method 2 for introducing terminal structures) To form the terminal structure of the above general formula (3), a tetracarboxylic dianhydride having a desired tetravalent organic group X is reacted with an alcohol having a photopolymerizable group (e.g., an unsaturated double bond) to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester body), and then a compound having an isocyanate group is reacted to prepare a partially esterified / amidated tetracarboxylic acid (hereinafter also referred to as an acid / ester / amide body). 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. Saturated aliphatic alcohols may be used in combination with the above alcohols having a photopolymerizable group.

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

[0021] In the case of a reactive terminal structure derived from a tetracarboxylic dianhydride, the polymerization conditions are acid-excessive, and the polymerization system of the resin does not become basic. Therefore, the deactivation of the polymerization active terminal is suppressed, and terminals that cause deterioration of the dielectric tangent are not easily formed, which is preferable from the viewpoint of dielectric tangent. In addition, when the linking structure of the reactive terminal structure is an imide bond or an amide bond represented by the above general formulas (1) to (3), the heat resistance and hydrolysis resistance are improved compared to ester bonds, etc., and the polymerizable functional group does not leave the terminal structure of the resin during a heat treatment process or a reliability test performed under high temperature and high humidity conditions, which is preferable from the viewpoint of chemical resistance. Furthermore, when 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] The "aliphatic hydrocarbon group concentration T" refers to 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 in the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350°C. The reason for the condition of heating and curing at 350°C is to clarify the standard of the aliphatic hydrocarbon group concentration T by using the state in which the polyimide precursor is almost 100% imidized as the standard, and it is not intended that the photosensitive resin composition is heated and cured at 350°C in actual use. Here, the "aliphatic hydrocarbon group" refers to a hydrocarbon group having at least one structure selected from the group consisting of a saturated aliphatic chain, an unsaturated aliphatic chain, and an alicyclic structure that does not contain a heteroatom branched from the main chain of the polyimide precursor, and may be either a straight chain or a branched chain. The part of the alkylene skeleton that constitutes a part of the main chain and the quaternary carbon (carbon that is disubstituted and constitutes a part of the main chain) that constitutes a part of the main chain are not included in the "aliphatic hydrocarbon group" in the calculation of the aliphatic hydrocarbon group concentration. Aliphatic hydrocarbon groups constituting side chains branched from the main chain are included in the "aliphatic hydrocarbon group" in calculating the aliphatic hydrocarbon group concentration, regardless of whether they are saturated or unsaturated, linear or alicyclic. Structural examples 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). [ka]

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

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

[0025] The aliphatic hydrocarbon group concentration T is calculated by 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 kinds of tetracarboxylic dianhydrides and / or diamine compounds are used, for example, when two kinds of tetracarboxylic dianhydrides and two kinds of diamine compounds are used, the following formula (II): [Mw(P1)×a1+Mw(P2)×a2+Mw(Q1)×b1+Mw(Q2)×b2] / [Mw(A1)×a1+Mw(A2)×a2+Mw(B1)×b1+Mw(B2)×b2-36] ×100 (II) In formula (II), Mw(P1) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the first tetracarboxylic dianhydride, Mw(P2) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the second tetracarboxylic dianhydride, Mw(Q1) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the first diamine compound, and Mw(Q2) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the second diamine compound. Mw(A1) represents the molecular weight of the first tetracarboxylic dianhydride, Mw(A2) represents the molecular weight of the second tetracarboxylic dianhydride, a1 represents the content ratio of the first tetracarboxylic dianhydride, and a2 represents the content ratio of the second tetracarboxylic dianhydride. Mw(B1) represents the molecular weight of the first diamine compound, Mw(B2) represents the molecular weight of the second diamine compound, b1 represents the content ratio of the first diamine compound, and b2 represents the content ratio of the second diamine compound. In addition, a1, a2, b1, and b2 satisfy a1+a2=1 and b1+b2=1, respectively.}. It can be calculated in the same manner when three or more types of tetracarboxylic dianhydrides and / or diamine compounds are used. 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 at least both of the following two conditions (2-i) and (2-ii). (2-i) 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, satisfy the following general formula (1): -77≦4T-3S≦44 (1) (2-ii)(A) ​​The polyimide precursor resin has a reactive unsaturated bond structure at the resin terminal that is polymerizable 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 the condition (2-i) has the same definition as the aliphatic hydrocarbon group concentration described in the above condition (1-ii). When the polyimide precursor satisfies 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 diamine compound used in preparing the polyimide precursor, as shown in 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. When two or more kinds of tetracarboxylic dianhydrides and / or diamine compounds are used, the calculation is performed according to the ratio of the raw materials, in the same manner as the definition of the aliphatic hydrocarbon group concentration T above. In the case of a copolymer of a photopolymerizable group-containing compound and a compound not containing a photopolymerizable group, the copolymer can be represented by the following formula (II): [Mw(R)×c1] / [Mw(A)+Mw(B)+Mw(R)×c1+Mw(S)×c2-36]×100 (II) {In formula (II), Mw(R) represents the sum of the molecular weights of the photopolymerizable group-containing compounds, Mw(S) represents the sum of the molecular weights of the compounds not containing a photopolymerizable group, Mw(A) represents the molecular weight of the tetracarboxylic dianhydride, and Mw(B) represents the molecular weight of the diamine compound. c1 represents the content of the photopolymerizable group-containing compounds, c2 represents the content of the compounds not containing a photopolymerizable group, and c1 and c2 each satisfy c1+c2=1.}. When tetracarboxylic acid and / or tetracarboxylic acid chloride is used as the raw material, the molecular weight of the corresponding tetracarboxylic dianhydride is used for the calculation.

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

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

[0032] The (A) polyimide precursor may be a polyamide precursor having a structural unit represented by the following general formula (4). [ka] {In the formula, X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, n1 is an integer from 2 to 150, and R4 and R5 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, provided that at least one of R4 and R5 is a group represented by the following general formula (5).} [ka] {In the formula, R6, R7 and R8 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m2 is an integer of 2 to 10.}In addition, R4 and R5 in the general formula (4) are also referred to as a side chain or a side chain structure of a polyimide precursor.In the above general formula (5), R6 is preferably a hydrogen atom or a methyl group, and R7 and R8 are preferably hydrogen atoms from the viewpoint of photosensitive properties.In addition, m2 is an integer of 2 to 10, preferably an integer of 2 to 4, from the viewpoint of photosensitive properties.

[0033] From the viewpoint of resolution and low dielectric properties, the ratio of photosensitive groups per repeating unit in the polyimide precursor resin is preferably 15wt% to 35wt%. From the viewpoint of dielectric properties, the fewer the photosensitive groups, the more the photosensitive groups. From the viewpoint of resolution, the more the photosensitive groups. In this specification, the "proportion 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 photopolymerizable groups include unsaturated double bonds.

[0034] In the above general formula (4), n1 is preferably an integer from 3 to 100, and more preferably an integer from 5 to 70, from the viewpoint of the photosensitive properties and mechanical properties of the photosensitive resin composition.

[0035] In the above general formula (4), the tetravalent organic group represented by X1 is preferably an organic group having 6 to 40 carbon atoms, from the viewpoint of achieving both heat resistance and photosensitive properties, and more preferably an aromatic group in which the -COOR1 group and the -COOR2 group are at the ortho position relative to the -CONH- group, or an alicyclic aliphatic group. Specific examples of the tetravalent organic group represented by X1 include organic groups having 6 to 40 carbon atoms containing an aromatic ring, such as the following general formula (7): [ka] {In formula (7), R 11is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 hydrocarbon group, and a C1-C10 fluorine-containing hydrocarbon group, m5 is an integer of 0 to 2, m6 is an integer of 0 to 3, and m7 is an integer of 0 to 4.}, but is not limited thereto. The structure of X1 may be one type or a combination of two or more types. The X1 group having the structure represented by the above formula (7) is particularly preferred in that it has both heat resistance and photosensitive properties.

[0036] In the above general formula (7), the divalent organic group represented by Y1 is preferably an aromatic group having 6 to 40 carbon atoms in order to achieve both heat resistance and photosensitive properties, and is, for example, a group represented by the following general formula (8): [ka] {In formula (8), R 11 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 hydrocarbon group, and a C1-C10 fluorine-containing hydrocarbon group, m5 is an integer of 0 to 2, m6 is an integer of 0 to 3, and m7 is an integer of 0 to 4.}, but is not limited thereto. The structure of Y1 may be one type or a combination of two or more types. The Y1 group having the structure represented by the above formula (8) is particularly preferred in that it has both heat resistance and photosensitive properties.

[0037] From the viewpoints of resolution, moisture permeability, and low dielectric properties, X1 and / or Y1 of the polyimide precursor resin (A) represented by the above general formula (4) preferably contain a structure represented by the following general formula (6). [ka] {where, R9, R 10 are each independently an organic group having 1 to 10 carbon atoms, m3 and m4 are integers from 1 to 4, Z1 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 polyimide precursor resin.}

[0038] By including the structure of the above general formula (6), a cured film with good relief pattern resolution and 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, making it easier to ensure contrast with the exposed area and improving the resolution of the relief pattern. In addition, by introducing an organic group into the aromatic ring, the hydrophobicity of the film is increased, making it less permeable to moisture.

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

[0040] In the above general formula (4), the structure represented by X1 preferably includes at least one structure selected from the group consisting of the following general formula (10). [ka]

[0041] In the above general formula (4), the structure represented by Y1 preferably includes at least one structure selected from the group consisting of the following general formula (11). [ka] The structure of the above general formula (6) is not limited to the structures listed in the above (9) to (11). The above structures may be one type or a combination of two or more types.

[0042] In the (A) polyimide precursor, at least one of X1, which is a skeleton component derived from a tetracarboxylic acid compound, and Y1, which is a skeleton component derived from a diamine compound, preferably has a structure in which two or more benzene rings are bonded. The number of benzene rings may be 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 obtained cured relief pattern tends to have low dielectric properties.

[0043] [(A) Method for preparing polyimide precursor] (Formation of reactive terminal structures) A method for forming a terminal structure having a reactive substituent at the main chain end of a polyimide precursor resin includes 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 the above (i) and / or (ii); A synthesis method including 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 introduction portion, a tetracarboxylic dianhydride, and a diamine compound is preferred. As described above, by using a synthesis method of introducing a second compound into a tetracarboxylic dianhydride and / or a diamine compound before polymerizing a polyimide precursor (hereinafter, also referred to as "pre-capping"), the polyimide precursor resin (A) can have a reactive substituent derived from the second compound at the main chain end. Examples of the first compound include alcohols having a photopolymerizable group, and examples of the second compound include an isocyanate compound having a photopolymerizable group.

[0044] (Preparation of Acid / Ester Forms) Examples of tetracarboxylic dianhydrides having a tetravalent organic group X1 having 6 to 40 carbon atoms, which are preferably used for preparing an ester bond-type polyimide precursor, include, in addition to the tetracarboxylic dianhydrides derived from the structures listed above, pyromellitic anhydride, 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, Examples of the dianhydride include, but are not limited to, 3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride, etc. In addition, these may be used alone or in combination of two or more.

[0045] Using these tetracarboxylic dianhydrides containing a tetravalent organic group X1 having 6 to 40 carbon atoms, a terminal structure is formed by the above-mentioned introduction method 1 or introduction method 2. The order of the reactions differs depending on the introduction method.

[0046] Examples of a compound having a photopolymerizable group (corresponding to the above-mentioned "second compound") that is suitably used for synthesizing an esterified tetracarboxylic acid having a reactive terminal represented by the above-mentioned general formulas (1) to (3) and for introducing an unsaturated bond structure via a urea bond or an amide bond derived from a diamine compound include 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 2-(2-methacryloyloxyethyloxy)ethyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, allylamine, methacrylic acid chloride, 5-norbornene-2-methylamine, and 4-vinylaniline. Furthermore, examples of alcohols having a photopolymerizable group (corresponding to the above-mentioned "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, and 2-hydroxy-3-t-butoxypropyl. Examples of the acrylate include 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, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

[0047] The saturated aliphatic alcohols that can be optionally used together with the alcohols having a photopolymerizable group are preferably saturated aliphatic alcohols having 1 to 4 carbon atoms, specific examples of which include methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol.

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

[0049] The reaction solvent is preferably one that completely dissolves the raw material tetracarboxylic dianhydride and alcohols, as well as the product acid / ester. More preferably, it is a solvent that completely dissolves the polyimide precursor, which is an amide polycondensation product of the acid / ester and diamine. Examples of the reaction solvent include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons. Specific examples of these include: Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of esters include methyl acetate, ethyl acetate, butyl acetate, and diethyl oxalate. Examples of lactones include γ-butyrolactone. Examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran. Examples of halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, and o-dichlorobenzene. Examples of hydrocarbons include hexane, heptane, benzene, toluene, and xylene. These may be used alone or in combination as needed.

[0050] (Preparation of polyimide precursor) The acid / ester body (typically in a solution state dissolved in the reaction solvent) is mixed with a suitable dehydration condensation agent, preferably under ice cooling, to convert the acid / ester body into a polyacid anhydride. Then, a diamine containing a divalent organic group Y1 having 6 to 40 carbon atoms dissolved or dispersed in a separate solvent is added dropwise to the acid / ester body, and the two are subjected to amide polycondensation to obtain a target polyimide precursor. Diaminosiloxanes may be used in combination with the diamine having the divalent organic group Y1. Examples of the dehydration condensation agent include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate. In this manner, a polyacid anhydride intermediate is obtained.

[0051] Diamines having a divalent organic group Y1 having 6 to 40 carbon atoms that can be suitably used in the reaction with the polyacid anhydride obtained as described above include, in addition to the diamines derived from the structures listed above, for example, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'- Diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene , bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2 ,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, bis{4-(4-aminophenoxy)phenyl}ketone, and those in which some of the hydrogen atoms on the benzene ring are replaced by alkyl chains such as methyl groups and ethyl groups, for example, 2,2'-dimethyl-4,Examples of the diamines include 4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof. However, the diamines are not limited to these. These can be used alone, or two or more of them can be mixed together.

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

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

[0054] The weight average molecular weight of the (A) polyimide precursor is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, and particularly preferably 18,000 to 40,000, as measured by gel permeation chromatography (GPC) in terms of polystyrene equivalent weight average molecular weight, from the viewpoint of 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, while 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. In addition, 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 KK.

[0055] [(B) Photopolymerization initiator] (B) Photopolymerization initiator is a compound that generates radicals by actinic rays and can polymerize an ethylenically unsaturated group-containing compound, etc. 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 include benzophenone, N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl aromatic ketones such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, and the like; benzoin ether compounds such as benzoin, methylbenzoin, and ethylbenzoin; 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (BASF Japan Ltd., Irgacure Oxe02), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(o-benzoyloxime) (manufactured by Joshu Kyokai Electronic Materials Co., Ltd., PBG305), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (manufactured by Nikko Chemtech Co., Ltd., product name TR-PBG-326), and other oxime ester compounds; benzyl derivatives such as benzyl dimethyl ketal; acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; N-phenylglycine derivatives such as N-phenylglycine; coumarin compounds; oxazole compounds; and phosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. The polymerization initiator (C) described above can be used alone or in combination of two or more kinds. Among the above photopolymerization initiators, oxime ester compounds are more preferable, especially from the viewpoint of resolution. Among these, it is particularly preferable that the radical species is derived from a methyl group.

[0056] The amount of the photopolymerization initiator is 0.5 parts by mass or more and 10 parts by mass or less, and preferably 1 part by mass or more and 8 parts by mass or less, relative to 100 parts by mass of the (A) polyimide precursor. The amount is preferably 0.5 parts by mass or more from the viewpoint of photosensitivity or patterning property, and 10 parts by mass or less from the viewpoint of physical properties of the photosensitive resin layer after curing of the photosensitive resin composition.

[0057] [(C) Solvent] The solvent (C) is not limited as long as it can uniformly dissolve or suspend the polyimide precursor (A) and the photopolymerization initiator (B). Examples of such a solvent include γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, N,N-dimethylacetoacetamide, ε-caprolactone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N,N-dimethylacetamide. These solvents may be used alone or in combination 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 1,000 parts by mass, relative to 100 parts by mass of the polyimide precursor (A) according to the desired coating thickness and viscosity of the photosensitive resin composition. When the solvent contains an alcohol having no olefinic double bond, the content of the alcohol having no olefinic double bond in the total solvent is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. When the content of the alcohol having no olefinic double bond is 5% by mass or more, the storage stability of the photosensitive resin composition is improved, and when it is 50% by mass or less, the solubility of the polyimide precursor (A) is improved.

[0059] [(D) Silane coupling agent] In order to improve the adhesion of the relief pattern, the photosensitive resin composition may optionally contain a silane coupling agent (D). The silane coupling agent (D) preferably has a structure represented by the following general formula (12). [ka] {where, R 12 is at least one selected from the group consisting of a substituent containing an epoxy group, a phenylamino group, a urea group, an isocyanuric group, and a ureido group; R 13 are each independently an alkyl group having 1 to 4 carbon atoms, R 14 is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, d is an integer of 1 to 3, and m8 is an integer of 1 to 6.}

[0060] In general formula (12), d is not limited as long as it is an integer of 1 to 3, but from the viewpoint of adhesion to the metal redistribution layer, it is preferably 2 or 3, and more preferably 3. m8 is not limited as long as it is an integer of 1 to 6, but from the viewpoint of adhesion to the metal redistribution layer, it is preferably 1 or more and 4 or less. From the viewpoint of developability, it is preferably 2 or more and 5 or less.

[0061] R 12 is not limited as long as it is a substituent containing any one of the structures of the group consisting of an epoxy group, a phenylamino group, a urea group, an isocyanuric group, and a ureido group. Among these, from the viewpoint of developability and adhesion of the metal redistribution layer, it is preferable that it is at least one selected from the group consisting of a substituent containing a phenylamino group, a substituent containing a urea group, and a substituent containing a ureido group, and a substituent containing a phenylamino group is more preferable. 13 is not limited as long as it is an alkyl group having 1 to 4 carbon atoms. Examples of R include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t-butyl group. 14 is not limited as long as it is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include R 13 The alkyl groups shown in the above are exemplified.

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

[0063] [(E) Radical polymerizable compound] In order to improve the resolution of the relief pattern, the photosensitive resin composition may optionally contain (E) a radically polymerizable compound. As such a compound, a (meth)acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferred, and examples thereof include, but are not limited to, mono- or diacrylates or methacrylates of ethylene glycol or polyethylene glycol, including diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, mono- or diacrylates or methacrylates of propylene glycol or polypropylene glycol, mono-, di- or triacrylates or methacrylates of glycerol, cyclohexane diacrylate or dimethacrylate, diacrylates or dimethacrylates of 1,4-butanediol, and 1,6 Examples of the monomer include diacrylate or dimethacrylate of 2-hexanediol, diacrylate or dimethacrylate of neopentyl glycol, mono- or diacrylate or methacrylate of bisphenol A, benzene trimethacrylate, isobornyl acrylate or methacrylate, acrylamide or a derivative thereof, methacrylamide or a derivative thereof, trimethylolpropane triacrylate or methacrylate, di- or triacrylate or methacrylate of glycerol, di-, tri- or tetraacrylate or methacrylate of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds. These monomers may be used alone or in a mixture of two or more.

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

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

[0066] The thermal crosslinking agent (F) refers to a compound that undergoes an addition reaction or a condensation polymerization reaction by heat. These reactions occur between the resin (A) and the thermal crosslinking agent (F), between the thermal crosslinking agents (F) themselves, and between the thermal crosslinking agent (F) and other components described below, and the reaction temperature is preferably 150°C or higher.

[0067] It is preferable that the (F) thermal crosslinking agent contains a nitrogen atom. This enhances the interaction with the polyimide resin, and higher chemical resistance can be expected. Examples of the (F) thermal crosslinking 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: [ka] [ka]

[0069] Examples of epoxy compounds include epoxy compounds containing a bisphenol A group and hydrogenated bisphenol A diglycidyl ether (e.g., Epolite 4000 manufactured by Kyoeisha Chemical Co., Ltd.). Examples of oxetane compounds include 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, bis[1-ethyl(3-oxetanyl)]methyl ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methyl]biphenyl, 4,4'-bis(3-ethyl-3-oxetanylmethoxy)biphenyl, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, diethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, bis(3-ethyl-3-oxetanylmethyl) Examples of such oxetane derivatives include diphenoate, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl)ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether, poly[[3-[(3-ethyl-3-oxetanyl)methoxy]propyl]silosequioxane] derivatives, oxetanyl silicate, phenol novolac-type oxetane, 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene, OXT121 (manufactured by Toagosei, trade name), and OXT221 (manufactured by Toagosei, trade name). Examples of bismaleimide compounds include 1,2-bis(maleimide)ethane, 1,3-bis(maleimide)propane, 1,4-bis(maleimide)butane, 1,5-bis(maleimide)pentane, 1,6-bis(maleimide)hexane, 2,2,4-trimethyl-1,6-bis(maleimide)hexane, N,N'-1,3-phenylenebis(maleimide), 4-methyl-N,N'-1,3-phenylenebis(maleimide), and 5-methyl-N,N'-1,3-phenylenebis(maleimide). Examples of the 4-maleimide-1,4-phenylene bis(maleimide) include N,N'-1,4-phenylene bis(maleimide), 3-methyl-N,N'-1,4-phenylene bis(maleimide), 4,4'-bis(maleimide)diphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-bis(maleimide)diphenylmethane, and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane.Examples of the allyl compound include allyl alcohol, allyl anisole, allyl benzoate ester, allyl cinnamate ester, N-allyloxyphthalimide, allylphenol, allyl phenyl sulfone, allyl urea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl isocyanurate, triallyl amine, triallyl isocyanurate, triallyl cyanurate, triallyl amine, triallyl 1,3,5-benzenetricarboxylate, triallyl trimellitate, triallyl phosphate, triallyl phosphite, and triallyl citrate. Examples of the blocked isocyanate compound include hexamethylene diisocyanate-based blocked isocyanates (e.g., Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B, and WM44-L70G manufactured by Asahi Kasei Corporation, Takenate B-882N manufactured by Mitsui Chemicals, Inc., and 7960, 7961, 7982, 7991, and 7992 manufactured by Baxenden), tolylene diisocyanate-based blocked isocyanates (e.g., Takenate B-830 manufactured by Mitsui Chemicals, Inc.), 4 ,4'-diphenylmethane diisocyanate-based blocked isocyanates (e.g., Takenate B-815N manufactured by Mitsui Chemicals, Inc., Bronate PMD-OA01 and PMD-MA01 manufactured by Daiei Sangyo Co., Ltd., etc.), 1,3-bis(isocyanatemethyl)cyclohexane-based blocked isocyanates (e.g., Takenate B-846N manufactured by Mitsui Chemicals, Inc., Coronate BI-301, 2507, and 2554 manufactured by Tosoh Corporation, etc.), and isophorone diisocyanate-based blocked isocyanates (e.g., 7950, 7951, and 7990 manufactured by Baxenden, etc.). Among these, blocked isocyanates and bismaleimide compounds are preferred from the viewpoint of storage stability. (F) Thermal crosslinking agents may be used alone or in combination of two or more 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 mass of the solid content of the resin composition, and from the viewpoints of low dielectric properties and chemical resistance, it is more preferably 1% by mass to 20% by mass, and further 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 may optionally contain a filler (G). The filler is not limited as long as it is an inactive substance added to improve strength and various properties.

[0072] The filler is preferably particulate from the viewpoint of suppressing an increase in viscosity when the resin composition is prepared. Examples of particulate shapes include needle-shaped, plate-shaped, and spherical shapes, and the filler is preferably spherical from the viewpoint of suppressing an increase in viscosity when the resin composition is prepared.

[0073] Examples of the needle-shaped filler include wollastonite, potassium titanate, xonotlite, aluminum borate, and needle-shaped calcium carbonate.

[0074] Examples of the plate-like filler include talc, mica, sericite, glass flakes, montmorillonite, boron nitride, and plate-like calcium carbonate.

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

[0076] The size of the filler is defined as the primary particle diameter in the case of a sphere, and the length of the long side in the case of a plate or needle, and is preferably 5 nm to 1000 nm, more preferably 10 nm to 1000 nm. 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, it is preferably 800 nm or less, more preferably 600 nm or less, and particularly preferably 300 nm or less. From the viewpoint of adhesion and resin composition uniformity, it is preferably 15 nm or more, more preferably 30 nm or more, and particularly preferably 50 nm or more.

[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, and from the viewpoint of dielectric properties, it is preferably 5 vol% to 20 vol%, and from the viewpoint of resolution, it is more preferably 5 vol% to 10 vol%.

[0078] [Other ingredients] The photosensitive resin composition may further contain components other than the above components (A) to (G). Examples of the other components include resin components other than the polyimide precursor (A), 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 component 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 parts 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. The organic group preferably contains a hydrocarbon group or a hydrocarbon group containing a heteroatom. By containing an organic compound, the imidization rate of the polyimide precursor contained in the photosensitive resin composition increases, and the dielectric loss tangent of the cured film decreases. Examples of organic titanium or zirconium compounds that can be used 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 below in I) to VII): I) As the chelate compound, a compound having two or more alkoxy groups is more preferable because it provides the storage stability of the photosensitive resin composition and a good pattern. Specific examples of the chelate compound include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and compounds in which the titanium atom of these compounds is replaced with a zirconium atom, but are not limited thereto.

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

[0083] III) Titanocene or zirconocene compounds include, for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η 5 -2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and compounds in which the titanium atom in these compounds is replaced with a zirconium atom, but are not limited to these.

[0084] IV) Examples of monoalkoxy compounds include titanium tris(dioctylphosphate)isopropoxide, titanium tris(dodecylbenzenesulfonate)isopropoxide, and compounds in which the titanium atom of these compounds is replaced with a zirconium atom, but are not limited to these.

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

[0086] VI) Examples of titanium tetraacetylacetonate or zirconium tetraacetylacetonate compounds include, but are not limited to, titanium tetraacetylacetonate and compounds in which the titanium atom of these compounds is replaced with a zirconium atom.

[0087] VII) Titanate coupling agents include, but are not limited to, isopropyl tridodecylbenzenesulfonyl titanate.

[0088] Among the above I) to VII), it is preferable that the organic titanium compound is at least one compound selected from the group consisting of the above I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of exhibiting a better dielectric tangent. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium is preferred.

[0089] When an organic titanium or zirconium compound is blended, the blending amount is 0.01 to 5 parts by mass, preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the (A) resin. If the blending amount is 0.01 parts by mass or more, a good imidization rate of the resin composition and a good dielectric loss tangent of the cured film are exhibited, while if it is 10 parts by mass or less, excellent storage stability is obtained, which is preferable.

[0090] The photosensitive resin composition contains an organic compound containing the above-mentioned metal element, thereby improving the imidization rate of the polyimide precursor contained in the resin composition and reducing the dielectric loss tangent of the cured film using the resin composition. Without being bound by theory, the reason for improving the imidization rate of the polyimide precursor is believed to be that the metal element contained in the organic compound containing a metal element is coordinated 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 may optionally contain a sensitizer to improve photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylaminocinnamylideneindanone. p-Dimethylaminobenzylideneindanone, 2-(p-Dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-Dimethylaminophenylvinylene)benzothiazole, 2-(p-Dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetone ethyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, and the like. These may be used alone or in combination of two or more (for example, two to five kinds). The amount of the sensitizer to be added is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the polyimide precursor (A).

[0092] The photosensitive resin composition may optionally contain a thermal polymerization inhibitor in order to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition during storage, particularly in the form 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 diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt. These thermal polymerization inhibitors may be used alone or in a mixture of two or more. The amount of the thermal polymerization inhibitor to be added is preferably within a range of 0.005 parts by mass to 12 parts by mass per 100 parts by mass of the (A) polyimide precursor.

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

[0094] The amount of the azole compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the polyimide precursor (A), and more preferably 0.5 to 5 parts by mass from the viewpoint of photosensitivity characteristics. If the amount of the azole compound is 0.1 part by mass or more relative to 100 parts by mass of the polyimide precursor (A), discoloration of the copper or copper alloy surface is suppressed when the photosensitive resin composition is formed on copper or a copper alloy, and on the other hand, if it is 20 parts by mass or less, photosensitivity is excellent, which is preferable.

[0095] When a substrate made of copper or a copper alloy is used, the photosensitive resin composition may contain a hindered phenol compound to suppress discoloration of the substrate. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6 -t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylene bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis(4-methyl -6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis〔3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate〕, tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)- 1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-Triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione Trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3 ,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, etc., 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 amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the polyimide precursor (A), and from the viewpoint of photosensitivity characteristics, more preferably 0.5 to 10 parts by mass. If the amount of the hindered phenol compound is 0.1 part by mass or more relative to 100 parts by mass of the polyimide precursor (A), for example, when the photosensitive resin composition is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented, while if it is 20 parts by mass or less, photosensitivity is excellent, which is preferable.

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

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

[0099] Specific steps in the method for producing a cured film can be performed according to steps (1) to (5) in the method for producing a cured film described above. A typical embodiment of each step will be described below.

[0100] (1) A step of applying a photosensitive resin composition onto a substrate to form a photosensitive resin layer on the substrate. In this step, the photosensitive resin composition of the present disclosure is applied onto a substrate, and then dried as necessary to form a photosensitive resin layer. As the application method, a method that has been conventionally used for applying a photosensitive resin composition, such as a method of applying using a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, or the like, or a method of spray application using a spray coater, can be used.

[0101] (2) A step of heating and drying the obtained photosensitive resin layer If necessary, the photosensitive resin composition film can be heated and dried. Drying methods include air drying, heat drying with an oven or a hot plate, vacuum drying, and the like. It is preferable to dry the coating film under conditions that do not cause imidization of the (A) polyimide precursor (polyamic acid ester) in the photosensitive resin composition. Specifically, when air drying or heat drying is performed, drying can be performed under conditions of 20°C to 140°C for 1 minute to 1 hour. In this manner, a photosensitive resin layer can be formed on the substrate.

[0102] (3) A step of exposing the photosensitive resin layer after heating and drying In this step, the photosensitive resin layer formed above is exposed to light. As the exposure device, for example, a contact aligner, a mirror projection, a stepper, or other exposure device is used. The exposure can be performed through a photomask or reticle having a pattern, or directly. The light used for exposure is, for example, an ultraviolet light source.

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

[0104] (4) A process of developing the exposed photosensitive resin layer In this step, the exposed photosensitive resin layer is developed to form a relief pattern. When the photosensitive resin composition is a negative type, the unexposed portion of the exposed photosensitive resin layer is developed and removed. As a development method for developing the exposed (irradiated) photosensitive resin layer, any method can be selected from conventionally known photoresist development methods, such as a rotary spray method, a paddle method, and a dipping method accompanied by ultrasonic treatment. After development, for the purpose of adjusting the shape of the relief pattern, post-development baking may be performed at any combination of temperature and time, as necessary. As a developer used for development, for example, a good solvent for the negative photosensitive resin composition, or a combination of the good solvent and a poor solvent is preferable. As a 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, water, etc. are preferable. When a good solvent and a 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 photosensitive resin composition. In addition, two or more kinds of each solvent, for example, several kinds, can be used in combination. In the process of developing the photosensitive resin layer after exposure, it is preferable to carry out the above-mentioned coating-developing process so as to obtain a photosensitive resin layer having a film thickness of 10 μm to 15 μm. The development time is preferably 30 seconds or less, more preferably 25 seconds or less, and even more preferably 20 seconds or less. Although not bound by theory, by the development time being 30 seconds or less, a difference in solubility with the exposed part is generated, and contrast is provided, and the resolution of the pattern is improved.

[0105] (5) A process of heat-treating the developed photosensitive resin layer to form a polyimide cured film. In this step, the relief pattern obtained by the above development is heated to disperse the photosensitive component and imidize the polyimide precursor (A) to convert it into a cured relief pattern made of polyimide. As a method of heat curing, various methods can be selected, such as using a hot plate, an oven, or a temperature-elevating oven that can set a temperature program. Heating can be performed, for example, under conditions of 160°C to 400°C for 30 minutes to 5 hours. As the atmospheric gas during heat curing, air or an inert gas such as nitrogen or argon can be used. In this manner, a cured relief pattern (polyimide cured film) can be produced.

[0106] The method for producing a polyimide cured film of the present disclosure includes, for example, applying the photosensitive resin composition of the present disclosure onto a substrate, exposing the substrate to light, developing the substrate, and then heating the substrate, and the cured film preferably has a dielectric loss tangent of 0.003 to 0.012 when measured at 40 GHz by a perturbation split cylinder resonator method. The dielectric loss tangent can be measured by the perturbation split cylinder resonator method 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 moisture permeability of less than 800, more preferably less than 700. From the viewpoint of dielectric loss tangent, the lower the moisture permeability, the better since the dielectric loss tangent tends to have less frequency dependency, while from the viewpoint of resolution, the lower the moisture permeability, the worse the solubility of the unexposed area during patterning and the worse the resolution, so that the moisture permeability is more preferably 500 or more and less than 800. When the moisture permeability is less than 800, a highly reliable cured film can be obtained. See below for details of the method for measuring the moisture permeability. From the viewpoints of resolution and the frequency dependency of the dielectric properties and dielectric loss tangent, the product of the dielectric loss tangent and the moisture permeability (tan δ 40 × WVTR) is preferably within a certain range, and when the dielectric tangent value at 40 GHz is used, the following formula (2): 3.0 <tanδ 40 ×WVTR<10.0 (2) It is preferable that tan δ 40 When ×WVTR is in the range of 3.0 to 10.0, a polyimide cured product having excellent resolution and dielectric properties and little frequency dependency can be obtained. The difference in dielectric tangent between 40 GHz and 10 GHz is preferably 0.0015 or less, and more preferably 0.001 or less.

[0108] From the viewpoint of achieving both dielectric tangent and chemical resistance, the polyimide cured film obtained according to the present disclosure is further characterized by the product (tan δ) of the dielectric tangent, the moisture permeability, and the dissolution rate of the cured film in a chemical solution during a chemical resistance test. 40 × WVTR × DR) is preferably within a certain range, and when the dielectric tangent value at 40 GHz is used, the following formula (3): 4.0 <tanδ 40 ×WVTR×DR<29.0 (3) It is preferable that tan δ 40 When ×WVTR×DR is in the range of 4.0 to 29.0, a polyimide cured product having excellent dielectric properties and chemical resistance and little frequency dependency can be obtained.

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

[0110] The polyimide contained in the cured relief pattern (cured polyimide film) formed from the polyimide precursor composition is represented by the following general formula (13): [ka] It is preferable that the compound has a structure represented by the following formula: {In the general formula (13), X1 and Y1 are the same as X1 and Y1 in the above general formula (4), and n2 is an integer of 2 to 150.}.

[0111] <Display device> The present disclosure can also provide a display device using the photosensitive resin composition of the present disclosure, the display device including a display element and a cured film provided on the upper part of the display element, the cured film being the above-mentioned cured relief pattern. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer sandwiched therebetween. For example, the cured film can be a surface protective film, an insulating film, and a planarizing film for a TFT liquid crystal display element and a color filter element, a protrusion for an MVA type liquid crystal display device, and a partition wall for an organic EL element cathode.

[0112] The photosensitive resin composition of the present disclosure is useful not only for application to the semiconductor devices described above, but also for applications such as interlayer insulation in multilayer circuits, cover coats for flexible copper-clad boards, solder resist films, and liquid crystal alignment films.

[0113] <Method for producing photosensitive resin composition> The method for producing a photosensitive resin composition according to the present disclosure is a method for producing a resin composition containing 100 parts by mass of (A) a polyimide precursor, 0.5 to 10 parts by mass of (B) a photopolymerization initiator, and 50 to 500 parts by mass of (C) 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 (B) photopolymerization initiator, and the (C) solvent in the range of parts by mass described above to obtain a photosensitive resin composition. The synthesis step includes 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; Includes.

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

[0115] In the present specification, the ratio of the number of moles of reactive substituents bonded per unit molar amount of carboxylic acid groups derived from tetracarboxylic dianhydride located at the main chain terminal of (A) polyimide precursor resin or per unit molar amount of amine groups derived from diamine compound located at the main chain terminal is referred to as "capping rate". The comparison of the capping rates is as follows: 1 It can be performed by H-NMR. That is, the area of ​​the proton peak (around 5.0 ppm to 6.5 ppm) of the polymerizable functional group derived from the terminal structure is taken as the "terminal capping value" when the area of ​​the aromatic amide peak (around 10.0 ppm to 11.0 ppm) derived from the main chain is taken as 1.0, and the capping rate can be compared by comparing this. When the proton peak of the polymerizable functional group derived from the repeating structure or other peaks unrelated to the polymerizable functional group 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 peak intensity tends to be higher in pre-capping than in post-capping. The reason for this, without being limited to theory, is thought to be that in pre-capping, the reaction rate is high due to the reaction between monomers (low molecular weight), whereas in post-capping, the reaction rate is low due to the inactivation of active ends during polymerization and the reaction between polymers (high molecules) and monomers (low molecular weight).

[0117] For example, FIG. 1 shows a polyimide precursor resin in which the carboxylic acid groups derived from the tetracarboxylic dianhydride at the ends of the main chain are pre-capped. 1 An example of H-NMR is shown in Figure 1. 1 In the case of H-NMR, the area of ​​the aromatic amide peak at 10.4 ppm is set to 1.0, and the area of ​​the proton peaks (symbol 1) of the polymerizable functional groups derived from the terminal structures at around 5.7 ppm and 6.1 ppm is calculated as the end-capping value. Since the proton peaks of the polymerizable functional groups derived from the repeating structures (two peaks around 5.6 ppm and two peaks around 6.0 ppm) (symbol 2) are confirmed near the proton peaks of the polymerizable functional groups derived from the terminal structures, these proton peaks are excluded from the calculation of the "end-capping value".

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

[0119] The photosensitive resin composition of the present disclosure comprises: (A) a polyimide precursor resin having a terminal structure derived from a tetracarboxylic dianhydride at an end of a main chain; 1 In H-NMR, when the peak area of ​​the amide group derived from the main chain structure is taken as 1.0, the terminal blocking value is preferably 0.02 or more, more preferably 0.04 or more, and even more preferably 0.06 or more. In the photosensitive resin composition of the present disclosure, the (A) polyimide precursor resin contains a terminal structure derived from a diamine at the end of the main chain, 1 In H-NMR, when the peak area of ​​the amide group derived from the main chain structure is taken as 1.0, the end blocking value is preferably 0.06 or more, more preferably 0.07 or more, and even more preferably 0.08 or more. A high blocking reaction rate means a high blocking rate. A high blocking rate improves chemical resistance under synthesis conditions with an excess of dianhydride, and improves dielectric loss tangent since deactivation of reactive terminals during polymerization is suppressed under synthesis conditions with an excess of diamine. 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 (standard polystyrene equivalent). The columns used for the measurement were Shodex 805M / 806M (trade name) 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 (trade name) manufactured by Showa Denko K.K.

[0122] (2) Resolution and development time of cured relief patterns on Cu substrates A 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25μm) was sputtered with 200nm thick Ti and 400nm thick Cu in that order using a sputtering device (L-440S-FHL model, manufactured by Canon Anelva Corporation). Next, a photosensitive resin composition prepared by the method described below was spin-coated on this wafer using a coater developer (D-Spin60A model, manufactured by SOKUDO Co., Ltd.), and then heated and dried on a hot plate at 110°C for 3 minutes to form a photosensitive resin layer with a thickness of approximately 13.5μm. Using a test pattern mask, this photosensitive resin layer was sprayed with 300mJ / cm using Prisma GHI (manufactured by Ultratech Co., Ltd.) equipped with an i-line filter. 2The photosensitive resin layer was then spray-developed with a coater developer (D-Spin60A type, manufactured by SOKUDO Co., Ltd.) using cyclopentanone as a developer, and rinsed with propylene glycol methyl ether acetate to obtain a relief pattern on Cu. The time for spray development at this time was defined as the development time. The wafer on which the relief pattern was formed on Cu was heated for 2 hours at 230°C in a nitrogen atmosphere using a temperature-rise programmable curing furnace (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd.) to obtain a cured relief pattern made of a resin having a thickness of about 10 μm on Cu. The relief pattern thus produced 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 considered to be resolved, and the resolution was evaluated according to the following evaluation criteria based on the length of the mask opening side (the size of the opening pattern) corresponding to the opening having the smallest area among the resolved openings. (Evaluation Criteria) A: The minimum opening pattern size is less than 10 μm B: The minimum opening pattern size is 10 μm or more and less than 15 μm C: The minimum opening pattern size is 15 μm or more and less than 20 μm D: The minimum opening pattern size is 20 μm or more.

[0123] (3) Chemical resistance test A 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25μm) was sputtered with 200nm thick Ti and 400nm thick Cu in that order using a sputtering device (L-440S-FHL model, manufactured by Canon Anelva Corporation). Next, a photosensitive resin composition prepared by the method described below was spin-coated on this wafer using a coater developer (D-Spin60A model, manufactured by SOKUDO Co., Ltd.), and then heated and dried on a hot plate at 110°C for 3 minutes to form a photosensitive resin layer with a thickness of approximately 13.5μm. Using a test pattern mask, this photosensitive resin layer was sprayed with 500mJ / cm using Prisma GHI (manufactured by Ultratech Co., Ltd.) equipped with an i-line filter. 2The coating film formed on the wafer was then spray-developed using cyclopentanone in a developing machine (D-SPIN636 type, manufactured by Dai Nippon Screen Mfg. Co., Ltd., Japan). The unexposed areas were then developed and removed by rinsing with propylene glycol methyl ether acetate to obtain a relief pattern of a polyimide precursor. The wafer on which the relief pattern was formed was heated in a temperature-programmable curing oven (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd.) for 2 hours at 230°C under a nitrogen atmosphere to obtain a cured relief pattern of about 10 μm thick made of resin. The obtained polyimide pattern was immersed in a solution consisting 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 drying in air, the polyimide coating film was evaluated by measuring the film thickness and observing under an optical microscope. The dissolution rate (DR) per unit minute was calculated from the measured film thickness, and the chemical resistance of the coating film after immersion was evaluated according to the following criteria. (Evaluation Criteria) A: The thickness of the coating film before and after immersion is within ±3% and no cracks have occurred. B: The thickness of the coating film before and after immersion is within ±5% and no cracks have occurred. C: The thickness of the coating film before and after immersion is within ±7% and no cracks have occurred. D: The thickness of the coating film before and after immersion varies by more than ±7%, or cracks occur.

[0124] (4) Measurement of dielectric properties (dielectric constant: Dk, dielectric tangent: Df) A 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputtered with 100 nm-thick aluminum (Al) using a sputtering device (L-440S-FHL model, manufactured by Canon Anelva Corporation) to prepare a sputtered Al wafer substrate. A photosensitive resin composition prepared by the method described below was spin-coated onto the sputtered Al wafer substrate using a spin coater (D-spin60A model, manufactured by SOKUDO Co., Ltd.), and the substrate was dried by heating at 110°C for 180 seconds to form a photosensitive resin layer with a thickness of approximately 13.5 μm. The resulting substrate was then exposed to light at a dose of 600 mJ / cm2 using an aligner (PLA-501F, manufactured by Canon Co., Ltd.). 2 The entire surface was exposed to ghi rays, and a heat curing process was performed for 2 hours at 230°C under a nitrogen atmosphere using a vertical curing furnace (Koyo Lindberg, model name VF-2000B), to produce a cured film made of resin with a thickness of about 10 μm on the Al wafer. This cured film was cut into 80 mm length and 62 mm width (for 10 GHz measurement) and 40 mm length and 30 mm width (for 40 GHz measurement) using a dicing saw (Disco, model name DAD-2H / 6T), and immersed in a 10% hydrochloric acid solution to peel off from the silicon wafer to obtain a film sample. After drying the film sample in an oven at 50°C for 24 hours, the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the film sample at 10 GHz and 40 GHz were measured using the resonator perturbation method. The details of the measurement method are as follows. (Measurement method) Perturbation split cylinder resonator method (Device configuration) Network Analyzer: PNA Network analyzer N5224B (Keysight) Split Cylinder Resonator: CR-710 (Kanto Electronics Application Development Co., Ltd., measurement frequency: approx. 10 GHz) CR-740 (Kanto Electronics Application Development Co., Ltd., measurement frequency: approx. 40 GHz)

[0125] (5) Moisture permeability test A 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputtered with 100 nm-thick aluminum (Al) using a sputtering device (L-440S-FHL model, manufactured by Canon Anelva Corporation) to prepare a sputtered Al wafer substrate. A photosensitive resin composition prepared by the method described below was spin-coated onto the sputtered Al wafer substrate using a spin coater (D-spin60A model, manufactured by SOKUDO Co., Ltd.), and the substrate was dried by heating at 110°C for 180 seconds to form a photosensitive resin layer with a thickness of approximately 13.5 μm. The resulting substrate was then exposed to light at a dose of 600 mJ / cm2 using an aligner (PLA-501F, manufactured by Canon Co., Ltd.). 2 The entire surface was exposed to ghi rays, and a heat curing treatment was performed for 2 hours at 230°C under a nitrogen atmosphere using a vertical curing furnace (Koyo Lindberg, model name VF-2000B), 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 length of 80 mm and a width of 62 mm using a dicing saw (Disco, model name DAD-2H / 6T), and immersed in a 10% hydrochloric acid solution to peel it off from the silicon wafer to obtain a film sample. The moisture permeability was measured according to the cup method of JIS Z0208. The amount of calcium chloride used was 40 g, and the moisture permeability conditions were a temperature of 65°C and a humidity of 90% RH. The test was performed for 24 hours, after which it was removed from the thermo-hygrostat and left at room temperature for 30 minutes, and the weight was measured. The water permeability (WVTR) was calculated using the following formula. WVTR = {(weight after test) - (weight before test)} / (0.03 2 ×π) (Formula X) {In the formula X, 0.03 represents the radius of the cup (m)} The WVTR here is a value for a 10um cured film, and is a value that depends on the film thickness. For example, when the film thickness is 20um, the WVTR value is 1 / 2 of the value obtained at 10um. The lower the WVTR value, the lower the water vapor transmission rate of the film. In addition, the more hydrophobic the film is and the higher the film density, the lower the WVTR tends to be.

[0126] [Production of diamine X-1] A 5L four-neck flask was purged with Ar, and 172.02g of 4,4'-butylindene bis(6-tert-butyl-m-cresol), 155.84g of 4-chloronitrobenzene, and 1.5L of DMF were added and stirred. 186.42g of K2CO3 was added and heated at 150℃ for 5 hours, and the disappearance of the raw materials and intermediates was confirmed by TLC. After cooling to room temperature, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure at 80℃. The concentrated residue was poured into 1.6L of ion-exchanged water, and 2.5L of ethyl acetate was added and purified three times by separation. The organic layer was collected and dried by adding MgSO4. After drying, it was filtered to remove impurities, and 800mL of toluene was added to dissolve it, and the mixture was added to 4.0L of methanol and stirred for 30 minutes. After stirring, the residue was collected by filtration and dried at 80℃ for 12 hours. The dried reaction product was placed in a 5 L 4-neck flask purged with Ar, and 19.04 g of 5% Pd / C (EA) and 1.9 L of THF were added and stirred. The flask was heated to 40°C, and reduction reaction was carried out for 24 hours with H2 bubbling (10 mL / min). The reaction solution was filtered through Celite, and the target fraction was collected by silica gel chromatography and concentrated under reduced pressure to obtain diamine X-1.

[0127] [(A) Preparation of polyimide precursor] Synthesis of polyimide precursor (polymer A-1): As an acid component, 93.7 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (BPADA) was placed in a 1-liter separable flask, and 175 g of γ-butyrolactone was added. While stirring at room temperature, a γ-butyrolactone solution prepared separately by dissolving 4.7 g of 2-isocyanatoethyl methacrylate and 28.9 g of pyridine in 20 g of γ-butyrolactone was added over 5 minutes and heated at 50°C for 1 hour. Next, 48.7 g of 2-hydroxyethyl methacrylate (HEMA) was added, and the mixture was further heated at 50°C for 4 hours. After the end of the heat generation due to the reaction, the mixture was allowed to cool to room temperature. The mixture was left to stand for another 16 hours to obtain a reaction mixture.

[0128] Next, under ice cooling, a solution of 69.5 g of dicyclohexylcarbodiimide (DCC) dissolved in 70 g of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Next, a solution of 34.0 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) dissolved in 110 g of γ-butyrolactone was added as a diamine component 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 liquid.

[0129] The reaction solution was added to 2700 g of ethyl alcohol to produce a precipitate consisting of a crude polymer. The crude polymer thus produced was filtered and dissolved in 1000 g of γ-butyrolactone to obtain a crude polymer solution. The crude polymer solution thus obtained was then washed with an anion exchange resin ("Amberlyst" manufactured by Organo Corporation). TM 15") to obtain a polymer solution. The obtained polymer solution was dropped into 8000 g of water to precipitate the polymer, and the resulting precipitate was collected by filtration and dried in vacuum to obtain a powdered polymer A-1. The weight average molecular weight (Mw) of this polymer A-1 was measured to be 22,000. The terminal blocking 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 in terms of the polyimide of the polyimide cured film obtained by heating and curing at 350°C (the same applies below).

[0130] Synthesis of polyimide precursor (polymer A-2): As an 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. 28.5 g of pyridine was added while stirring at room temperature, and the mixture was heated at 50°C for 4 hours. After the reaction heat generation was terminated, the mixture was allowed to cool to room temperature. The mixture was allowed to stand for another 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 reaction heat generation was terminated, the mixture was allowed to cool to room temperature. The mixture was allowed to stand for another 16 hours to obtain a reaction mixture.

[0131] Next, under ice cooling, a solution of 73.2 g of dicyclohexylcarbodiimide (DCC) dissolved in 70 g of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Next, a solution of 34.0 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) dissolved in 110 g of γ-butyrolactone was added as a diamine component 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 liquid.

[0132] The reaction solution was added to 2700 g of ethyl alcohol to produce a precipitate consisting of a crude polymer. The crude polymer thus produced was filtered and dissolved in 1000 g of γ-butyrolactone to obtain a crude polymer solution. The crude polymer solution thus obtained was then washed with an anion exchange resin ("Amberlyst" manufactured by Organo Corporation). TM15") to obtain a polymer solution. The obtained polymer solution was dropped into 8000 g of water to precipitate the polymer, and the obtained precipitate was collected by filtration and dried in vacuum to obtain a powdered polymer A-2. The weight average molecular weight (Mw) of this polymer A-2 was measured to be 15,000. The terminal blocking 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 an 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. 28.5 g of pyridine was added while stirring at room temperature, and the mixture was heated at 50°C for 4 hours. After the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature. The mixture was then left to stand for another 16 hours to obtain a reaction mixture.

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

[0135] In parallel with the reaction in the 0.5-liter three-neck flask, a solution of 73.2 g of dicyclohexylcarbodiimide (DCC) dissolved in 70 g of γ-butyrolactone was added to the reaction mixture in the 1-liter separable flask under ice cooling over a period of 40 minutes while stirring. Then, as a diamine component, the reaction mixture solution with the diamine obtained above was added over a period of 60 minutes while 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 liquid.

[0136] The reaction solution was added to 2700 g of ethyl alcohol to produce a precipitate consisting of a crude polymer. The crude polymer thus produced was filtered and dissolved in 1000 g of γ-butyrolactone to obtain a crude polymer solution. The crude polymer solution thus obtained was then washed with an anion exchange resin ("Amberlyst" manufactured by Organo Corporation). TM 15") to obtain a polymer solution. The obtained polymer solution was dropped into 8000 g of water to precipitate the polymer, and the resulting precipitate was collected by filtration and dried in vacuum to obtain a powdered polymer A-3. The weight average molecular weight (Mw) of this polymer A-3 was measured to be 17,000. The terminal blocking 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, 55.8 g of 4,4'-oxydiphthalic dianhydride (ODPA) was used instead of 93.7 g of BPADA, and 65.7 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) was used instead of 34.0 g of m-TB, but the reaction was carried out in the same manner as in the synthesis of polymer A-1 to obtain polymer A-4. The weight average molecular weight (Mw) of this polymer A-4 was measured and found to be 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, 55.8 g of ODPA was used instead of 93.7 g of BPADA, and 70.2 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane (MBAPP) was used instead of 34.0 g of m-TB, but the reaction was carried out in the same manner as in the synthesis of polymer A-1 to obtain polymer A-5. The weight average molecular weight (Mw) of this polymer A-5 was measured and found to be 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, 53.0 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) 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, but the reaction was carried out in the same manner as in the synthesis of polymer A-1 to obtain polymer A-6. The weight average molecular weight (Mw) of this polymer A-6 was measured and found to be 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): Polymer A-7 was obtained by carrying out the reaction in the same manner as in the synthesis of polymer A-1, except that 70.2 g of MBAPP was used instead of 34.0 g of m-TB in the synthesis of polymer A-1. The weight average molecular weight (Mw) of this polymer A-7 was measured to be 23,000. The terminal blocking 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): Polymer A-8 was obtained by carrying out the reaction in the same manner as 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. The weight average molecular weight (Mw) of this polymer A-8 was measured and found to be 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): Polymer A-9 was obtained by carrying out the reaction in the same manner as 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 in the synthesis of polymer A-1. The weight average molecular weight (Mw) of this polymer A-9 was measured to be 19,000. The terminal blocking 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, 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, but the reaction was carried out in the same manner as in the synthesis of polymer A-1 to obtain polymer A-10. The weight average molecular weight (Mw) of this polymer A-10 was measured to be 13,000. The terminal blocking 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, 55.8 g of ODPA was used instead of 93.7 g of BPADA, and 35.1 g of MBAPP and 16.0 g of diaminodiphenyl ether (DADPE) were used instead of 34.0 g of m-TB, but the reaction was carried out in the same manner as in the synthesis of polymer A-1 to obtain polymer A-11. The weight average molecular weight (Mw) of this polymer A-11 was measured to be 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, 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, but the reaction was carried out in the same manner as in the synthesis of polymer A-1 to obtain polymer A-12. The weight average molecular weight (Mw) of this polymer A-12 was measured to be 15,000. The terminal blocking 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, 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, but the reaction was carried out in the same manner as in the synthesis of polymer A-1 to obtain polymer A-13. The weight average molecular weight (Mw) of this polymer A-13 was measured to be 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, except that 59.2 g of hydroxybutyl methacrylate (HBMA) was used instead of 48.7 g of HEMA, the reaction was carried out in the same manner as in the synthesis of polymer A-1 to obtain A-14. The weight average molecular weight (Mw) of this polymer A-14 was measured and found to be 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, 4.7g of 2-isocyanatoethyl methacrylate was replaced with 4.1g of 2-isocyanatoethyl methacrylate and 0.9g of 1,1-(bisacryloyloxymethyl)ethyl isocyanate, but the reaction was carried out in the same manner as in the synthesis of polymer A-1 to obtain A-15. The weight average molecular weight (Mw) of this polymer A-15 was measured and found to be 18,000. The end-capping value was 0.04, the aliphatic hydrocarbon group concentration T was 8.6wt%, and the photosensitive group concentration S was 27.2wt%.

[0149] Synthesis of polyimide precursor (polymer A-16): As an 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. 28.5 g of pyridine was added while stirring at room temperature, and the mixture was heated at 50°C for 4 hours. After the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature. The mixture was then left to stand for another 16 hours to obtain a reaction mixture.

[0150] Next, under ice cooling, a solution of 73.2 g of dicyclohexylcarbodiimide (DCC) dissolved in 70 g of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Then, 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, and a solution of 35.7 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) dissolved in 110 g of γ-butyrolactone was added as a diamine component 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, after which 150 g of γ-butyrolactone was added, and 0.05 g of 4-methoxyphenol was further added and stirred at 50°C for 0.5 hours. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

[0151] The reaction solution was added to 2700 g of ethyl alcohol to produce a precipitate consisting of a crude polymer. The crude polymer thus produced was filtered and dissolved in 1000 g of γ-butyrolactone to obtain a crude polymer solution. The crude polymer solution thus obtained was then washed with an anion exchange resin ("Amberlyst" manufactured by Organo Corporation). TM 15") to obtain a polymer solution. The obtained polymer solution was dropped into 8000 g of water to precipitate the polymer, and the resulting precipitate was collected by filtration and dried in vacuum to obtain a powdered polymer A-16. The weight average molecular weight (Mw) of this polymer A-16 was measured to be 16,000. The terminal blocking 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, 55.8 g of ODPA was used instead of 93.7 g of BPADA, 84.6 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane (MBAPP) was used instead of 34.0 g of m-TB, and 3.2 g of 2-isocyanatoethyl methacrylate and 0.7 g of 1,1-(bisacryloyloxymethyl)ethyl isocyanate were used instead of 4.7 g of 2-isocyanatoethyl methacrylate, except that A-16 was obtained by carrying out the reaction in the same manner as in the synthesis of polymer A-3. The weight average molecular weight (Mw) of this polymer A-16 was measured and found to be 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, 34.0 g of m-TB was changed to 40.9 g, and 2.5 g of methacrylic acid chloride was used instead of 4.7 g of 2-isocyanatoethyl methacrylate, but the reaction was carried out in the same manner as in the synthesis of polymer A-3 to obtain A-16. The weight average molecular weight (Mw) of this polymer A-16 was measured and found to be 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, except that 2.95 g of 5-norbornene-2-methylamine was used instead of 1.4 g of allylamine, the reaction was carried out in the same manner as in the synthesis of polymer A-16 to obtain A-19. The weight average molecular weight (Mw) of this polymer A-19 was measured to be 16,000. The terminal blocking 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 an acid component, 55.8 g of ODPA was placed in a 1-liter separable flask, and 48.7 g of HEMA and 175 g of γ-butyrolactone were added. 28.5 g of pyridine was added with stirring at room temperature to obtain a reaction mixture. After the heat generation due to the reaction had ceased, the mixture was allowed to cool to room temperature and then left to stand for another 16 hours.

[0156] Next, under ice cooling, a solution of 69.5 g of dicyclohexylcarbodiimide (DCC) dissolved in 70 g of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring, followed by a suspension of 30.9 g of DADPE suspended in 100 g of γ-butyrolactone as a diamine component, which 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, after which 150 g of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

[0157] The reaction solution was added to 2700 g of ethyl alcohol to produce a precipitate consisting of a crude polymer. The crude polymer thus produced was filtered and dissolved in 1000 g of γ-butyrolactone to obtain a crude polymer solution. The crude polymer solution thus obtained was then washed with an anion exchange resin ("Amberlyst" manufactured by Organo Corporation). TM 15") to obtain a polymer solution. The obtained polymer solution was dropped into 8000 g of water to precipitate the polymer, and the obtained precipitate was collected by filtration and dried in vacuum to obtain a powdered polymer A-20. The weight average molecular weight (Mw) of this polymer A-20 was measured and found to be 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): 155.1 g of ODPA was placed in a 2-liter separable flask as an acid component, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. 79.1 g of pyridine was added while stirring at room temperature to obtain a reaction mixture. After the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature and then allowed to stand for another 16 hours.

[0159] Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Next, a suspension of 120.1 g of 4,4'-diaminodiphenyl ether (DADPE) as a diamine component suspended in 360 ml of γ-butyrolactone was added over 60 minutes while 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 terminal 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 liquid.

[0160] The reaction solution obtained was added to 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The crude polymer solution obtained was dropped into 28 liters of water to precipitate the polymer, and the precipitate obtained was filtered and then vacuum dried to obtain a powdered polymer A-21. The weight average molecular weight (Mw) of this polymer A-21 was measured to be 20,000. The terminal blocking 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): A-22 was obtained by carrying out the reaction in the same manner as in the synthesis of polymer A-20, except that 56.8 g of BAPB was used instead of 30.9 g of DADPE in the synthesis of polymer A-20. The weight average molecular weight (Mw) of this polymer A-22 was measured and found to be 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): Polymer A-18 was obtained by carrying out the reaction in the same manner as in the synthesis of polymer A-20, except that 32.8 g of m-TB was used instead of 30.9 g of DADPE. The weight average molecular weight (Mw) of this polymer A-18 was measured and found to be 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, except that 127.37 g of m-TB was used instead of 120.14 g of DADPE, the reaction was carried out in the same manner as in the synthesis of polymer A-21 to obtain A-24. The weight average molecular weight (Mw) of this polymer A-24 was measured and found to be 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, 91.0 g of m-TB was used instead of 120.1 g of DADPE, and 24.5 g of 4-vinylaniline was used instead of 37.2 g of 2-isocyanatoethyl methacrylate, but the reaction was carried out in the same manner as in the synthesis of polymer A-21 to obtain A-25. The weight average molecular weight (Mw) of this polymer A-25 was measured and found to be 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)~(G)] Photopolymerization initiator B1: 3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]propanone-1-(O-acetyloxime) (trade name: PBG-304, Changzhou Strong Electronics Co., Ltd.) Photopolymerization initiator B2: 1,2-propanedione-3-cyclopentyl-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime) (trade name: PBG-305, Changzhou Strong Electronics Co., Ltd.) Photopolymerization initiator B3: 1-[4-(phenylthio)phenyl]-3-propane-1,2-dione-2-(O-acetyloxime) (trade name: PBG-3057, Changzhou Strong Electronics Co., Ltd.) Solvent C1: γ-butyrolactone Solvent C2: Dimethyl sulfoxide (DMSO) Silane coupling agent D-1: 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) Silane coupling agent D-2: N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) Silane coupling agent D-3: (3-triethoxysilylpropyl)-tert-butylcarbamate Silane coupling agent D-4: Ureidopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd.) Silane coupling agent D-5: X-12-1214A (product name manufactured by Shin-Etsu Chemical Co., Ltd.) Silane coupling agent D-6: Tris(trimethoxysilylpropyl)isocyanurate (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-modified bisphenol A (Kyoeisha Chemical Co., Ltd.) Thermal crosslinking agent F-1: BMI-5100 (manufactured by Daiwa Chemical Industry Co., Ltd.) Thermal crosslinking agent F-2: SBB70P (Asahi Kasei) Filler G-1: K180SP-CY1 (Admatechs)

[0166] [Examples and Comparative Examples] <Example 1> As shown in Table 1, 100 g of polymer A-1 as component (A), 5 g of photopolymerization initiator B-1 as component (B), and (C) were dissolved in a mixed solvent (weight ratio 90:10) of γ-butyrolactone and DMSO as solvent, and the amount of solvent was adjusted so that the viscosity was about 40 poise, to prepare a photosensitive resin composition solution. This composition was evaluated by the above-mentioned method. The characteristics and evaluation results are shown in Table 2. Table 9 also shows the characteristics of component (A).

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

[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 an end structure into the monomer before polymerization (pre-capping), it was possible to produce a cured resin film with good resolution and chemical resistance and low dielectric properties. In contrast, in the Comparative Examples, sufficient results were not obtained. In addition, the Examples showed lower values ​​for the parameters consisting of moisture permeability and dielectric tangent than the Comparative Examples, suggesting that in addition to the above characteristics, the dielectric tangent has little frequency dependency. [Industrial Applicability]

[0178] By using the photosensitive resin composition of the present disclosure, it is possible to produce a cured resin film having excellent relief pattern resolution, low dielectric properties, low moisture permeability, and good chemical resistance, and the composition can be suitably used in the field of photosensitive materials that are useful for producing electric and electronic materials such as semiconductor devices and multilayer wiring boards. [Explanation of symbols]

[0179] 1. Proton peak of polymerizable functional group derived from the terminal 2. Proton peaks of polymerizable functional groups derived from repeating units

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 having 1 to 5 carbon atoms, 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. Based on a polyimide obtained by 100% imidizing the polyimide precursor resin, 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 units derived from the tetracarboxylic dianhydride and the diamine compound, is 4 wt % to 25.1 wt %, and the aliphatic hydrocarbon group is a linear or branched hydrocarbon group branched from the main chain, which does not contain a heteroatom and has at least one structure selected from the group consisting of a saturated aliphatic chain, an unsaturated aliphatic chain, and an alicyclic structure, and the aliphatic hydrocarbon group is represented by the following general formula (A1): 【Chemistry 2】 The structure is represented by In general formula (A1), L is a single bond or an a-valent organic group which may be a linear or branched saturated hydrocarbon group or a linear or branched unsaturated hydrocarbon group, and * means that it is bonded to the main chain of the resin. The aliphatic hydrocarbon group concentration T is calculated by 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.} However, when n (n≧2) types of tetracarboxylic dianhydrides and / or diamine compounds are used, the molecular weight can be calculated using the following formula (II): [Mw(P1)×a １ +・・・+Mw(Pn)×a ｎ +Mw(Q1)×b １ +・・・+Mw(Qn)×b ｎ ] / [Mw(A1)×a １ +・・・+Mw(An)×a ｎ +Mw(B1)×b １ +・・・+Mw(Bn)×b ｎ -36]×100 (II) In formula (II), Mw(P1) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the first tetracarboxylic dianhydride, Mw(Pn) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the nth tetracarboxylic dianhydride, Mw(Q1) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the first diamine compound, and Mw(Qn) represents the sum of the molecular weights of the aliphatic hydrocarbon groups in the nth diamine compound. Mw(A1) represents the molecular weight of the first tetracarboxylic dianhydride, Mw(An) represents the molecular weight of the nth tetracarboxylic dianhydride, １ represents the content ratio of the first tetracarboxylic dianhydride, ｎ represents the content ratio of the nth tetracarboxylic dianhydride; Mw(B1) represents the molecular weight of the first diamine compound; Mw(Bn) represents the molecular weight of the nth diamine compound; b １ represents the content ratio of the first diamine compound, and b ｎ represents the content ratio of the nth diamine compound. １ ...a ｎ , b １ ...b ｎ are respectively a １ + ... + a ｎ = 1, b １ + ... + b ｎ = 1. 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, and R 4 and R 5 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, with the proviso that at least one of R 4 and R 5 is a group represented by the following general formula (5).} 【Chemistry 3】 {wherein 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.}, and The polyimide precursor resin (A) comprises a structure represented by the following general formula (6): 【Chemistry 4】 {In the formula, R 9 and R 10 are each independently an organic group having 1 to 10 carbon atoms, m 3 and m 4 are integers 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.}, a photosensitive resin composition.

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

3. The photosensitive resin composition according to claim 1 or 2, further comprising (D) a silane coupling agent.

4. The photosensitive resin composition according to any one of claims 1 to 3, further comprising (E) a radically polymerizable compound.

5. The photosensitive resin composition according to any one of claims 1 to 4, further comprising (F) a thermal crosslinking agent.

6. The photosensitive resin composition according to any one of claims 1 to 5, further comprising (G) a filler.

7. The polyimide precursor resin (A) contains a terminal structure derived from a tetracarboxylic dianhydride at an end of a main chain, １ 7. The photosensitive resin composition according to claim 1, 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.

8. 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 7 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:

9. A method for producing a cured film, comprising applying the resin composition according to any one of claims 1 to 7 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:

10. A method for producing the photosensitive resin composition according to any one of claims 1 to 7, comprising the steps of: (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, Thereby, the terminal structure having a reactive substituent derived from the second compound is formed at a main chain terminal of the polyimide precursor resin (A). A method for producing a photosensitive resin composition.

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