Photosensitive resin composition, method for manufacturing polyimide curing film using the same, and polyimide curing film.

Abstract

According to the present invention, a photosensitive resin composition having low dielectric properties, low hardening shrinkage, good storage stability, reduced phase separation during coating, and the ability to form a hardened embossed pattern with high resolution and high copper adhesion is provided; a method for manufacturing a polyimide hardened film using the same; and a polyimide hardened film. The photosensitive resin composition of the present invention comprises: 100 parts by weight of a copolymer resin containing polyimide and a polyimide precursor, 0.5 to 30 parts by weight of a photopolymerization initiator, and 100 to 1000 parts by weight of a solvent. The copolymer resin has a polyimide block portion and a polyimide precursor block portion with a specific structure, wherein the copolymer resin containing polyimide and the polyimide precursor satisfies 0.10 < n² / (n² + n³) < 0.90.

Description

Technical Field

[0001] This invention relates to a photosensitive resin composition, a method for manufacturing a polyimide curing film using the same, and the polyimide curing film. Prior Technology

[0002] Previously, polyimide resins and polystyrene resins, which possess excellent heat resistance, electrical properties, and mechanical properties, were used for insulating materials of electronic components and passivation films, surface protective films, and interlayer insulating films of semiconductor devices. Azole resins, phenolic resins, etc. Among these resins, those provided in the form of photosensitive resin compositions can be obtained through coating, exposure, development, and ring-closing treatments (such as acetylation, benzo[] ] curing. It can be easily formed into a heat-resistant textured film by azoleization or thermal crosslinking. Compared with previous non-photosensitive materials, this photosensitive resin composition has the characteristic of significantly shortening the steps and is used in the fabrication of semiconductor devices.

[0003] However, semiconductor devices (hereinafter also referred to as "components") are mounted on printed circuit boards using various methods depending on their purpose. Previously, components were typically manufactured using wire bonding, a method that connects fine wires from the external terminals (pads) of the component to the lead frame. However, with the continuous increase in component speed and operating frequencies reaching GHz, the difference in wire lengths between the terminals during mounting has affected component operation. Therefore, in the mounting of high-end components, precise control of the mounting wire length is required, and wire bonding is insufficient to meet these requirements.

[0004] Therefore, flip-chip mounting has been proposed, in which a rewiring layer is formed on the surface of a semiconductor wafer, and bumps (electrodes) are formed on it. The wafer is then flip-chip mounted directly onto a printed circuit board. This flip-chip mounting method allows for precise control of wiring distances and is therefore used in high-end components processing high-speed signals. Furthermore, due to its smaller mounting size, it is used in mobile phones and other applications where demand is rapidly increasing. More recently, a semiconductor wafer mounting technology called fan-out wafer-level packaging (FOWLP) has been proposed. This involves dicing a wafer after previous steps to create a single wafer, then reconstructing the single wafer onto a support and sealing it with molding resin. The support is then peeled off to form the rewiring layer (e.g., Patent Document 1). In fan-out wafer-level packaging, the rewiring layer is formed with a thinner film thickness, thus enabling highly thin packages and achieving high-speed transmission and low cost.

[0005] In recent years, with the significant increase in information and communication volume, there is a need to achieve communication speeds exceeding previous levels. This has necessitated a shift towards 5G communication using frequencies above 3 GHz, or near-millimeter wave bands (20 GHz~30 GHz) to millimeter wave bands (above 30 GHz) where wider bandwidth can be easily ensured. This shift applies not only to printed circuit boards but also to semiconductor chips mounted on those boards. Therefore, to reduce transmission loss, antenna-in-package (AiP) devices have been developed that integrate the front-end module (FEM) for transmitting and receiving radio waves with the antenna (see, for example, Patent Document 2 below). AiPs have shorter wiring lengths, thus suppressing transmission losses that increase proportionally to wiring length. However, as communication bandwidth increases, low dielectric properties are required for the rewiring materials. Furthermore, like previous FOWLP devices, AiPs require multiple rewiring layers, thus necessitating planarization of these layers.

[0006] As a solution to the aforementioned problems, two main methods are considered to reduce transmission loss at high frequencies: methods to reduce dielectric loss and methods to reduce conductor loss. Regarding the former, low dielectric properties (low dielectric loss factor, low dielectric constant) are required for the photosensitive resin composition, as exemplified by Patent Documents 3, 4, and 5. However, in Patent Document 3, since the measurement frequency is as low as 1 GHz, the redistribution layer for AiP applications at high frequencies is insufficient. In Patent Document 4, since polyimide precursor resin is blended with polyimide resin, concerns arise regarding the storage stability of the photosensitive resin composition or phase separation during coating. In Patent Document 5, a partially amided polyimide precursor is produced in the varnish by heating and curing a varnish containing polyimide precursor resin. However, due to the difficulty in controlling the amide ratio, there are problems with the uniformity of spin coating, making it difficult to achieve high resolution.

[0007] As a method for planarizing the rewiring layer, methods to suppress the hardening shrinkage of the rewiring layer are considered, with Patent Document 6 as an example. In Patent Document 6, high planarization is achieved by using polyfunctional (meth)acrylates on the polyimide resin. However, no description is made of the dielectric properties, raising concerns that the large amount of polyfunctional (meth)acrylates may lead to a deterioration of the dielectric properties at high frequencies. [Previous Technical Documents] [Patent Literature]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 2005-167191 [Patent Document 2] U.S. Patent Application Publication No. 2016 / 0104940 [Patent Document 3] International Publication No. 2019 / 044874 [Patent Document 4] Taiwan Publication No. 2020 / 026762 [Patent Document 5] Japanese Patent Application Publication No. 2022-54416 [Patent Document 6] Japanese Patent Application Publication No. 2021-152634 Summary of the Invention

[0009] [The problem the invention aims to solve] In recent years, the diversification of packaging and mounting technologies has led to a greater variety of support types and multi-layered rewiring layers. Consequently, the dielectric constant or dielectric loss factor (tanδ) of the insulating materials used to form the wiring has become more influential. Higher dielectric constants or dielectric loss factors result in increased dielectric loss, leading to increased transmission losses. Polyimide resins are considered reliable due to their excellent insulation and thermomechanical properties. However, the influence of polar functional groups derived from propylene, polar functional groups added for photosensitive properties, and additives can result in higher dielectric constants or dielectric loss factors, which is considered a problem. Furthermore, there are instances where the multi-layered rewiring layers have caused flatness issues due to low curing shrinkage.

[0010] The purpose of this invention is to provide a photosensitive resin composition having low dielectric properties, low hardening shrinkage, good storage stability, reduced phase separation during coating, and the ability to form a hardened embossed pattern with high resolution and high copper adhesion, as well as a method for manufacturing a polyimide hardened film using the same and the polyimide hardened film. [Technical means to solve the problem]

[0011] The following items [1] to

[16] are listed as examples of embodiments of the present invention. [1] A photosensitive resin composition comprising: (A) 100 parts by weight of a copolymer resin containing polyimide and polyimide precursor; (B) 0.5-30 parts by weight of a photopolymerization initiator; and (C) 100~1000 parts by weight of solvent; and The copolymer resin containing polyimide and polyimide precursor described above has the structure represented by the following general formula (1). [Chemistry 1] In the above formula (1), X1, X2, and X3 are independently tetravalent organic groups with 6 to 40 carbon atoms, Y1 and Y2 are independently divalent organic groups with 6 to 40 carbon atoms, n1 is an integer from 2 to 30, n2 and n3 are independently integers from 2 to 150, Z3, Z4, Z5, and Z6 are independently monovalent organic groups, and at least one of Z3, Z4, Z5, and Z6 is a photopolymerizable functional group. The aforementioned copolymer resin containing polyimide and polyimide precursor satisfies 0.10 <n 2 / (n 2+n 3)<0.90。 [2] The photosensitive resin composition described in Project 1, wherein the aforementioned photopolymerizable functional group comprises The structure represented by the following general formula (2). [Chemistry 2] (In formula (2), R5, R6 and R7 are each independently a hydrogen atom or a monovalent organic group with 1 to 3 carbon atoms, and m1 is an integer from 2 to 10) [3] The photosensitive resin composition as described in item 1 or 2, wherein the above n 2 / (n 2+n 3) satisfies 0.40. <n 2 / (n 2+n 3)<0.90。 [4] The photosensitive resin composition described in any of items 1 to 3, wherein the copolymer resin comprising polyimide and polyimide precursor of (A) above does not contain halogen atoms. [5] As described in any of Items 1 to 4, in the polyimide of the polyimide hardened film obtained by heating and curing the above-mentioned photosensitive resin composition at 350°C, the ratio of the molecular weight of amide groups to the molecular weight of repeating units containing structures derived from tetracarboxylic dianhydride and diamine, i.e., the amide group concentration U, is 12 wt% to 26 wt%. [6] The photosensitive resin composition described in any of items 1 to 5, wherein X1, X2 and X3 of the copolymer resin comprising polyimide and polyimide precursor in (A) above comprises the structure represented by the following general formula (4), [Chemistry 3] In formula (4), R8 and R9 are organic groups with 1 to 10 carbon atoms, m2 and m3 are integers selected from 0 to 4, satisfying m2 + m3 ≥ 1, Z1 is selected from any group consisting of single bonds, organic groups with 1 to 30 carbon atoms, and organic groups containing heteroatoms, * two of which mean bonded to the main chain of the resin, and the other two mean bonded to the side chains in the above general formula (1); and / or, Y1 and / or Y2 contain the structure represented by the following general formula (7), [Chemistry 4] In formula (7), R8 and R9 are organic groups with 1 to 10 carbon atoms, m2 and m3 are integers selected from 0 to 4, satisfying m2+m3≧1, and Z1 is a group composed of single bonds, organic groups with 1 to 30 carbon atoms, and organic groups containing heteroatoms. * means bonded to the main chain of the resin. [7] The photosensitive resin composition described in any one of items 1 to 6, wherein the copolymer resin comprising polyimide and polyimide precursor has other reactive substituents at the resin end that are different from the photopolymerizable functional groups contained in the repeating unit and are polymerizable by heat or light. [8] The photosensitive resin composition described in any of items 1 to 7 further comprises (D) a silane coupling agent. [9] The photosensitive resin composition described in any of items 1 to 8 further comprises (E) free radical polymerizable compounds.

[10] The photosensitive resin composition described in any of items 1 to 9 further comprises (F) a thermal crosslinking agent.

[11] The photosensitive resin composition described in any of items 1 to 10 further comprises (G) filler.

[12] A method for manufacturing a polyimide curable film, comprising the following steps (1) to (5): (1) The step of coating a photosensitive resin composition as described in any one of items 1 to 11 onto a substrate to form a photosensitive resin layer on the substrate; (2) The steps of heating and drying the obtained photosensitive resin layer; (3) The step of exposing the heated and dried photosensitive resin layer; (4) The step of developing the exposed photosensitive resin layer; and (5) The step of heating the developed photosensitive resin layer to form a polyimide hardened film.

[13] A method for manufacturing a hardened film, comprising coating a resin composition as described in any one of items 1 to 11 onto a substrate, performing exposure treatment, development treatment, and then heat treatment to obtain a hardened film, wherein the dielectric loss factor of the hardened film measured at 40 GHz by the perturbation split cylinder resonator method is 0.003 to 0.011.

[14] A polyimide curable film exhibits a dielectric loss factor of 0.003–0.011 and an RFA of 0.81–0.93 at a frequency of 40 GHz, as measured by the perturbation-type split-cylinder resonator method, and satisfies the following equation: 85 <RFA / tanδ 40<175 {In the formula, RFA represents the residual film ratio after thermosetting, and tanδ 40 represents the dielectric loss factor at a frequency of 40 GHz measured by the perturbation-type split cylindrical resonator method}.

[15] A method for manufacturing a copolymer comprising polyimide and a polyimide precursor, the method comprising the following steps: (i) A condensation reaction is carried out between a first tetracarboxylic acid dianhydride or its acid / substituent adduct and a first diamine compound to induce amide imidization, thereby obtaining a diamine oligomer having repeating units with a polyamide structure; (ii) To synthesize a polyimide-polyimide precursor moiety having a polyimide block portion by subjecting the above-mentioned diamine oligomer to a condensation reaction with a second tetracarboxylic acid dianhydride or its acid / substituent adduct; and (iii) The polyimide-polyimide precursor moiety is synthesized by condensation reaction of the above-mentioned polyimide-polyimide precursor moiety with a third tetracarboxylic acid dianhydride or its acid / substituent adduct and a second diamine compound; The first tetracarboxylic dianhydride, the second tetracarboxylic dianhydride, and the third tetracarboxylic dianhydride may be the same as or different from each other. At least one of the second tetracarboxylic dianhydride and the third tetracarboxylic dianhydride is in the form of an acid / substituent adduct with a photopolymerizable functional group. The first diamine compound and the second diamine compound may be the same as or different from each other.

[16] A method for manufacturing a photosensitive resin composition, comprising: The steps for manufacturing a copolymer resin comprising polyimide and a polyimide precursor by means of the method described in Item 15; and The step of mixing (A) 100 parts by weight of the above-mentioned copolymer resin containing polyimide and polyimide precursor, (B) 0.5 to 30 parts by weight of photopolymerization initiator, and (C) 100 to 1000 parts by weight of solvent to obtain a photosensitive resin composition. [Effects of the Invention]

[0012] According to the present invention, a photosensitive resin composition having low dielectric properties, low hardening shrinkage, good storage stability, reduced phase separation during coating, and the ability to form a hardened embossed pattern with high resolution and high copper adhesion is provided, as well as a method for manufacturing a polyimide hardened film using the same and the polyimide hardened film. Implementation

[0013] The embodiments of the present invention will now be described in detail. In this specification, when multiple structures represented by the same symbol in a general formula exist in a molecule, unless otherwise specified, they are selected independently, and may be the same or different. Similarly, structures represented by a common symbol in different general formulas are also selected independently, unless otherwise specified, and may be the same or different.

[0014] <Photosensitive Resin Composition> The photosensitive resin composition of the present invention comprises: (A) 100 parts by weight of a copolymer resin containing a specific polyimide and a polyimide precursor, (B) 0.5 to 30 parts by weight of a photopolymerization initiator, and (C) 100 to 1000 parts by weight of a solvent. The photosensitive resin composition of the present invention may, as needed, further comprise, in addition to the above-mentioned components (D) a silane coupling agent, (E) a free radical polymerizable compound, (F) a thermal crosslinking agent, (G) a filler, and other components.

[0015] (A) Copolymer resin containing polyimide and polyimide precursor The copolymer resin containing polyimide and polyimide precursor (hereinafter also referred to as "copolymer resin") preferably contains the structure represented by the following general formula (1). General formula (1): [Chemistry 5] In formula (1), X1, X2, and X3 are each independently a tetravalent organic group with 6 to 40 carbon atoms, and Y1 and Y2 are each independently a divalent organic group with 6 to 40 carbon atoms. X1, X2, and X3 may be the same or different, and Y1 and Y2 may be the same or different. n1 is an integer from 2 to 30. n2 and n3 are each independently an integer from 2 to 150. In this invention, the unit of n1 in formula (1) is called the "polyimide block portion", the unit of n2 is called the "polyimide-polyimide precursor portion", and the unit of n3 is called the "polyimide precursor portion". In formula (1), for simplicity, only one polyimide-polyimide precursor portion and one polyimide precursor portion are recorded, but the copolymer resin may randomly have multiple polyimide-polyimide precursor portions and multiple polyimide precursor portions.

[0016] In formula (1), Z3, Z4, Z5, and Z6 are each independently a monovalent organic group, but at least one of them is a photopolymerizable functional group. The photopolymerizable functional group preferably contains a reactive unsaturated bond that polymerizes by light. Z3, Z4, Z5, and Z6 are more preferably formed with the carbonyl group (-C(=O)-) to which they are directly bonded to form an ester bond (hereinafter referred to as "ester bond type") or an amide bond (hereinafter referred to as "amide bond type"). When Z3, Z4, Z5, and Z6 are ester-type side chains, they can be represented as R1O-, R2O-, R3O-, and R4O-, respectively. When Z3, Z4, Z5, and Z6 are amide-type side chains, they can be represented as R1NH-, R2NH-, R3NH-, and R4NH-, respectively. Z3, Z4, Z5, and Z6 can all be ester-type, all be amide-type, or a combination of ester-type and amide-type.

[0017] In formula (1), R1, R2, R3, and R4 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms. However, at least one of R1, R2, R3, and R4 is a photopolymerizable functional group, which may be selected from at least one group selected from (meth)acryloxyalkyl, allyl, ethynyl, and styryl, with (meth)acryloxyalkyl being more preferred. Z3, Z4, Z5, and Z6 are further preferably photopolymerizable functional groups comprising the general formula (2) below. General formula (2): [Chemistry 6] In formula (2), R5, R6, and R7 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 is an integer of 2 to 10. Examples of the monovalent organic group having 1 to 3 carbon atoms include methyl, ethyl, n-propyl, and isopropyl, with methyl being preferred. R5 is preferably a hydrogen atom or methyl, R6 and R7 are preferably a hydrogen atom or methyl, and more preferably a hydrogen atom. m1 is preferably an integer of 2 to 5, and more preferably an integer of 2 to 3. Z3, Z4, Z5, and Z6 are preferably an ester bond type represented by R1O-, R2O-, R3O-, and R4O-, an amide bond type represented by R1NH-, R2NH-, R3NH-, and R4NH-, or a combination thereof, and R1, R2, R3, and R4 are further preferably each independently a photopolymerizable functional group represented by the above general formula (2).

[0018] In the copolymer resin containing polyimide and a polyimide precursor, the ratio of the number of moles of the polyimide-imide precursor portion (units of n2) to the total number of moles of the polyimide-imide precursor portion (units of n2) and the polyimide precursor portion (units of n3) (hereinafter, also referred to as "imide structure introduction rate") satisfies 0.10 < n2 / (n2 + n3) < 0.90. Thereby, a photosensitive resin composition can be obtained in which the cured polyimide has low dielectric properties, low curing shrinkage, good storage stability, and can form a cured embossed pattern with high resolution.

[0019] By including the structure represented by the above general formula (1), a cured film with good resolution of the embossed pattern, low dielectric properties, and low curing shrinkage can be obtained. Although not bound by theory, it is considered that by having a polyimide block portion (units of n1) and a polyimide precursor structure (i.e., the imide precursor structure in the units of n2 and n3) in the same molecule, and allowing the polyimide-imide precursor portion to exist at a specific ratio, the swelling of the exposed portion is suppressed, and it is easy to ensure the contrast with the unexposed portion, so the resolution of the embossed pattern is improved. Also, it is considered that since a part of the copolymer resin has a polyimide block portion, the detached portion of the side chain structure during ring closure is reduced, whereby the curing shrinkage is suppressed and low dielectric properties can be exhibited. Furthermore, by having a polyimide block portion and a polyimide precursor structure in the same molecule, a polyimide structure with low solubility can be stably present in the photosensitive resin composition solution (hereinafter, also referred to as "varnish"). It is considered that the storage stability of the varnish is not impaired thereby. On the other hand, when an imide structure is formed by heating a varnish containing a polyimide precursor resin, since a photosensitive group detached from the side chain structure remains in the varnish, the curing shrinkage becomes large.

[0020] From the perspective of resolution, low dielectric properties, and low hardening shrinkage, the amide structure incorporation rate is preferably 0.10~0.90. From the perspective of resolution, the amide structure incorporation rate is preferably low. From the perspective of low dielectric properties and low hardening shrinkage, n2 / (n2+n3) is preferably high. Therefore, the amide structure incorporation rate is more preferably 0.20~0.90, further preferably 0.30~0.90, further preferably 0.40~0.90, especially preferably 0.43~0.80, and even more preferably 0.45~0.75.

[0021] Based on the considerations of resolution, low dielectric properties, and low curing shrinkage, the ratio of the copolymer resin represented by the above general formula (1) to the total mass of the copolymer containing polyimide and polyimide precursor in (A) is preferably 25% by mass or more, more preferably 35% by mass or more, even more preferably 50% by mass or more, particularly preferably 75% by mass or more, particularly preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 100% by mass.

[0022] From the perspective of the photosensitivity and mechanical properties of the photosensitive resin composition, n2 in the above general formula (1) is preferably an integer from 3 to 100, and more preferably an integer from 5 to 70. From the perspective of photosensitivity and mechanical properties, n3 is preferably an integer from 3 to 100, and more preferably an integer from 5 to 70. From the perspective of coatability and dielectric loss factor, n1 is preferably an integer from 2 to 30, and more preferably an integer from 5 to 20. The larger n1 is, the higher the amide structure induction rate and the better the dielectric loss factor. On the other hand, if n1 is too large, the coatability will be impaired, so its balance is more important.

[0023] In the above general formula (1), considering both heat resistance and photosensitivity, the tetravalent organogroups represented by X1, X2, and X3 are preferably organogroups with 6 to 40 carbon atoms, more preferably aromatic groups with -COOR1 and -COOR2 groups adjacent to -CONH- groups, or alicyclic aliphatic groups. Specifically, as the tetravalent organogroups represented by X1, X2, and X3, examples can be organogroups with 6 to 40 carbon atoms containing an aromatic ring, such as those having the following general formula (3): [Chemistry 7] {In formula (3), R 11 is a monovalent group selected from the group composed of hydrogen atoms, fluorine atoms, C1~C10 hydrocarbon groups, and C1~C10 fluorinated hydrocarbon groups, m 5 is an integer of 1~2, m 6 is an integer of 1~3, and m 7 is an integer of 1~4}, but is not limited to these. The tetravalent organic groups represented by X 1, X 2, and X 3 can be one type or a combination of two or more types. The X 1, X 2, and X 3 groups having the structure represented by the above formula (3) are particularly advantageous in terms of both heat resistance and photosensitive properties.

[0024] Based on the viewpoints of resolution and low dielectric properties, X1, X2 and X3 in the above general formula (1) are preferably structures that include the structure represented by the following general formula (4). General formula (4): [Chemistry 8] {In the formula, R8 and R9 are organic groups with 1 to 10 carbon atoms, m2 and m3 are integers selected from 0 to 4, satisfying m2 + m3 ≥ 1, Z1 is selected from any group consisting of single bonds, organic groups with 1 to 30 carbon atoms, and organic groups containing heteroatoms; *The two in the formula refer to the bonds bonded to the main chain of the resin, and the other two refer to the bonds bonded to the side chains in the above general formula (1) (i.e., Z3-(C=O)- and Z4-(C=O)-, or Z5-(C=O)- and Z6-(C=O)-)} [Chemistry 9] {In the formula, Z2 is selected from any of the following groups: single bonds, organic groups with 1 to 30 carbon atoms, and organic groups containing heteroatoms; *in the formula, two refer to bonds to the main chain of the resin, and the other two refer to bonds to the side chains in the above general formula (1)}

[0025] In the above general formula (4), the organic groups represented by R8 and R9, which have 1 to 10 carbon atoms, are preferably linear or branched alkyl groups. By introducing alkyl groups into the aromatic ring, the solubility of the (A) copolymer resin in the developer is improved, making it easier to ensure the contrast with the exposed area and improve the resolution of the raised pattern. Furthermore, by introducing alkyl groups into the aromatic ring, the polarizability is reduced, thus achieving low dielectric properties.

[0026] From the perspective of chemical resistance, R8 and R9 in the above general formula (4) are preferably organic groups with 1 to 4 carbons, more preferably alkyl groups with 1 to 4 carbons, such as methyl, ethyl, propyl and butyl, and especially methyl.

[0027] In the above general formula (1), the structures represented by X1, X2 and X3 are preferably at least one of the structures selected from the group consisting of the following general formula (5). General formula (5): [Chemistry 10] {*The two in the above refer to the main chain of the resin, and the other two refer to the side chains in the above general formula (1)} The structures of X1, X2 and X3 in the above general formula (1) are not limited to the structures listed in (3), (4) and (5) above. The above structures can be one type or a combination of two or more types.

[0028] In the above general formula (1), the divalent organic groups represented by Y1 and Y2 are aliphatic chains (alkyl groups) with 6 to 40 carbon atoms, preferably 6 to 20 carbon atoms, such as heptyl, octyl, nonyl, decyl, and undecyl; and aromatic groups with 6 to 40 carbon atoms. Considering both heat resistance and photosensitivity, aromatic groups are preferred, and more preferably aromatic groups with 6 to 40 carbon atoms, such as those having the following general formula (6): [Chemistry 11] {In formula (6), R11 is a monovalent group selected from the group consisting of hydrogen atoms, fluorine atoms, C1~C10 hydrocarbon groups, and C1~C10 fluorinated hydrocarbon groups, m6 is an integer from 1 to 3, and m7 is an integer from 1 to 4}, but is not limited to these. The divalent organic groups represented by Y1 and Y2 can be one type or a combination of two or more types. Y1 and Y2 groups having the structure represented by formula (6) above are particularly advantageous in terms of both heat resistance and photosensitive properties.

[0029] From the perspective of resolution and low dielectric properties, Y1 and / or Y2 in the above general formula (1) are preferably structures that include the structure represented by the following general formula (7). General formula (7): [Chemistry 12] {In the formula, R8 and R9 are organic groups with 1 to 10 carbon atoms, m2 and m3 are integers selected from 0 to 4, satisfying m2 + m3 ≥ 1, and Z1 is selected from any group consisting of single bonds, organic groups with 1 to 30 carbon atoms, and organic groups containing heteroatoms; *means bonded to the main chain of the resin}

[0030] In the above general formula (7), the organic groups represented by R8 and R9, which have 1 to 10 carbon atoms, are preferably linear or branched alkyl groups. By introducing alkyl groups into the aromatic ring, the solubility of the (A) copolymer resin in the developer is improved, making it easier to ensure the contrast with the exposed area and improving the resolution of the embossed pattern. Furthermore, by introducing alkyl groups into the aromatic ring, the polarizability is reduced, thus achieving low dielectric properties.

[0031] From the perspective of chemical resistance, R8 and R9 in the above general formula (7) are preferably organic groups having 1 to 4 carbon atoms, more preferably alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl and butyl, and especially methyl. As an example of the above general formula (7), it is preferable to include at least one structure selected from the group consisting of the following general formula (8). General formula (8): [Chemistry 13] *This refers to the bonds formed in the main chain of the resin.

[0032] In the above general formula (1), the structures represented by Y1 and Y2 are preferably at least one of the structures selected from the group consisting of the following general formula (9). General formula (9): [Chemistry 14] * indicates that it is bonded to the main chain of the resin. The structures of Y1 and Y2 in the above general formula (1) are not limited to the structures exemplified in (6) to (9) above. The above structures can be one type or a combination of two or more types.

[0033] From the perspective of suppressing copper corrosion during the thermosetting process, it is preferable that at least one or all of X1, X2, X3, Y1, and Y2 in the above general formula (1) are free of halogen atoms. That is, the copolymer resin (A) is more preferably free of halogen atoms.

[0034] In the copolymer resin (A), it is preferable that at least one of X1, X2, and X3, which are backbone components derived from a tetracarboxylic acid compound, and Y1 and Y2, which are backbone components derived from a diamine compound, has two or more benzene rings. The two or more benzene rings can be bonded to each other directly or through divalent or higher organic groups. The number of benzene rings can be three or more, or four or more, but less than six, five or less, or less than four, more preferably four. Furthermore, it is preferable that the total number of carbon atoms constituting X1, X2, and X3, which represent the structure derived from the tetracarboxylic acid compound, and Y1 and Y2, which represent the structure derived from the diamine compound, is greater than 39. By giving the copolymer resin (A) this structure, there is a tendency to maintain the resolution of the negative photosensitive resin composition and achieve low dielectric properties in the obtained hardened embossed pattern.

[0035] In the photosensitive resin composition of the present invention, the amide group concentration U in the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition is 12 wt% to 26 wt%. In the specification of this application, "amide group concentration U" refers to the ratio of the molecular weight of amide groups to the molecular weight of repeating units comprising structures derived from tetracarboxylic dianhydride and diamine compounds in the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350°C. The reason for using 350°C for heating and curing is to clarify the basis for the aliphatic hydrocarbon group concentration T by using a state in which the (A) copolymer resin is approximately 100% amide-iminated as a benchmark, and it is not intended that the photosensitive resin composition be heated and cured at 350°C in actual use.

[0036] If the amide group concentration U is 12.0 wt% or higher, the resolution of the raised pattern tends to improve. The amide group concentration U is preferably 15 wt% or higher, and more preferably 17.5 wt% or higher. On the other hand, by keeping the amide group concentration U at 26 wt% or lower, the dielectric loss factor of the obtained polyimide cured film tends to improve. The amide group concentration U is more preferably 23.0 wt% or lower, and even more preferably 20.5 wt% or lower.

[0037] The amide group concentration U in the repeating unit of the polyimide hardened film is determined by the molecular weight of the tetracarboxylic dianhydride and the molecular weight of the diamine compound used in the preparation of the (A) copolymer resin, as shown in the following formula (I): 70.02×2 / [Mw(A)+Mw(B)-36]×100 (I) {In formula (I), Mw(A) represents the molecular weight of the tetracarboxylic dianhydride, and Mw(B) represents the molecular weight of the diamine}. Furthermore, when using two or more tetracarboxylic dianhydrides and / or diamine compounds, for example, when preparing the product using two tetracarboxylic dianhydrides and / or diamines, it is represented by the following formula (II): 70.02×2 / [Mw(A1)×a 1+Mw(A2)×a 2+Mw(B1)×b 1+Mw(B2)×b 2-36]×100 (II) In formula (II), Mw(A1) represents the molecular weight of the first tetracarboxylic dianhydride, Mw(A2) represents the molecular weight of the second tetracarboxylic dianhydride, a1 represents the content of the first tetracarboxylic dianhydride, a2 represents the content of the second tetracarboxylic dianhydride, Mw(B1) represents the molecular weight of the first diamine compound, Mw(B2) represents the molecular weight of the second diamine compound, b1 represents the content of the first diamine compound, and b2 represents the content of the second diamine compound; wherein a1, a2, b1, and b2 satisfy a1+a2=1 and b1+b2=1, respectively. When using three or more tetracarboxylic dianhydrides and / or diamines, the same method is used. When using tetracarboxylic acids and / or tetracarboxylic dichloro as raw materials, the calculation is performed using the corresponding mass of the tetracarboxylic dianhydride.

[0038] (A) The copolymer resin may also have other reactive substituents at the ends of the main chain, which are different from the photopolymerizable functional groups contained in its repeating units and are crosslinkable by heat or light. The reactive substituents at the ends are preferably groups having reactive unsaturated bonds that can crosslink with each other by heat or light. (A) The copolymer resin preferably has at least one of the structures represented by the following general formulas (E1) and (E2) at the ends of the main chain. By having such reactive substituents at the ends of the main chain of (A) the copolymer resin, a high-resolution negative photosensitive resin composition with further improved post-curing film retention or dielectric properties can be obtained.

[0039] General formula (E1): [Chemistry 15] In formula (E1), a1 contains at least one bond selected from amide, amide, urea, and carbamate bonds; b1 is a reactive substituent that is cross-linked by heat or light; and e1 is a monovalent organic group with 1 to 30 carbon atoms. R12 and R15 are independently hydrogen atoms or monovalent organic groups with 1 to 30 carbon atoms, respectively. R13 and R14 are independently hydrogen atoms, monovalent or divalent organic groups with 1 to 30 carbon atoms, respectively, or both are part of an aromatic ring or an aliphatic ring. R13 and R14 are not simultaneously hydrogen atoms, and R13 and / or R14 are linked to the main chain structure.

[0040] General formula (E2): [Chemistry 16] In formula (E2), f1 contains at least one bond selected from amide, amide, urea, carbamate, and ester bonds; g1 is a reactive substituent that is cross-linked by heat or light; and R16 to R20 are independently hydrogen atoms, monovalent or divalent organic groups with 1 to 30 carbon atoms, or together form an aromatic or aliphatic ring. R17, R18, and R19 are not simultaneously hydrogen atoms, and any one or both of R17, R18, and R19 are linked to the main chain structure. For ease of cross-linking and high chemical resistance due to low hydrolysis, f1 preferably contains at least one group selected from amide, amide, urea, and carbamate groups.

[0041] The reactive substituent b1, which undergoes crosslinking by heat or light, is preferably selected from at least one of the following: acrylic, methacrylic, vinyl, alkenyl, cycloalkenyl, alkyldienyl, cycloalkyldienyl, styryl, ethynyl, imino, isocyanate, cyanate, cycloalkyl, epoxy, oxetyl, carbonate, hydroxy, mercapto, hydroxymethyl, and alkoxyalkyl. From the viewpoint of film thickness uniformity, b1 is preferably selected from at least one of the following: acrylic, methacrylic, vinyl, alkenyl, cycloalkenyl, alkyldienyl, cycloalkyldienyl, styryl, and ethynyl. Methacrylic is particularly preferred.

[0042] The reactive substituent g1, which undergoes crosslinking by heat or light, is, for example, selected from at least one of acrylate, methacrylate, vinyl, alkenyl, cycloalkenyl, alkyldienyl, cycloalkyldienyl, styryl, ethynyl, imino, isocyanate, cyanate, cycloalkyl, epoxy, oxetyl, carbonate, hydroxy, mercapto, hydroxymethyl, and alkoxyalkyl. From the viewpoint of film thickness uniformity, g1 is preferably selected from at least one of acrylate, methacrylate, vinyl, alkenyl, cycloalkenyl, alkyldienyl, cycloalkyldienyl, styryl, and ethynyl. g1 is particularly preferably methacrylate.

[0043] The following shows specific examples of compounds having reactive substituents that react with heat or light and having sites that also react with carboxyl groups, and the main chain ends of polyimide precursors modified by reactive substituents.

[0044] [Chemistry 17]

[0045] (A) A method for manufacturing a copolymer comprising polyimide and a polyimide precursor. The method for manufacturing the copolymer comprising polyimide and polyimide precursor of the present invention includes the following steps: (i) A condensation reaction is carried out between a first tetracarboxylic acid dianhydride or its acid / substituent adduct and a first diamine compound to induce amide imidization, thereby obtaining a diamine oligomer having repeating units with a polyamide structure; (ii) To synthesize a polyimide-polyimide precursor moiety having a polyimide block portion by subjecting the above-mentioned diamine oligomer to a condensation reaction with a second tetracarboxylic acid dianhydride or its acid / substituent adduct; and (iii) The polyimide-polyimide precursor moiety is synthesized by reacting the above-mentioned polyimide-polyimide precursor moiety with a third tetracarboxylic dianhydride or its acid / substituent adduct and a second diamine compound. The above-mentioned first tetracarboxylic dianhydride, the above-mentioned second tetracarboxylic dianhydride and the above-mentioned third tetracarboxylic dianhydride may be the same or different from each other. At least one of the above-mentioned second tetracarboxylic dianhydride and the above-mentioned third tetracarboxylic dianhydride is in the form of an acid / substituent adduct with a photopolymerizable functional group. The above-mentioned first diamine compound and the above-mentioned second diamine compound may be the same or different from each other.

[0046] (Preparation of acid / substituent adducts) The first, second, and third tetracarboxylic dianhydrides used in steps (i), (ii), and (iii) may be in the form of acid dianhydrides, or they may be in the form of acid moiety (HO-C(=O)-) and substituent addition moiety (ZC(=O)-, Z corresponding to Z3~Z6 of general formula (1)) formed by adding substituents to the acid dianhydride beforehand (in this invention, they are also referred to as "acid / substituent adducts"). Among them, at least one of the second and third tetracarboxylic dianhydrides is in the form of an acid / substituent adduct with photopolymerizable functional groups. Z3, Z4, Z5, and Z6, as described above, can be ester-type (hereinafter also referred to as "acid / ester body") or amide-type (hereinafter also referred to as "acid / amide body"). By using such acid / ester body or acid / amide body, ester-type or amide-type polyimide precursors can be prepared. As a preferred candidate for preparing ester-type or amide-type polyimide precursors, a tetravalent organic group X having 6 to 40 carbon atoms... The tetracarboxylic acid dianhydride 1 is not limited to tetracarboxylic acid dianhydrides derived from the structures listed above. Examples include: pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic acid dianhydride, benzophenone-3,3',4,4'-tetracarboxylic acid dianhydride, biphenyl-3,3',4,4'-tetracarboxylic acid dianhydride, diphenyl sulfonate-3,3',4,4'-tetracarboxylic acid dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic acid 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. Tetracarboxylic acid dianhydrides can be used alone or in combination with two or more.

[0047] Using a tetracarboxylic acid dianhydride containing a tetravalent organic group X1 with 6 to 40 carbon atoms, reacting it with a compound having a reactive substituent (photopolymerizable functional group) that reacts with light (also referred to as a "substituent-introducing compound" in this invention), esterified or acetaminated tetracarboxylic acids (acid / ester or acid / acetamiprid) can be obtained. Alternatively, the aforementioned substituent-introducing compound can be used to introduce reactive substituents to the ends of the backbone of copolymer (A). The reaction sequence varies depending on the introduction method.

[0048] As a substituent-introducing compound (also referred to as "first substituent-introducing compound" in this invention) that can be preferably used to synthesize esterified tetracarboxylic acids (acid / ester body), examples include alcohols having photopolymerizable functional groups. Alcohols having photopolymerizable functional groups are preferably examples of alcohols containing the structure of general formula (2), such as 2-hydroxyethyl methacrylate (HEMA), 2-acryloyloxyethanol, 1-acryloyloxy-3-propanol, 2-acrylamidoethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy- 3-Tertiary butoxypropyl ester, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloxyethanol, 1-methacryloxy-3-propanol, 2-methacrylamide ethanol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tertiary butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate, etc.

[0049] Saturated aliphatic alcohols that can be used in conjunction with the aforementioned alcohols having photopolymerizable functional groups are preferably saturated aliphatic alcohols having 1 to 4 carbon atoms. Specific examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, and tributanol.

[0050] As a substituent-introducing compound (also referred to as "first substituent-introducing compound" in this invention) that can be preferably used to synthesize acetylated tetracarboxylic acids (acid / acetylated bodies), examples include amines having photopolymerizable functional groups. Examples of amines having photopolymerizable functional groups include amines comprising the structure of general formula (2), such as 2-aminoethyl methacrylate, 2-aminoethyl acrylate, and 2-(tertiary butylamino)ethyl methacrylate.

[0051] By mixing the above-mentioned tetracarboxylic acid dianhydride with the first substituent-introduced compound in the presence of a basic catalyst such as pyridine, and preferably in a suitable reaction solvent, at a temperature of 20-50°C for 4-10 hours, the substituent can be added to the acid anhydride (e.g., esterification or acetylation reaction) to obtain the desired acid / substituent adduct.

[0052] The preferred solvent for the above reaction is one that completely dissolves the tetracarboxylic acid dianhydride (as a starting material), the first substituent-introduced compound, and the acid / substituent adduct (as a product). More preferably, it is a solvent that also completely dissolves the polyimide precursor, which is the acetylamine condensation product of the acid / substituent adduct and the diamine. Examples include: N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, etc. Specific examples of these include: ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; esters such as methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, etc.; and lactones such as γ-butyrolactone, etc. Examples of ethers include: ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, etc. Examples of halogenated hydrocarbons include: dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, etc. Examples of hydrocarbons include: hexane, heptane, benzene, toluene, xylene, etc. These can be used alone or in combination as needed.

[0053] (Preparation of diamine oligomers) Step (i): By condensing a first tetracarboxylic dianhydride or its acid / substituent adduct with a first diamine compound to induce amide imidization, a diamine oligomer having a polyamide structure can be obtained. From the viewpoint of increasing the amide ring-closure rate, the first tetracarboxylic dianhydride used in the condensation reaction is preferably in the form of an acid dianhydride rather than an acid / substituent adduct. For example, a first tetracarboxylic dianhydride containing a tetravalent organic group X1 with 6 to 40 carbon atoms can undergo a condensation reaction with an excess of a first diamine compound containing a divalent organic group Y1 with 6 to 40 carbon atoms to achieve ring closure upon heating. The conditions for amide imidization are not limited; for example, heating at a temperature between 160°C and 300°C for 1 to 10 hours is sufficient. A higher amide ring-closure rate is preferred, but not limited; for example, 90% or higher, preferably 95% or higher, more preferably 99% or higher, or 100%.

[0054] Examples of first diamine compounds having a divalent organic group Y1 with 6 to 40 carbon atoms, which are used as raw materials for diamine oligomers having a polyimide structure, include: diamines having an aliphatic chain (alkyl group) with 6 to 40 carbon atoms, preferably 6 to 20 carbon atoms, such as 1,7-diaminoheptane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane; and diamines having an aromatic group with 6 to 40 carbon atoms. In addition to diamines derived from the structures listed above, examples of diamines containing aromatic groups include: p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobiphenyl, and 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] ion, bis[4-(3-aminophenoxy)phenyl] ion, 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-aminophenyl)hexafluoropropane, Diamine compounds include [{{4-(4-aminophenoxy)phenyl}hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, o-toluidine, 9,9-bis(4-aminophenyl)benzene, and bis{{4-(4-aminophenoxy)phenyl}one, as well as those in which a portion of the hydrogen atom on the benzene ring is substituted with an alkyl chain such as methyl or ethyl, such as 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof. However, diamine compounds are not limited to these. These diamine compounds can be used alone or in mixtures of two or more. These diamine compounds can also be used as secondary diamine compounds.

[0055] (Preparation of copolymers containing polyimide and polyimide precursors) Step (ii): The diamine oligomer obtained by the above method can be used as a diamine to undergo a condensation reaction with a second tetracarboxylic dianhydride or its acid / substituent adduct to synthesize a polyimide-polyimide precursor moiety (n2 unit) having a polyimide block moiety (n1 unit). The second tetracarboxylic dianhydride is preferably in the form of an acid / substituent adduct with photopolymerizable functional groups. The acid / substituent adduct is typically in a solution dissolved in the reaction solvent after the acid / substituent adduct has been prepared by the above method. Preferably, a suitable dehydrating condensing agent is added under ice bath cooling to convert the acid / substituent adduct into a polyanhydride. Subsequently, a solvent containing the diamine oligomer obtained by the above method is added dropwise to induce amide polycondensation, thereby obtaining the polyimide-polyimide precursor moiety (n2 unit). Alternatively, diamine siloxanes can be used in combination with the aforementioned diamines having a divalent organic group Y1, which are raw materials for diamine oligomers having a polyimide structure. Examples of the aforementioned dehydrating condensing agents include: dicyclohexylcarbodiimide (DCC), 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-dibutyldiimide carbonate. Polyanhydrides are obtained as intermediates in the manner described above.

[0056] Step (iii): The obtained polyimide-polyimide precursor moiety can be further condensed with a third tetracarboxylic dianhydride or its acid / substituent adduct, and a second diamine compound to synthesize a polyimide precursor moiety (unit of n 3). When the second tetracarboxylic dianhydride (or its acid / substituent adduct) and the third tetracarboxylic dianhydride (or its acid / substituent adduct) are identical, excess second tetracarboxylic dianhydride (or its acid / substituent adduct) present in the reaction solvent after the synthesis of the polyimide-polyimide precursor moiety can be directly used as the third tetracarboxylic dianhydride (or its acid / substituent adduct). Alternatively, the desired tetracarboxylic dianhydride (or its acid / substituent adduct) can be added to the system. When the first diamine compound and the second diamine compound are identical, excess first diamine compound present in the reaction solvent after the synthesis of the diamine oligomer can be directly used as the second diamine compound. The desired diamine compound can also be added to the system.

[0057] (Reactive resin end formation) Other reactive substituents that are polymerized by heat or light, and which are different from the photopolymerizable functional groups contained in the repeating units of copolymer (A), can be introduced to the end of the main chain by the following methods. (1) An acid / substituent adduct having photopolymerizable functional groups and reactive substituents is prepared by reacting a second and / or third tetracarboxylic dianhydride with a first substituent-introducing compound having photopolymerizable functional groups, followed by reacting a second substituent-introducing compound having reactive substituents that are different from the first substituent-introducing compound, or by reacting a second and / or third tetracarboxylic dianhydride with a second substituent-introducing compound, followed by reacting a first substituent-introducing compound; and / or (2) A diamine oligomer with a second reactive substituent is prepared by reacting a diamine oligomer with a compound containing a second substituent; (3) Using the acid / substituent adduct with photopolymerizable functional groups and reactive substituents obtained by (1) above, and / or the diamine oligomer with reactive substituents obtained by (2) above, steps (ii) and (iii) in the method for manufacturing copolymer (A) are carried out, thereby introducing reactive substituents derived from the second substituent-introducing compound to the acid terminus and / or amine terminus of the main chain of copolymer (A).

[0058] As the second substituent-introducing compound, it is preferred to introduce compounds with the structures represented by the above general formulas (E1) and (E2). Although there is no limitation, examples include: ethyl 2-isocyanate acrylate, ethyl 2-isocyanate methacrylate, ethyl 2-(2-methacryloxyethoxy)isocyanate, ethyl 1,1-(bisacryloxymethyl)isocyanate, allylamine, and methacryl chloride, etc.

[0059] In order to improve the adhesion between the photosensitive resin layer formed on the substrate by coating the photosensitive resin composition onto the substrate and various substrates, when preparing (A) a copolymer containing polyimide and polyimide precursor, diaminosiloxanes such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane can also be copolymerized.

[0060] After the polyamide condensation reaction is completed, the water-absorbing byproducts of the dehydrating condensing agent coexisting in the reaction solution are filtered and separated as needed. Then, a suitable unsuitable solvent, such as water, aliphatic lower alcohols, or a mixture thereof, is added to the solution containing the polymer components to precipitate the polymer. Subsequently, as needed, the re-dissolution and re-precipitation operations are repeated to purify the polymer. Vacuum drying is then performed to isolate the target copolymer containing polyimide and polyimide precursors. To further improve purification, the polymer solution can also be passed through a column packed with anion and / or cation exchange resins swelled with a suitable organic solvent to remove ionic impurities.

[0061] Regarding (A) the weight-average molecular weight of the copolymer containing polyimide and polyimide precursor, considering the heat resistance and mechanical properties of the film obtained after heat treatment, when determining the weight-average molecular weight using polystyrene converted by gel permeation chromatography (GPC), a value of 8,000 to 150,000 is preferred, more preferably 9,000 to 50,000, and even more preferably 18,000 to 40,000. A weight-average molecular weight of 8,000 or higher results in good mechanical properties, which is preferable. On the other hand, a value of 150,000 or lower results in good dispersibility in the developing solution and good resolution of the raised pattern, which is also preferable. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. Furthermore, the molecular weight is determined based on a calibration curve prepared using standard monodisperse polystyrene. As a standard monodisperse polystyrene, it is recommended to select from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko Corporation.

[0062] (B) Photopolymerization initiator (B) Photopolymerization initiators are compounds that can generate free radicals through active light, thereby enabling the polymerization of compounds containing vinyl unsaturated groups. Examples of initiators that generate free radicals through active light include compounds containing structures such as benzophenone, N-alkylaminoacetophenone, oxime esters, acridine, and phosphine oxide. Examples include: benzophenone, N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone (milchnerone), N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4- (Linylphenyl)-Butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2- Aromatic ketones such as linyl-acetone-1, propenyl benzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide; benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin compounds such as benzoin, methyl benzoin, and ethyl benzoin; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)], acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetylgoxyme) (manufactured by BASF Japan, Irgacure) Oxime esters such as OxeO2), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(o-benzoyl oxime) (manufactured by Shangzhou Qiangli Electronic Materials (Stock), PBG305), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3-yl]-,2-(O-acetylated oxime) (manufactured by Nikko Chemtech (Stock), TR-PBG-326, product name); benzodiazepine derivatives such as benzodiazepine dimethyl ketal; acridine derivatives such as 9-phenylacridinium and 1,7-bis(9,9'-acridyl)heptane; N-phenylglycine derivatives such as N-phenylglycine; coumarin compounds; Zyrazole compounds; phosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, but not limited to these. The polymerization initiators described above (C) can be used alone, or two or more can be used in combination. Among the above photopolymerization initiators, oxime ester compounds are preferred, especially from the viewpoint of resolution. in,

[0063] Compared to 100 parts by weight of the copolymer containing polyimide and polyimide precursor in (A), the amount of photopolymerization initiator is 0.5 parts by weight or more and 30 parts by weight or less, preferably 3 parts by weight or more and 15 parts by weight or less. From the viewpoint of photosensitivity or patternability, the above-mentioned amount is 0.5 parts by weight or more; on the other hand, from the viewpoint of the physical properties of the photosensitive resin layer after the photosensitive resin composition has cured, the above-mentioned amount is preferably 30 parts by weight or less.

[0064] (C) Solvent (C) The solvent is not limited to any solvent that can uniformly dissolve or suspend (A) the copolymer containing polyimide and the polyimide precursor, and (B) the photopolymerization initiator. Examples of such solvents include: γ-butyrolactone, dimethyl sulfoxide, tetrahydrofuran, ethyl acetoacetate, N,N-dimethylacetoacetamide, ε-caprolactone, 1,3-dimethyl-2-imidazolidineone, 3-methoxy-N,N-dimethylpropionic acid, 3-butoxy-N,N-dimethylpropionic acid, N,N-dimethylmethoxylamine, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetoacetamide, etc. One of these solvents may be used alone, or two or more may be mixed.

[0065] Depending on the required coating film thickness and viscosity of the photosensitive resin composition, the solvent can be used within the following range: for example, 30 to 1500 parts by weight, more preferably 100 to 1000 parts by weight, relative to 100 parts by weight of the copolymer containing polyimide and polyimide precursor in (A). When the solvent contains an alcohol without olefinic double bonds, the content of the alcohol without olefinic double bonds in the total solvent is preferably 5 to 50% by weight, more preferably 10 to 30% by weight. When the content of the alcohol without olefinic double bonds is 5% by weight or more, the storage stability of the photosensitive resin composition becomes good; when its content is 50% by weight or less, the solubility of the copolymer containing polyimide and polyimide precursor in (A) becomes good.

[0066] (D) Silane coupling agent To improve the adhesion of the embossed pattern, the photosensitive resin composition may optionally contain a (D) silane coupling agent. The (D) silane coupling agent preferably has the structure represented by the following general formula (9). General formula (9): [Chemistry 18] In formula (9), R 21 is selected from at least one of the substituents consisting of an epoxy group, a phenylamino group, and a urea group; R 22 is independently an alkyl group having 1 to 4 carbon atoms; R 23 is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms; d is an integer from 1 to 3; and m 4 is an integer from 1 to 6.

[0067] In general formula (9), d can be any integer from 1 to 3 and is not limited. Considering the adhesion to the metal rewiring layer, it is preferably 2 or 3, and more preferably 3. m4 can be any integer from 1 to 6 and is not limited. Considering the adhesion to the metal rewiring layer, it is preferably 1 or more and 4 or less. Considering the developability, it is preferably 2 or more and 5 or less.

[0068] R 21 is any substituent comprising any structure from the group consisting of epoxy, phenylamino, urea, isocyanate, and isocyanurate groups, and is not limited thereto. From the viewpoint of developability or adhesion to the metal redistribution layer, it is preferable to select at least one substituent from the group consisting of phenylamino and urea groups, and more preferably a substituent comprising phenylamino. R 22 is any alkyl group having 1 to 4 carbon atoms, and is not limited thereto. Examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tributyl. R 23 is any hydroxyl group or an alkyl group having 1 to 4 carbon atoms, and is not limited thereto. Examples of alkyl groups having 1 to 4 carbon atoms include the same alkyl group as R 22.

[0069] Examples of epoxy-containing silane coupling agents include: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane. Examples of phenylamino-containing silane coupling agents include N-phenyl-3-aminopropyltrimethoxysilane. Examples of urea-containing silane coupling agents include 3-ureopropyltrialkoxysilane. Examples of isocyanate-containing silane coupling agents include 3-isocyanopropyltriethoxysilane.

[0070] Compared to 100 parts by weight of the copolymer containing polyimide and polyimide precursor (A), the content of silane coupling in the resin composition (D) is 0.2% to 10% by weight, more preferably 1% to 8% by weight, and even more preferably 2% to 6% by weight, based on the viewpoint of copper adhesion.

[0071] (E) Free radical polymers To improve the resolution of the embossed pattern and suppress curing shrinkage during thermosetting, the photosensitive resin composition may optionally contain an (E) radical polymerizable compound. Preferably, such a compound is a (meth)acrylate compound that undergoes free radical polymerization via a photopolymerization initiator. Examples include: di(meth)acrylates of ethylene glycol or polyethylene glycol, such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate; di(meth)acrylates of propylene glycol or polypropylene glycol; di(meth)acrylates or tri(meth)acrylates of glycerol; cyclohexane di(meth)acrylate; di(meth)acrylates of 1,4-butanediol; 1, Compounds such as 6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, bisphenol A di(meth)acrylate, (meth)acrylamide, their derivatives, trimethylolpropane tri(meth)acrylate, glycerol di(meth)acrylate or tri(meth)acrylate, pentaerythritol di(meth)acrylate, tri(meth)acrylate or tetra(meth)acrylate, and ethylene oxide or propylene oxide adducts of these compounds, are not particularly limited to these. Among these free radical polymerizable compounds, from the viewpoint of inhibiting hardening shrinkage, it is preferable to have three or more free radical polymerizable groups. Furthermore, one monomer may be used, or a mixture of two or more monomers may be used.

[0072] Compared to 100 parts by weight of the copolymer containing polyimide and polyimide precursor (A), the content of free radical polymerizable compound (E) in the resin composition is 0.5% to 50% by weight, more preferably 5% to 40% by weight, and even more preferably 10% to 30% by weight, based on the viewpoint of resolution and inhibition of hardening shrinkage.

[0073] (F) Thermal crosslinking agent To suppress the hardening shrinkage of the cured film, the photosensitive resin composition may optionally contain (F) a thermal crosslinking agent.

[0074] (F) Thermal crosslinking agent refers to a compound that undergoes an addition reaction or a condensation reaction by heat. These reactions occur between (A) the copolymer resin containing polyimide and polyimide precursor and (F) thermal crosslinking agent, (F) thermal crosslinking agents with each other, and (F) thermal crosslinking agent with other components described below, with the reaction temperature preferably above 150°C.

[0075] Examples of (F) thermal crosslinking agents include: alkoxymethyl compounds, epoxy compounds, oxetane compounds, bismaleimide compounds, allyl compounds, and block isocyanate compounds. From the perspective of inhibiting hardening shrinkage, (F) thermal crosslinking agents are preferably those containing nitrogen atoms.

[0076] Examples of alkoxymethyl compounds include the following compounds, but are not limited to them. [Chemistry 19] [Chemistry 20]

[0077] Examples of epoxy compounds include those containing bisphenol A groups or hydrogenated bisphenol A diglycidyl ethers (e.g., Epolight 4000 manufactured by Kyoei Chemical Co., Ltd.). Examples of oxetane compounds include: 1,4-bis{[(3-ethyl-3-oxetane)methoxy]methyl}benzene, bis[1-ethyl(3-oxetane)]methyl ether, 4,4'-bis[(3-ethyl-3-oxetane)methyl]biphenyl, 4,4'-bis(3-ethyl-3-oxetane)methoxy)biphenyl, ethylene glycol bis(3-ethyl-3-oxetane)methyl ether, diethylene glycol bis(3-ethyl-3-oxetane)methyl ether, and bis(3-ethyl-3-oxetane)bis(3-ethyl-3-oxetane)methyl ether. Trimethylolpropane tri(3-ethyl-3-oxetane butyl methyl) ether, pentaerythritol tetra(3-ethyl-3-oxetane butyl methyl) ether, poly[[3-[(3-ethyl-3-oxetane)methoxy]propyl]sesquioxane] derivatives, oxetane silicate butyl ester, phenolic varnish-type oxetane, 1,3-bis[(3-ethyloxetane-3-yl)methoxy]benzene, OXT121 (manufactured by Toa Synthetic, trade name), OXT221 (manufactured by Toa Synthetic, trade name), etc. 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-epenylphenylbis(maleimide), and 4-methyl-N,N'- -1,3-Einylphenylbis(maleimide), N,N'-1,4-Einylphenylbis(maleimide), 3-methyl-N,N'-1,4-Einylphenylbis(maleimide), 4,4'-bis(maleimide)diphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-bis(maleimide)diphenylmethane, or 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane. Examples of allyl compounds include: allyl alcohol, allyl anisole, allyl benzoate, allyl cinnamate, N-allyloxyphthalimide, allyl phenol, allyl phenyl ether, allyl urea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl isocyanate, triallylamine, triallyl isocyanate, triallyl cyanurate, triallylamine, 1,3,5-benzenetricarboxylic acid, triallyl trimellitate, triallyl phosphate, triallyl phosphite, and triallyl citrate.Examples of block isocyanate compounds include: hexamethylene diisocyanate block isocyanates (such as 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 Corporation; and 7960, 7961, 7982, 7991, and 7992 manufactured by Baxenden Corporation); toluene diisocyanate block isocyanates (such as Takenate B-830 manufactured by Mitsui Chemicals Corporation); and 4,4'-diphenylmethane diisocyanate block isocyanates (such as Takenate B-815N manufactured by Mitsui Chemicals Corporation and Boronate manufactured by Daiei Sangyo Corporation). PMD-OA01 and PMD-MA01, etc.), 1,3-bis(isocyanatomethyl)cyclohexane block isocyanates (e.g., Takenate B-846N manufactured by Mitsui Chemicals, Coronate BI-301, 2507, and 2554 manufactured by Tosoh), and isophorone diisocyanate block isocyanates (e.g., 7950, 7951, and 7990 manufactured by Baxenden). Among these, block isocyanates or bismaleimide compounds are preferred from the perspective of storage stability. (F) Thermal crosslinking agents can be used alone or in combination of two or more.

[0078] Compared to 100 parts by weight of the copolymer containing polyimide and polyimide precursor (A), the content of thermal crosslinking agent (F) in the resin composition is 0.2% to 40% by weight, and more preferably 1% to 20% by weight, and even more preferably 2% to 10% by weight, based on the viewpoint of low dielectric properties and inhibition of hardening shrinkage.

[0079] (G) packing To suppress curing shrinkage of the cured film, the photosensitive resin composition may optionally contain (G) filler. The filler is any inert substance added to improve strength or various properties, and is not limited thereto.

[0080] From the viewpoint of suppressing the increase in viscosity during the preparation of the resin composition, the filler is preferably in particulate form. Examples of particulate form include needle-like, plate-like, and spherical shapes. From the viewpoint of suppressing the increase in viscosity during the preparation of the resin composition, the filler is preferably spherical.

[0081] Examples of needle-like fillers include: wollastonite, potassium titanate, hard calcium silicate, aluminum borate, and needle-shaped calcium carbonate.

[0082] Examples of plate-shaped fillers include: talc, mica, sericite, glass flakes, montmorillonite, boron nitride, and plate-shaped calcium carbonate.

[0083] Examples of spherical fillers include: calcium carbonate, silicon dioxide, aluminum oxide, titanium dioxide, clay, magnesium aluminum carbonate, magnesium hydroxide, zinc oxide, and barium titanate. Among these, silicon dioxide, aluminum oxide, titanium dioxide, and barium titanate are preferred, and silicon dioxide and aluminum oxide are more preferred, based on considerations of electrical properties or storage stability when forming resin compositions.

[0084] Regarding the size of the filler, in the case of spherical particles, the primary particle size is defined as the size; in the case of plate-like or needle-like particles, the length of the long side is defined as the size. Preferably, it is 5 nm to 1000 nm, more preferably 10 nm to 1000 nm. If it is 10 nm or more, it tends to become sufficiently uniform when preparing the resin composition; if it is 1000 nm or less, it can impart photosensitivity. From the viewpoint of imparting photosensitivity, it is preferably 800 nm or less, more preferably 600 nm or less, and especially preferably 300 nm or less. From the viewpoint of adhesion or uniformity of the resin composition, it is preferably 15 nm or more, more preferably 30 nm or more, and especially preferably 50 nm or more.

[0085] Relative to 100 parts by weight of (A) a copolymer containing polyimide and polyimide precursor, the content of filler (G) in the resin composition is 1 vol% to 20 vol%, preferably 5 vol% to 20 vol% from the viewpoint of dielectric properties, and even more preferably 5 vol% to 10 vol% from the viewpoint of resolution.

[0086] (H) Other components The photosensitive resin composition may further contain components other than those described in (A) to (G). Examples of other components include: resin components other than those in (A) which contain copolymers of polyimide and polyimide precursors; organic compounds containing metal elements; sensitizers; thermal polymerization inhibitors; azole compounds; and hindered phenolic compounds.

[0087] The photosensitive resin composition may further contain resin components other than (A) a copolymer comprising polyimide and a polyimide precursor. Examples of resin components that may be contained in the photosensitive resin composition include, for example, polyimide, poly... azole, poly The resins include azole precursors, phenolic resins, polyamides, epoxy resins, silicone resins, and acrylic resins. The amount of these resin components is preferably in the range of 0.01 to 20 parts by weight, relative to 100 parts by weight of the copolymer containing polyimide and polyimide precursors in (A).

[0088] The photosensitive resin composition may contain an organic compound comprising a metal element. Preferably, the organic compound comprising a metal element selected from the group consisting of titanium and zirconium is contained in one molecule. More preferably, it contains a hydrocarbon group comprising a hydrocarbon group or a heteroatom as the organic group. By including the organic compound, the amidedation rate of the polyimide precursor contained in the photosensitive resin composition increases, and the dielectric loss factor of the hardened film decreases. Examples of usable organotitanium or zirconium compounds include those with organic groups bonded to titanium or zirconium atoms via covalent or ionic bonds.

[0089] Specific examples of organotitanium or zirconium compounds are shown in sections I) to VII) below: As for the chelating compound (I), considering the preservation stability of the photosensitive resin composition and the ability to obtain good patterns, it is more preferably a compound having two or more alkoxy groups. Specific examples of chelating compounds include: bis(triethanolamine)diisopropoxide titanium, bis(2,4-glutaric acid)di(n-butanol) titanium, bis(2,4-glutaric acid)diisopropoxide titanium, bis(tetramethylpimelic acid)diisopropoxide titanium, bis(ethylacetic acid)diisopropoxide titanium, and compounds obtained by substituting zirconium atoms for titanium atoms in these compounds, but are not limited to these.

[0090] Examples of tetraalkoxy compounds include, but are not limited to, tetra(n-butanol)titanium, tetraethanoltitanium, tetra(2-ethylhexanol)titanium, tetraisobutanoltitanium, tetraisopropanoltitanium, tetramethanoltitanium, tetramethoxypropanoltitanium, tetramethylphenoltitanium, tetra(n-nonanol)titanium, tetra(n-propanol)titanium, tetrastearyl titanium, tetra[bis{2,2-(allyloxymethyl)butanol}]titanium, and compounds obtained by substituting zirconium atoms for titanium atoms in these compounds.

[0091] Examples of (III) diacetic or zirconium-based compounds include, for example, pentamethylcyclopentadienyltrimethyltitanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl)titanium, and compounds obtained by substituting zirconium atoms for titanium atoms in these compounds, but are not limited to these.

[0092] Examples of monoalkoxy compounds (IV) include, for example, titanium tris(dioctylphosphate)isopropoxide, titanium tris(dodecylbenzenesulfonic acid)isopropoxide, and compounds obtained by replacing titanium atoms of these compounds with zirconium atoms, but are not limited to these.

[0093] Examples of V) titanium oxy or zirconium oxy compounds include, for example, bis(glutaric acid) titanium oxy, bis(tetramethylpimelic acid) titanium oxy, phthalocyanine titanium oxy, and compounds obtained by replacing titanium atoms of these compounds with zirconium atoms, but are not limited to these.

[0094] As VI) titanium tetraacetate or zirconium tetraacetate compounds, examples include: titanium tetraacetate, compounds obtained by replacing titanium atoms of such compounds with zirconium atoms, but not limited to such compounds.

[0095] Examples of titanate coupling agents (VII) include isopropyltris(dodecylbenzenesulfonyl) titanate, but are not limited to these.

[0096] Of the compounds described in I) to VII) above, from the viewpoint of achieving a better dielectric loss factor, the organotitanium compound is preferably selected from at least one compound of the group consisting of I) titanium chelate compounds, II) tetraalkoxy titanium compounds, and III) diacetic titanium compounds. Particularly preferred are bis(ethylacetic acid)diisopropoxide titanium, tetra(n-butanol) titanium, and bis(n-5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl) titanium.

[0097] Compared to copolymers containing polyimide and polyimide precursors (A), the amount of organotitanium or zirconium compounds incorporated is 0.01 to 5 parts by mass, preferably 0.1 to 3 parts by mass. If the amount is 0.01 parts by mass or more, good amide ratio and dielectric loss factor of the cured film are observed in the resin composition; on the other hand, if it is 10 parts by mass or less, excellent storage stability is observed, which is preferred.

[0098] By including the aforementioned organic compound containing a metal element in the photosensitive resin composition, the amide formation rate of the polyimide precursor contained in the resin composition can be increased, thereby reducing the dielectric loss factor of the hardened film obtained using the resin composition. Although not bound by theory, it is believed that the reason for increasing the amide formation rate of the polyimide precursor is that by coordinating the metal element contained in the organic compound containing the metal element to the carbonyl group derived from the ester group, amide group, and / or carboxyl group of the polyimide precursor, the electron density of the carbonyl carbon atom can be reduced, promoting the ring-closing reaction.

[0099] To improve photosensitivity, the photosensitive resin composition may optionally contain a sensitizer. Examples of sensitizers include: milchnerone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzyl)cyclopentane, 2,6-bis(4'-diethylaminobenzyl)cyclohexanone, 2,6-bis(4'-diethylaminobenzyl)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamoyl indanone, p-dimethylaminobenzyl indanone, 2-(p-dimethylaminophenylbenzyl)benzothiazole, 2-(p-dimethylaminophenylvinyl)benzothiazole, 2-(p-dimethylaminophenylbenzyl)benzothiazole, etc. Phenylacetin) isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzyl)acetone, 1,3-bis(4'-diethylaminobenzyl)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetylated-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4- Linoylbenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzo[] Zyrazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, etc. These can be used alone or in combination of multiples (e.g., 2 to 5). The amount of sensitizer is preferably 0.1 to 25 parts by weight relative to 100 parts by weight of the copolymer comprising polyimide and polyimide precursor in (A).

[0100] To improve the stability of viscosity and photosensitivity of photosensitive resin compositions, especially when stored in a solvent-containing solution, the photosensitive resin composition may optionally contain a thermal polymerization inhibitor. Examples of thermal polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, and phenoxythiazolinone. 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-phenylhydroxyamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxyamine ammonium salt, etc. Furthermore, one or a mixture of two or more of these thermal polymerization inhibitors may be used. The amount of thermal polymerization inhibitor preferably ranges from 0.005 parts by weight to 12 parts by weight relative to 100 parts by weight of the copolymer comprising polyimide and polyimide precursor in (A).

[0101] When using a substrate containing copper or a copper alloy, the photosensitive resin composition may optionally contain azole compounds to suppress substrate discoloration. Examples of azole compounds include: 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-tert-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] 1-Benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc. Tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole are particularly preferred. Furthermore, one or a mixture of two or more azole compounds may be used.

[0102] Compared to 100 parts by weight of the copolymer containing polyimide and polyimide precursor in (A), the amount of azole compound is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 5 parts by weight from the viewpoint of photosensitivity. If the amount of azole compound is 0.1 parts by weight or more compared to 100 parts by weight of the copolymer containing polyimide and polyimide precursor in (A), discoloration of the copper or copper alloy surface can be suppressed when the photosensitive resin composition is formed on copper or copper alloy. On the other hand, if it is 20 parts by weight or less, the photosensitivity is excellent, which is preferred.

[0103] When using a substrate containing copper or a copper alloy, the photosensitive resin composition may contain a hindered phenolic compound in order to suppress substrate discoloration. Examples of hindered phenolic compounds include: 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, isooctyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2- Thio-diethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyphenylpropionamide), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)- ... -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)- ... -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-dibutyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-trione -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]- ... -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]- ... -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-tris(2,4 ... -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl)- ... -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)- ... -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)- ... -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)- ... -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)- ... -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2-methylbenzyl)- ... -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)- ... -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)- ... -2,4,6-(1H,3H,5H)-triones, etc., but not limited to these. Particularly preferred are 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)- ... -2,4,6-(1H,3H,5H)-trione.

[0104] Compared to 100 parts by weight of the copolymer containing polyimide and polyimide precursor in (A), the amount of hindered phenolic compound is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight from the perspective of photosensitivity characteristics. If the amount of hindered phenolic compound is 0.1 parts by weight or more compared to 100 parts by weight of the copolymer containing polyimide and polyimide precursor in (A), then, for example, when the photosensitive resin composition is formed on copper or copper alloy, discoloration and corrosion of copper or copper alloy can be prevented. On the other hand, if it is 20 parts by weight or less, the photosensitivity is excellent, which is preferred.

[0105] <Polyimide Curing Film and Its Manufacturing Method> Furthermore, the present invention also provides a method for manufacturing a polyimide curable film, which includes the step of converting a photosensitive resin composition into polyimide. The method for manufacturing the polyimide curable film of the present invention includes, for example, the following steps (1) to (5): (1) The step of coating the photosensitive resin composition of the present invention onto a substrate to form a photosensitive resin layer on the substrate; (2) The steps of heating and drying the obtained photosensitive resin layer; (3) The step of exposing the heated and dried photosensitive resin layer; (4) The step of developing the exposed photosensitive resin layer; and (5) The step of heating the developed photosensitive resin layer to form a polyimide hardened film.

[0106] The photosensitive resin composition used in the method for manufacturing the hardened film preferably comprises: 100 parts by weight of a copolymer comprising polyimide and a polyimide precursor, 0.5 to 30 parts by weight of a photosensitizer, and 100 to 1000 parts by weight of a solvent. More preferably, it comprises a photoradical polymerization initiator as a photosensitizer, and even more preferably, the photosensitive resin composition is negative.

[0107] The specific steps in the manufacturing method of the hardened film can be carried out according to steps (1) to (5) of the manufacturing method of the hardened film described above. Hereinafter, typical examples of each step will be described.

[0108] (1) Steps for forming the photosensitive resin layer In this step, the photosensitive resin composition of the present invention is coated onto a substrate, and then dried as needed to form a photosensitive resin layer. As a coating method, methods previously used for coating photosensitive resin compositions can be used, such as coating methods performed using a spin coater, bar coater, doctor blade coater, curtain coater, screen printing machine, etc., or spray coating methods performed using a spray coater, etc.

[0109] (2) Heating and drying steps The photosensitive resin composition film can be dried by heating as needed. Drying methods include air drying, drying using an oven or heating plate, and vacuum drying. Ideally, the film should be dried under conditions that do not cause amide formation of the polyimide precursor portion (polyamide ester) of the (A) copolymer in the photosensitive resin composition. Specifically, when air drying or heat drying is performed, drying can be carried out at 20°C to 140°C for 1 minute to 1 hour. By using the above methods, a photosensitive resin layer can be formed on the substrate.

[0110] (3) Exposure steps In this step, the photosensitive resin layer formed by the above method is exposed. Exposure apparatus can be, for example, a contact alignment machine, a mirror projection exposure machine, or a stepper. Exposure can be performed through a patterned photomask or reticle, or directly. The light used for exposure is, for example, an ultraviolet light source.

[0111] After exposure, post-exposure baking (PEB) and / or pre-development baking can be performed as needed, with any combination of temperature and time, to improve light sensitivity, etc. Regarding the range of baking conditions, the temperature is preferably 40~120°C and the time is preferably 10 seconds~240 seconds, but it is not limited to this range as long as it does not affect the various characteristics of the negative photosensitive resin composition of this embodiment.

[0112] (4) Development step In this step, the exposed photosensitive resin layer is developed to form a raised pattern. When the photosensitive resin composition is negative, the unexposed portions of the exposed photosensitive resin layer are developed and removed. As a developing method for the exposed (irradiated) photosensitive resin layer, any method can be selected from previously known photoresist developing methods, such as spin spraying, liquid coating, or immersion with ultrasonic treatment. Furthermore, after development, baking can be performed as needed, using any combination of temperature and time, to adjust the shape of the raised pattern. The developing solution is preferably a good solvent for negative photosensitive resin compositions, or a combination of such a good solvent and a poor solvent. Good solvents include, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. Poor solvents include, for example, toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate, and water, etc. When good and poor solvents are mixed, it is preferable to adjust the ratio of poor solvent to good solvent according to the solubility of the polymer in the negative photosensitive resin composition. Alternatively, two or more solvents, such as several, may be used in combination. In the step of developing the exposed photosensitive resin layer, it is preferable to perform the above coating-development step in a manner that yields a photosensitive resin layer with a film thickness of 10 μm to 15 μm.

[0113] (5) Polyimide curing film formation steps In this step, the raised pattern obtained by the above development is heated to dilute the photosensitive components and to amide-enzyme (A) copolymer, thus transforming it into a hardened raised pattern containing polyimide. Various methods can be used for heat curing, such as using a heating plate, using an oven, or using a temperature-programmable heating oven. Heating can be performed, for example, at 160°C to 400°C for 30 minutes to 5 hours. Air, or inert gases such as nitrogen or argon, can be used as the ambient gas during heat curing. By means of the above method, a hardened raised pattern (polyimide hardened film) can be manufactured.

[0114] The method for manufacturing the polyimide curable film of the present invention includes, for example, a method for manufacturing a curable film comprising the steps of coating the photosensitive resin composition of the present invention onto a substrate, performing exposure treatment, development treatment, and subsequently heat treatment. The dielectric loss factor of this curable film, when measured at 40 GHz using the perturbation-type split-cylinder resonator method, is preferably 0.003 to 0.011. Furthermore, the dielectric loss factor can be measured using the perturbation-type split-cylinder resonator method shown in the following examples.

[0115] Furthermore, the present invention also provides a polyimide cured film obtained from the photosensitive resin composition described above. From the perspective of transmission loss caused by the dielectric, the dielectric loss factor at a frequency of 40 GHz measured by the perturbed split cylinder resonator method for this cured film is preferably 0.003 to 0.011, and the lower the better. Also, from the perspective of multilayer formation of the rewiring layer, the cured film preferably has low curing shrinkage, and the residual film rate after curing is preferably 81% to 93%. By making the residual film rate after curing 81% or more, the strain of the rewiring layer caused by the copper wiring during rewiring becomes slight. As a rewiring material for copper wiring for high-speed transmission, it is preferable that the quotient of the residual film rate (RFA) and the dielectric loss factor (tanδ 40) (RFA / tanδ 40) is within a certain range. Preferably, the value of the dielectric loss factor at 40 GHz satisfies 0.003 < tanδ 40 < 0.011, and the residual film rate after curing satisfies 0.81 < RFA < 0.93 in terms of ratio (satisfies 81% < RFA < 93% in terms of percentage), and satisfies the following formula: 85 < RFA (ratio) / tanδ 40 < 175 . By making RFA (ratio) / tanδ 40 within the range greater than 85 and less than 175, a polyimide cured product that is preferably used as a rewiring material for copper wiring for high-speed transmission can be obtained. RFA (ratio) / tanδ 40 is more preferably greater than 100 and less than 170.

[0116] <Semiconductor device> The present invention can also provide a semiconductor device having a cured bump pattern obtained by the method for manufacturing the cured bump pattern using the photosensitive resin composition of the present invention. Therefore, the present invention provides a semiconductor device having: a semiconductor element as a substrate, and a cured bump pattern of polyimide formed on the substrate by the above-described method for manufacturing the cured bump pattern. Also, the present invention can also be applied to a method for manufacturing a semiconductor device that uses a semiconductor element as a substrate and includes the above-described method for manufacturing the cured bump pattern as a part of the steps. The semiconductor device can be manufactured by forming a cured bump pattern formed by the above-described method for manufacturing the cured bump pattern as a surface protection film, an interlayer insulating film, an insulating film for rewiring, a protection film for a flip chip device, or a protection film for a semiconductor device having a bump structure, etc., and combining it with a known method for manufacturing a semiconductor device.

[0117] The polyimide contained in the hardened textured pattern (polyimide hardened film) formed by the photosensitive resin composition preferably has the following general formula (10): [Chemistry 21] {In general formula (10), X1, X2, X3, Y1, and Y2 are the same as X1, X2, X3, Y1, and Y2 in general formula (1) above, n1 is an integer from 2 to 30, and n2 and n3 are integers from 2 to 150} represents the structure.

[0118] <Display Device> The present invention also provides a display device that uses the photosensitive resin composition of the present invention, comprising a display element and a hardened film disposed on the upper part of the display element, wherein the hardened film is the aforementioned hardened embossed pattern. Here, the hardened embossed pattern can be directly deposited on the display element in contact with it, or it can be deposited on the display element with other layers in between. Examples of such hardened films include: surface protective films, insulating films, and planarization films for TFT (Thin-Film Transistor) liquid crystal display elements and color filter elements; protrusions for MVA (Multi-Domain Vertical Alignment) type liquid crystal display devices; and spacers for cathodes of organic EL (Electroluminescence) elements.

[0119] In addition to its application in semiconductor devices as described above, the photosensitive resin composition of this invention can also be used for interlayer insulation of multilayer circuits, coating of flexible copper clad laminates, solder resist films, liquid crystal alignment films, and other applications.

[0120] <Method for manufacturing photosensitive resin composition> The method for manufacturing the photosensitive resin composition of the present invention includes: a step of manufacturing (A) a copolymer resin by the method of the present invention as described in "(A) Method for manufacturing a copolymer resin comprising polyimide and a polyimide precursor" above; and a step of mixing (A) 100 parts by weight of the copolymer resin, (B) 0.5 to 30 parts by weight of a photopolymerization initiator, and (C) 100 to 1000 parts by weight of a solvent to obtain the photosensitive resin composition. Alternatively, (D) the silane coupling agent, (E) the free radical polymerizable compound, (F) the thermal crosslinking agent, (G) the filler, and (H) other components described above may be mixed selectively. [Example]

[0121] The physical properties of the photosensitive resin compositions in the embodiments, comparative examples, and manufacturing examples of the present invention were measured and evaluated according to the following methods.

[0122] <Measurement and Evaluation Methods> (1) Weight average molecular weight The weight-average molecular weight (Mw) of the diamine oligomers and copolymer resins was determined by gel permeation chromatography (conversion from standard polystyrene). The column used for the determination was a series of Shodex 805M / 806M manufactured by Showa Denko Corporation. The standard monodisperse polystyrene was Shodex STANDARD SM-105 manufactured by Showa Denko Corporation. The developing solvent was N-methyl-2-pyrrolidone, and the detector was Shodex RI-930 manufactured by Showa Denko Corporation.

[0123] (2) Determination of the amide structure incorporation rate of the copolymer resin 10 g of copolymer resin was dissolved in a mixed solvent containing γ-butyrolactone and DMSO (dimethyl sulfoxide) (weight ratio 90:10), and the amount of solvent was adjusted to a viscosity of approximately 25 poise to prepare a polymer solution. The polymer solution was then spin-coated onto a 6-inch silicon wafer (manufactured by Fujimi Electronics Industry Co., Ltd., thickness 625±25 μm) using a coating and developing apparatus (D-Spin60A type, manufactured by SOKUDO Co., Ltd.), and dried on a hot plate at 110°C for 3 minutes to form a photosensitive resin layer with a thickness of approximately 10 μm. The photosensitive resin layer was measured using an ATR-FTIR (Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy) apparatus (Nicolet Continuum, Thermo Fisher Scientific) with a Si prism, in a measurement range of 4000 cm⁻¹ to 700 cm⁻¹, for 50 measurements. The acetilimation index 1 was obtained by dividing the peak height of the hardened film near 1380 cm⁻¹ (1350 cm⁻¹ to 1450 cm⁻¹, where the peak intensity is greatest when multiple peaks are present) by the peak height near 1500 cm⁻¹ (1460 cm⁻¹ to 1550 cm⁻¹, where the peak intensity is greatest when multiple peaks are present). The amide structure induction rate is calculated by dividing the amide imidization index 1 by the amide imidization index 2 of another cured film cured under the same conditions at 350°C.

[0124] (3) Resolution and development time of hardened raised pattern on Cu substrate On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industry Co., Ltd., thickness 625±25 μm), a 200 nm thick Ti layer and a 400 nm thick Cu layer were sequentially sputtered using a sputtering apparatus (L-440S-FHL type, manufactured by CANON ANELVA). Subsequently, a photosensitive resin composition prepared by the following method was spin-coated onto the wafer using a coating and developing apparatus (D-Spin60A type, manufactured by SOKUDO), and then dried at 110°C for 3 minutes on a hot plate to form a photosensitive resin layer with a thickness of approximately 13.5 μm. Using a photomask with a test pattern, the photosensitive resin layer was irradiated with an energy of 600 mJ / cm² using a Prisma GHI (manufactured by Ultratech) equipped with an i-ray filter. Subsequently, using cyclopentanone as the developer, the photosensitive resin layer was spray-developed using a coating and developing apparatus (D-Spin 60A, manufactured by SOKUDO), and rinsed with propylene glycol methyl ether acetate to obtain a raised pattern on Cu. The spray-developing time was taken as the development time. A temperature-programmed curing oven (VF-2000, manufactured by Koyo Lindberg) was used to heat-treat the wafer with the raised pattern on Cu at 230°C for 2 hours under nitrogen atmosphere, thereby obtaining a resin-containing hardened raised pattern with a thickness of approximately 10 μm on Cu. The fabricated raised pattern was observed under an optical microscope to determine the size of the minimum opening pattern. At this point, if the area of ​​the opening of the obtained pattern is more than 1 / 2 of the opening area of ​​the corresponding pattern mask, it is considered to be resolved. Based on the length of the mask opening edge (the size of the opening pattern) corresponding to the smallest area in the resolved opening, the resolution is judged according to the following evaluation criteria. (Evaluation Criteria) A: The smallest opening pattern size is less than 10 μm. B: The minimum opening size of the pattern is 10 μm or more but less than 15 μm. C: The minimum opening size of the pattern is 15 μm or more but less than 20 μm. D: The minimum opening size of the pattern is 20 μm or larger. In this invention, results of C and above are considered to be preferred.

[0125] (4) Determination of dielectric properties (relative permittivity: Dk, dielectric loss factor: Df) An Al wafer substrate was prepared by sputtering a 100 nm thick aluminum layer onto a 6-inch silicon wafer (manufactured by Fujimi Electronics Industry Co., Ltd., with a thickness of 625±25 μm) using a sputtering apparatus (L-440S-FHL type, manufactured by CANON ANELVA). A photosensitive resin composition prepared by the following method was then spin-coated onto the sputtered Al wafer substrate using a spin coating apparatus (D-spin60A type, manufactured by SOKUDO). The substrate was then heated and dried at 110°C for 180 seconds to form a photosensitive resin layer with a thickness of approximately 13.5 μm. Subsequently, a full exposure was performed using an alignment machine (PLA-501F, manufactured by Canon) with ghi rays at an exposure dose of 600 mJ / cm², followed by heat curing at 230°C for 2 hours in a nitrogen atmosphere using a vertical curing oven (Koyo Lindberg, model VF-2000B), to fabricate a resin-containing hardened film with a thickness of approximately 10 μm on the Al wafer. Using a dicing machine (DISCO, model DAD-2H / 6T), the hardened film was cut into pieces measuring 80 mm x 62 mm (for 10 GHz measurements) and 40 mm x 30 mm (for 40 GHz measurements), which were then immersed in a 10% hydrochloric acid aqueous solution and peeled off from the silicon wafer to prepare film samples. For the film samples, the relative permittivity (Dk) and dielectric loss factor (Df) at 10 GHz and 40 GHz were measured using the resonator perturbation method, respectively. Details of the measurement methods are described below. (Determination Method) Disturbance-type split cylindrical resonator method (Sample humidity adjustment) Let stand at 23℃ / 50%RH for 24 hours (Measurement conditions) 23℃ / 50%RH (Device Composition) Network analyzer: PNA Network Analyzer N5224B (Manufactured by KEYSIGHT) Split-cylinder resonator: CR-710 (manufactured by Kanto Electronics Application Development Co., Ltd., measured frequency: approximately 10 GHz) CR-740 (manufactured by Kanto Electronics Application Development Co., Ltd., measured frequency: approximately 40 GHz)

[0126] (5) Determination of residual film rate after hardening On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industry Co., Ltd., thickness 625±25 μm), a 200 nm thick Ti layer and a 400 nm thick Cu layer were sequentially sputtered using a sputtering apparatus (L-440S-FHL type, manufactured by CANON ANELVA). Subsequently, a photosensitive resin composition prepared by the method described below was spin-coated onto the wafer using a coating and developing apparatus (D-Spin60A type, manufactured by SOKUDO), and then dried at 110°C for 3 minutes on a heated plate to form a photosensitive resin layer with a thickness of approximately 13.5 μm. Afterwards, a full-surface exposure was performed using a alignment machine (PLA-501F, manufactured by Canon) with ghi rays at an exposure dose of 800 mJ / cm². Subsequently, the coating formed on the wafer was spray-developed using cyclopentanone and a developer (D-SPIN636 model, manufactured by Dainippon Screen Mfg, Japan). After rinsing with propylene glycol methyl ether acetate, it was dried by spin drying. The thickness of the developed film was measured and designated as film thickness 1. Next, the developed film was heat-cured for 2 hours at 230°C under nitrogen atmosphere using a vertical curing oven (Koyo Lindberg, model VF-2000B). The thickness of the heat-cured film was measured and designated as film thickness 2. Using these film thicknesses, the residual film percentage (ratio and %) after curing was calculated using the following formula. Residual film rate after hardening (ratio) = film thickness 2 / film thickness 1 Residual film rate after hardening (%) = film thickness 2 / film thickness 1×100 Furthermore, calculate the quotient of the residual film rate (ratio) and the dielectric loss factor (tanδ 40) after curing (RFA (ratio) / tanδ 40).

[0127] (6) Evaluation of copper tightness On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industry Co., Ltd., thickness 625±25 μm), a 200 nm thick Ti layer and a 400 nm thick Cu layer were sequentially sputtered using a sputtering apparatus (L-440S-FHL type, manufactured by CANON ANELVA). Subsequently, a photosensitive resin composition prepared by the following method was spin-coated onto the wafer using a coating and developing apparatus (D-Spin60A type, manufactured by SOKUDO), and then heated and dried at 110°C for 3 minutes on a hot plate to form a photosensitive resin layer with a thickness of approximately 13.5 μm. Subsequently, a full-surface exposure was performed using an alignment machine (PLA-501F, manufactured by Canon) with ghi rays at an exposure dose of 800 mJ / cm², followed by heat curing at 230°C for 2 hours in a nitrogen atmosphere using a vertical curing oven (Koyo Lindberg, model VF-2000B), to fabricate a resin-containing hardened film with a thickness of approximately 10 μm on the Cu wafer. For the heat-treated film, the adhesion characteristics between the copper substrate and the hardened resin coating were evaluated based on the following criteria using the cross-cutting method according to JIS K 5600-5-6 standard. (Evaluation Criteria) A: The grid number of the hardened resin coating bonded to the substrate is 80 or higher to 100. B: The grid number of the hardened resin coating bonded to the substrate is 60 or more but less than 80. C: The grid number of the hardened resin coating bonded to the substrate is 40 or more but less than 60. D: The number of grids in the hardened resin coating bonded to the substrate is less than 40. In this invention, results of B or higher are considered preferred.

[0128] (7) Preservation stability The following photosensitive resin composition was prepared and allowed to stand at room temperature for 24 hours. Viscosity was then measured at 23°C using an E-type viscometer (VISCOMATE VM-150III, manufactured by Toki Sangyo). This initial viscosity was recorded as Viscosity 1. The measured photosensitive resin composition was then stored at 40°C for 3 days, and viscosity was measured again under the same conditions. This viscosity after heat treatment was recorded as Viscosity 2. Storage stability was calculated using the following formula based on these viscosities. Viscosity change rate (%) = (|viscosity2 - viscosity1| / viscosity1) × 100 (Evaluation Criteria) A: The viscosity change rate did not reach 3%. B: Viscosity change rate is 3% or more but less than 5%. C: Viscosity change rate is greater than 5% but less than 10%. D: Viscosity change rate is above 10% In this invention, results of C and above are considered to be preferred.

[0129] <Manufacturing of Diamine X-1> Ar displacement was performed on a 5 L four-necked flask. 172.02 g of 4,4'-butylindobis(6-tert-butyl-m-cresol), 155.84 g of 4-chloronitrobenzene, and 1.5 L of DMF (dimethylformamide) were added, and the mixture was stirred. 186.42 g of K₂CO₃ was added, and the mixture was heated at 150 °C for 5 hours. The disappearance of the starting materials and intermediates was confirmed by TLC (Thin-Layer Chromatography). After cooling to room temperature, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure at 80 °C. The concentrated residue was added to 1.6 L of deionized water, followed by the addition of 2.5 L of ethyl acetate, and purified three times by separation. The organic layer was recovered and dried by adding MgSO₄. After drying, the mixture was filtered to remove impurities, dissolved in 800 mL of toluene, and the resulting solution was added to 4.0 L of methanol and stirred for 30 minutes. After stirring, the mixture was filtered to recover the filtrate, which was then dried at 80°C for 12 hours. The dried reactant was transferred to a 5 L four-necked flask purged with Ar, followed by the addition of 19.04 g of 5% Pd / C (EA) and 1.9 L of THF (tetrahydrofuran), and stirred. The flask was heated to 40°C, and H₂ was introduced at 10 mL / min for a reduction reaction over 24 hours. The reaction solution was filtered through diatomaceous earth, and the target component was recovered by silica gel chromatography. The solution was then concentrated under reduced pressure to obtain diamine X-1.

[0130] <(A) Manufacturing of diamine compounds having repeating units of polyimide structure> Synthesis of polyimide (diamine oligomer W-1): 41.6 g of 4,4'-(4,4'-isopropylidenediphenoxy)phthalic anhydride (BPADA) as the acid component, 34.0 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) as the diamine component, and 176.4 g of N-methylpyrrolidone (NMP) as the solvent were added to a 0.5-liter separable flask equipped with a Dean-Stark tube and a condenser, and stirred until dissolved. Then, 42.3 g of toluene was added and stirred, and the mixture was heated to 185°C under a nitrogen atmosphere. After stirring at 185°C for 2.5 hours, the toluene and water generated by amide imidization were removed from the system over a period of 1.5 hours. The mixture was then cooled to room temperature to obtain a solution of diamine oligomer W-1 containing repeating polyamide units. The weight-average molecular weight (Mw) of the diamine oligomer W-1 was determined to be 3,000. Nuclear magnetic resonance (NMR) analysis of diamine oligomer W-1 was performed, and the peaks originating from the amide bond of the polyimide were compared with those originating from the aromatic ring to confirm the amide ring closure rate. The amide ring closure rate was over 99%.

[0131] Synthesis of polyimide (diamine oligomer W-2): Using the above-described method for synthesizing diamine oligomer W-1, 52.6 g of 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane (MBAPP) was used instead of 34.0 g of m-TB, and 220 g of NMP and 52.8 g of toluene were used as solvents. The reaction was carried out in the same manner as described in the method for synthesizing diamine oligomer W-1, thereby obtaining a solution of diamine oligomer W-2. The weight-average molecular weight (Mw) of diamine oligomer W-2 was determined to be 5,000. The amide ring-closure rate obtained by 1H-NMR determination in the same manner as that of diamine oligomer W-1 was ≥99%.

[0132] Synthesis of polyimide (diamine oligomer W-3): Using the above-described method for synthesizing diamine oligomer W-1, 24.8 g of 4,4'-oxophthalic dianhydride (ODPA) was used instead of 41.6 g of BPADA, 65.7 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) was used instead of 34.0 g of m-TB, and 211 g of NMP and 50.7 g of toluene were used as solvents. The reaction was carried out in the same manner as described in the method for synthesizing diamine oligomer W-1, thereby obtaining a solution of diamine oligomer W-3. The weight-average molecular weight (Mw) of diamine oligomer W-3 was determined to be 2,700. The amide ring-closure rate obtained by 1H-NMR determination in the same manner as that of diamine oligomer W-1 was over 99%.

[0133] Synthesis of polyimide (diamine oligomer W-4): Using the same method for synthesizing diamine oligomer W-1 as described above, 24.8 g of ODPA was used instead of 41.6 g of BPADA, 70.2 g of MBAPP was used instead of 34.0 g of m-TB, and 222 g of NMP and 53.0 g of toluene were used as solvents. The reaction was carried out in the same manner as described in the synthesis method for diamine oligomer W-1, thereby obtaining a solution of diamine oligomer W-4. The weight-average molecular weight (Mw) of diamine oligomer W-4 was determined to be 3,000. The amide ring-closure rate obtained by 1H-NMR determination in the same manner as for diamine oligomer W-1 was ≥99%.

[0134] Synthesis of polyimide (diamine oligomer W-5): Using the same method for synthesizing diamine oligomer W-1 as described above, 24.8 g of ODPA was used instead of 41.6 g of BPADA, 90.4 g of diamine X-1 was used instead of 34.0 g of m-TB, and 269 g of NMP and 64.5 g of toluene were used as solvents. The reaction was carried out in the same manner as described in the synthesis method for diamine oligomer W-1, thereby obtaining a solution of diamine oligomer W-5. The weight-average molecular weight (Mw) of diamine oligomer W-5 was determined to be 3,500. The amide ring-closure rate obtained by 1H-NMR determination in the same manner as for diamine oligomer W-1 was over 99%.

[0135] Synthesis of polyimide (diamine oligomer W-6): Using the above-described method for synthesizing diamine oligomer W-1, 55.8 g of 9,9-bis(4-aminophenyl)ferrugin (BAFL) was used instead of 34.0 g of m-TB, and 188 g of NMP and 45.1 g of toluene were used as solvents. The reaction was carried out in the same manner as described in the method for synthesizing diamine oligomer W-1, thereby obtaining a solution of diamine oligomer W-6. The weight-average molecular weight (Mw) of diamine oligomer W-6 was determined to be 2,900. The amide ring-closure rate obtained by 1H-NMR determination in the same manner as that of diamine oligomer W-1 was over 99%.

[0136] Synthesis of polyimide (diamine oligomer W-7): Using the same method for synthesizing diamine oligomer W-1 as described above, 37.2 g of BAFL was used instead of 34.0 g of m-TB, and 145 g of NMP and 34.7 g of toluene were used as solvents. The reaction was carried out in the same manner as described in the synthesis method for diamine oligomer W-1, thereby obtaining a solution of diamine oligomer W-7. The weight-average molecular weight (Mw) of diamine oligomer W-7 was determined to be 8,200. The amide ring-closure rate obtained by 1H-NMR determination in the same manner as for diamine oligomer W-1 was over 99%.

[0137] Synthesis of polyimide (diamine oligomer W-8): Using the above-described method for synthesizing diamine oligomer W-1, 24.8 g of ODPA was used instead of 41.6 g of BPADA, 51.2 g of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB) was used instead of 34.0 g of m-TB, and 177 g of NMP and 42.6 g of toluene were used as solvents. The reaction was carried out in the same manner as described in the synthesis method for diamine oligomer W-1, thereby obtaining a solution of diamine oligomer W-8. The weight-average molecular weight (Mw) of diamine oligomer W-8 was determined to be 2,500. The amide ring-closure rate obtained by 1H-NMR determination in the same manner as for diamine oligomer W-1 was ≥99%.

[0138] Synthesis of polyimide (diamine oligomer W-9): Using the above-described method for synthesizing diamine oligomer W-1, 35.5.8 g of 4,4'-(hexafluoroisopropylidene)phthalic anhydride (6FDA) was used instead of 41.6 g of BPADA, 65.7 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) was used instead of 34.0 g of m-TB, and 236 g of NMP and 56.7 g of toluene were used as solvents. The reaction was carried out in the same manner as described in the method for synthesizing diamine oligomer W-1, thereby obtaining a solution of diamine oligomer W-9. The weight-average molecular weight (Mw) of diamine oligomer W-9 was determined to be 3,200. The amide ring-closure rate obtained by 1H-NMR determination in the same manner as that of diamine oligomer W-1 was over 99%.

[0139] Synthesis of polyimide (diamine oligomer W-10): Using the above-described method for synthesizing diamine oligomer W-1, 20.7 g of 1,10-diaminodecane was used instead of 34.0 g of m-TB, and 249 g of NMP and 34.9 g of toluene were used as solvents. The reaction was carried out in the same manner as described in the method for synthesizing diamine oligomer W-1, thereby obtaining a solution of diamine oligomer W-10. The weight-average molecular weight (Mw) of diamine oligomer W-10 was determined to be 3,700. The amide ring-closure rate obtained by 1H-NMR determination in the same manner as diamine oligomer W-1 was ≥99%.

[0140] <(A) Manufacturing of a copolymer resin containing polyimide and polyimide precursor> Synthesis of Polymer A-1: 20.9 g of BPADA (as the acid component) was added to a 1-liter separable flask, along with 10.9 g of 2-hydroxyethyl methacrylate (HEMA) and 42 g of γ-butyrolactone (GBL). While stirring, 6.4 g of pyridine was added at room temperature, and the mixture was heated at 50°C for 4 hours. After the exothermic reaction was complete, the mixture was allowed to cool to room temperature and then allowed to stand for 16 hours to obtain the reaction mixture.

[0141] Subsequently, under ice bath cooling, while stirring, a solution obtained by dissolving 16.3 g of dicyclohexylcarbodiimide (DCC) in 16.3 g of GBL was added to the reaction mixture over 40 minutes, followed by the addition of 91.0 g of GBL. Then, while stirring, a solution obtained by mixing 101.7 g of NMP solution of the diamine oligomer W-2 prepared as a diamine component with 66.5 g of GBL was added over 20 minutes. Next, while stirring, a solution obtained by dissolving 2.4 g of m-TB in 7 g of GBL was added over 5 minutes. Then, after stirring at room temperature for 4 hours, 6.4 g of ethanol was added and stirring for 30 minutes, followed by the addition of 49.0 g of GBL. The precipitate formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0142] The obtained reaction solution was added to 1000 g of ethanol to generate a precipitate containing crude polymer. The crude polymer was filtered off and dissolved in 270 g of γ-butyrolactone to obtain a crude polymer solution. The crude polymer solution was purified using an anion exchange resin (Amberlyst TM15JWET manufactured by Organo Co., Ltd.) to obtain a polymer solution. The obtained polymer solution was added dropwise to 3800 g of water to precipitate the polymer. The precipitate was filtered off and then vacuum dried to obtain polymer A-1 in powder form. The weight average molecular weight (Mw) of polymer A-1 is 30,000, and the amide group content is 0.43. Furthermore, the amide group concentration U of each repeating unit of the polyamide obtained from polymer A-1 is 16.0 wt%. Furthermore, the "polyimide concentration U" is calculated by converting it to the polyimide content of the polyimide-cured film obtained by heating and curing at 350°C (the same applies below).

[0143] Synthesis of Polymer A-2: 15.2 g of BPADA (as the acid component) was added to a 1-liter separable flask, along with 7.9 g of HEMA and 30.8 g of γ-butyrolactone (GBL). While stirring, 4.6 g of pyridine was added at room temperature, and the mixture was heated at 50°C for 4 hours. After the exothermic reaction was complete, the mixture was allowed to cool to room temperature. It was then allowed to stand for 16 hours to obtain the reaction mixture.

[0144] Subsequently, under ice bath cooling and stirring, a solution obtained by dissolving 11.9 g of dicyclohexylcarbodiimide (DCC) in 11.9 g of GBL was added to the reaction mixture over 40 minutes, followed by the addition of 91.0 g of GBL. Then, under stirring, a solution obtained by mixing 111.5 g of an NMP solution of the diamine oligomer W-1 prepared as a diamine component with 72.9 g of GBL was added over 20 minutes. After stirring at room temperature for 4 hours, 49.0 g of GBL was added. The precipitate formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0145] The subsequent purification steps were carried out in the same manner as described in the synthesis method of polymer A-1, thereby obtaining polymer A-2. Polymer A-2 has a weight-average molecular weight (Mw) of 24,000 and an imide group incorporation rate of 0.58. Furthermore, the imide group concentration U of each repeating unit of the polyimide obtained from polymer A-2 is 20.1 wt%.

[0146] Synthesis of Polymer A-3: 15.2 g of BPADA (as the acid component) was added to a 1-liter separable flask, along with 7.9 g of HEMA (the first substituent-introduced compound) and 30.8 g of GBL. While stirring, 4.6 g of pyridine was added at room temperature, and the mixture was heated at 50°C for 4 hours. After the exothermic reaction was complete, the mixture was allowed to cool to room temperature. It was then allowed to stand for 16 hours to obtain the reaction mixture (first reaction).

[0147] In a separately prepared 0.5-liter three-necked flask, 111.5 g of NMP solution of diamine oligomer W-1 (as the diamine component) was mixed with 72.9 g of GBL. While the mixture was cooled in an ice bath, 3.1 g of 2-isocyanate methacrylate (the second substituent-introducing compound) was dissolved in 15.5 g of GBL and stirred for 1 hour under ice bath cooling to obtain a reaction mixture solution with diamine oligomer W-1 (second reaction).

[0148] Simultaneously with the second reaction described above, under ice bath cooling and stirring, a solution obtained by dissolving 11.9 g of DCC in 20 g of GBL was added to the reaction mixture of the first reaction for 40 minutes. Then, under stirring and stirring, a reaction mixture solution of the diamine oligomer W-1 obtained in the second reaction was added for 60 minutes. After stirring at room temperature for 4 hours, 49.0 g of GBL was added. The precipitate formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0149] The subsequent purification steps were carried out in the same manner as described in the synthesis method of polymer A-1, thereby obtaining polymer A-3. Polymer A-3 has a weight-average molecular weight (Mw) of 18,000 and an imide group incorporation rate of 0.58. Furthermore, the imide group concentration U of each repeating unit of the polyimide obtained from polymer A-3 is 20.1 wt%.

[0150] Synthesis of Polymer A-4: In the synthesis method of polymer A-1 described above, 17.0 g of BPADA was used instead of 20.9 g, 8.8 g of HEMA was used instead of 10.9 g, 13.3 g of DCC was used instead of 16.3 g, and 127.2 g of NMP solution of diamine oligomer W-2 was used instead of 101.7 g of NMP solution of diamine oligomer W-2 and 2.4 g of mTB. Otherwise, the reaction was carried out in the same manner as described in the synthesis method of polymer A-1, thereby obtaining polymer A-3. The weight average molecular weight (Mw) of polymer A-3 is 35,000, and the amide group induction rate is 0.53. Furthermore, the amide group concentration U of each repeating unit of the polyamide obtained from polymer A-4 is 15.2 wt%.

[0151] Synthesis of Polymer A-5: In the synthesis method of polymer A-2 described above, 8.1 g of ODPA was used instead of 15.2 g of BPADA, 7.1 g of HEMA was used instead of 7.9 g, 10.7 g of DCC was used instead of 11.9 g, and 169.6 g of NMP solution of diamine oligomer W-3 was used instead of 111.5 g of NMP solution of diamine oligomer W-1. Otherwise, the reaction was carried out in the same manner as described in the synthesis method of polymer A-2, thereby obtaining polymer A-5. The weight average molecular weight (Mw) of polymer A-5 is 22,000, and the imide group induction rate is 0.63. Furthermore, the imide group concentration U of each repeating unit of the polyimide obtained from polymer A-4 is 20.5 wt%.

[0152] Synthesis of Polymer A-6: In the synthesis method of polymer A-2 described above, 8.1 g of ODPA was used instead of 15.2 g of BPADA, 7.1 g of HEMA was used instead of 7.9 g, 10.7 g of DCC was used instead of 11.9 g, and 176.7 g of NMP solution of diamine oligomer W-4 was used instead of 111.5 g of NMP solution of diamine oligomer W-1. Otherwise, the reaction was carried out in the same manner as described in the synthesis method of polymer A-2, thereby obtaining polymer A-6. The weight-average molecular weight (Mw) of polymer A-6 is 23,000, and the amide group induction rate is 0.63. Furthermore, the amide group concentration U of each repeating unit of the polyamide obtained from polymer A-6 is 19.6 wt%.

[0153] Synthesis of Polymer A-7: In the synthesis method of polymer A-1 described above, 12.4 g of ODPA was used instead of 20.9 g of BPADA, 143.1 g of NMP solution of diamine oligomer W-5 was used instead of 101.7 g of NMP solution of diamine oligomer W-2 and 2.4 g of m-TB. Otherwise, the reaction was carried out in the same manner as described in the synthesis method of polymer A-1, thereby obtaining polymer A-7. The weight-average molecular weight (Mw) of polymer A-7 is 21,000, and the amide group induction rate is 0.43. Furthermore, the amide group concentration U of each repeating unit of the polyamide obtained from polymer A-7 is 16.7 wt%.

[0154] Synthesis of Polymer A-8: 12.4 g of ODPA (as the acid component) was added to a 1-liter separable flask, along with 10.8 g of HEMA (the first substituent-introduced compound) and 26.0 g of GBL. 6.3 g of pyridine was added while stirring at room temperature to obtain the reaction mixture (first reaction). After the exothermic reaction was complete, the mixture was allowed to cool to room temperature and then allowed to stand for 16 hours.

[0155] Subsequently, under ice bath cooling, while stirring, a solution obtained by dissolving 16.3 g of dicyclohexylcarbodiimide (DCC) in 16.3 g of GBL was added to the reaction mixture of the first reaction over 40 minutes. Next, 1.1 g of allylamine (the second substituent-introducing compound) was dissolved in 5.5 g of GBL, and this GBL solution was added over 5 minutes while stirring (second reaction). While stirring, a solution obtained by dissolving 143.1 g of NMP solution of diamine oligomer W-5 (the diamine component) in 93.6 g of GBL was added to the reaction mixture of the second reaction over 60 minutes. Then, after stirring at room temperature for 4 hours, 6.4 g of ethanol was added and stirring for 30 minutes, followed by the addition of 49.0 g of GBL. The precipitate formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0156] The subsequent purification steps were carried out in the same manner as described in the synthesis method of polymer A-1, thereby obtaining polymer A-8. Polymer A-8 has a weight-average molecular weight (Mw) of 19,000 and an imide group incorporation rate of 0.43. Furthermore, the imide group concentration U of each repeating unit of the polyimide obtained from polymer A-8 is 16.7 wt%.

[0157] Synthesis of Polymer A-9: In the synthesis method of polymer A-1 described above, 105.6 g of NMP solution of diamine oligomer W-6 was used instead of 101.7 g of NMP solution of diamine oligomer W-2 and 2.4 g of m-TB. Otherwise, the reaction was carried out in the same manner as described in the synthesis method of polymer A-1, thereby obtaining polymer A-9. The weight-average molecular weight (Mw) of polymer A-9 is 29,000, and the amide group induction rate is 0.43. Furthermore, the amide group concentration U of each repeating unit of the polyamide obtained from polymer A-9 is 16.8 wt%.

[0158] Synthesis of Polymer A-10: In the synthesis method of polymer A-2 described above, 4.6 g of BPADA was used instead of 15.2 g of BPADA, 2.4 g of HEMA was used instead of 7.9 g of HEMA, 3.6 g of DCC was used instead of 11.9 g of DCC, and 174.4 g of NMP solution of diamine oligomer W-7 was used instead of 111.5 g of NMP solution of diamine oligomer W-1. Otherwise, the reaction was carried out in the same manner as described in the synthesis method of polymer A-2, thereby obtaining polymer A-10. The weight average molecular weight (Mw) of polymer A-10 is 40,000, and the amide group induction rate is 0.88. Furthermore, the amide group concentration U of each repeating unit of the polyamide obtained from polymer A-10 is 16.8 wt%.

[0159] Synthesis of Polymer A-11: In the synthesis method of polymer A-3 described above, 4.6 g of BPADA was used instead of 15.2 g of BPADA, 2.4 g of HEMA was used instead of 7.9 g of HEMA, 3.6 g of DCC was used instead of 11.9 g of DCC, 174.4 g of NMP solution of diamine oligomer W-7 was used instead of 111.5 g of NMP solution of diamine oligomer W-1, and 2.1 g of methacrylic acid chloride and 1.4 g of pyridine were used instead of 3.1 g of 2-isocyanate methacrylate. Otherwise, the reaction was carried out in the same manner as described in the synthesis method of polymer A-3, thereby obtaining polymer A-11. The weight average molecular weight (Mw) of polymer A-11 is 36,000, and the imine group induction rate is 0.88. Furthermore, the amide group concentration U of each repeating unit of the polyamide obtained from polymer A-11 is 16.8 wt%.

[0160] Synthesis of Polymer A-12: In the synthesis method of polymer A-1 described above, 12.1 g of ODPA was used instead of 20.9 g of BPADA, 85.5 g of NMP solution of diamine oligomer W-8 was used instead of 101.7 g of NMP solution of diamine oligomer W-2 and 2.4 g of m-TB. Otherwise, the reaction was carried out in the same manner as described in the synthesis method of polymer A-1, thereby obtaining polymer A-12. The weight-average molecular weight (Mw) of polymer A-12 is 26,000, and the amide group induction rate is 0.58. Furthermore, the amide group concentration U of each repeating unit of the polyamide obtained from polymer A-12 is 23.6 wt%.

[0161] Synthesis of Polymer A-13: In the synthesis method of polymer A-1 described above, 17.3 g of 6FDA was used instead of 20.9 g of BPADA, 113.8 g of NMP solution of diamine oligomer W-9 was used instead of 101.7 g of NMP solution of diamine oligomer W-2 and 2.4 g of m-TB. Otherwise, the reaction was carried out in the same manner as described in the synthesis method of polymer A-1, thereby obtaining polymer A-13. The weight-average molecular weight (Mw) of polymer A-13 is 28,000, and the amide group induction rate is 0.44. Furthermore, the amide group concentration U of each repeating unit of the polyamide obtained from polymer A-13 is 17.1 wt%.

[0162] Synthesis of Polymer A-14: In the synthesis method of polymer A-2 described above, 7.7 g of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) was used instead of 15.2 g of BPADA, 7.1 g of HEMA was used instead of its 7.9 g, 10.7 g of DCC was used instead of its 11.9 g, and 150.1 g of NMP solution of diamine oligomer W-4 was used instead of 111.5 g of NMP solution of diamine oligomer W-1. Otherwise, the reaction was carried out in the same manner as described in the synthesis method of polymer A-2, thereby obtaining polymer A-14. The weight-average molecular weight (Mw) of polymer A-14 is 21,000, and the amide group induction rate is 0.63. Furthermore, the amide group concentration U of each repeating unit of the polyamide obtained from polymer A-14 is 19.8 wt%.

[0163] Synthesis of Polymer A-15: In the synthesis method of polymer A-1 described above, 30.6 g of BPADA was used instead of 20.9 g, 15.9 g of HEMA was used instead of 10.9 g, 9.3 g of pyridine was used instead of 6.4 g, 23.9 g of DCC was used instead of 16.3 g, and 45.0 g of NMP solution of diamine oligomer W-6 and 14.7 g of MBAPP were used instead of 101.7 g of NMP solution of diamine oligomer W-2 and 2.4 g of m-TB. Otherwise, the reaction was carried out in the same manner as described in the synthesis method of polymer A-1, thereby obtaining polymer A-15. The weight-average molecular weight (Mw) of polymer A-15 is 28,000, and the imine group induction rate is 0.16. Furthermore, the amide group concentration U of each repeating unit of the polyamide obtained from polymer A-15 is 15.8 wt%.

[0164] Synthesis of Polymer A-16: In the synthesis method of polymer A-1 described above, 20.2 g of BPADA was used instead of 20.9 g, 10.5 g of HEMA was used instead of 10.9 g, 15.8 g of DCC was used instead of 16.3 g, and 70 g of NMP solution of diamine oligomer W-10 was used instead of 101.7 g of NMP solution of diamine oligomer W-2. Otherwise, the reaction was carried out in the same manner as described in the synthesis method of polymer A-1, thereby obtaining polymer A-16. The weight-average molecular weight (Mw) of polymer A-16 is 26,000, and the imide group induction rate is 0.44. Furthermore, the imide group concentration U of each repeating unit of the polyimide obtained from polymer A-16 is 21.1 wt%.

[0165] Synthesis of Polymer A-17: In the synthesis method of polymer A-2 described above, 13.9 g of glycerol dimethacrylate was used instead of 7.9 g of HEMA. Otherwise, the reaction was carried out in the same manner as described in the synthesis method of polymer A-2, thereby obtaining polymer A-17. The weight-average molecular weight (Mw) of polymer A-17 is 24,000, and the amide group induction rate is 0.58. Furthermore, the amide group concentration U of each repeating unit of the polyamide obtained from polymer A-17 is 20.1 wt%.

[0166] Synthesis of Polymer A-18: In the synthesis method of polymer A-2 described above, 7.8 g of 2-aminoethyl methacrylate was used instead of 7.9 g of HEMA. Otherwise, the reaction was carried out in the same manner as described in the synthesis method of polymer A-2, thereby obtaining polymer A-18. The weight-average molecular weight (Mw) of polymer A-18 is 24,000, and the amide group induction rate is 0.58. Furthermore, the amide group concentration U of each repeating unit of the polyamide obtained from polymer A-18 is 20.1 wt%.

[0167] Synthesis of Polymer A-19: In the synthesis method of polymer A-2 described above, 7.7 g of 2-hydroxybutyl methacrylate (HBMA) and 0.7 g of allyl alcohol were used instead of 7.9 g of HEMA. Otherwise, the reaction was carried out in the same manner as described in the synthesis method of polymer A-2, thereby obtaining polymer A-19. The weight-average molecular weight (Mw) of polymer A-19 is 24,000, and the amide group induction rate is 0.58. Furthermore, the amide group concentration U of each repeating unit of the polyamide obtained from polymer A-19 is 20.1 wt%.

[0168] Synthesis of polyimide precursor (polymer A-20): 60.2 g of ODPA (as an acid component) was added to a 1-liter separable flask, along with 54.2 g of HEMA and 137.5 g of GBL. 31.6 g of pyridine was added while stirring at room temperature to obtain the reaction mixture. After the exothermic reaction was complete, the mixture was allowed to cool to room temperature and then allowed to stand for 16 hours.

[0169] Subsequently, under ice bath cooling, while stirring, a solution obtained by dissolving 81.3 g of DCC in 81.3 g of GBL was added to the reaction mixture over 40 minutes. Then, while stirring, a solution obtained by dissolving 36.4 g of m-TB (a diamine component) in 109.2 g of GBL was added over 60 minutes. After stirring at room temperature for 2.5 hours, 15 g of ethanol was added and stirring for 30 minutes, followed by the addition of 150 g of γ-butyrolactone, and stirring at 50°C for 0.5 hours. The precipitate formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0170] The obtained reaction solution was added to 2700 g of ethanol to generate a precipitate containing crude polymer. The crude polymer was filtered off and dissolved in 1000 g of γ-butyrolactone to obtain a crude polymer solution. The crude polymer solution was purified using an anion exchange resin (Amberlyst TM15 manufactured by Organo Corporation) to obtain a polymer solution. The obtained polymer solution was added dropwise to 8000 g of water to precipitate the polymer. The precipitate was filtered off and then vacuum dried to obtain polymer A-20 in powder form. The weight average molecular weight (Mw) of polymer A-20 is 19,000, and the amide group content is 0. Furthermore, the amide group concentration U of each repeating unit of the polyamide obtained from polymer A-20 is 28.8 wt%.

[0171] Synthesis of polyimide precursor (polymer A-21): In the synthesis method of polymer A-20 described above, 63.3 g of BAPP was used instead of 36.4 g of m-TB. Otherwise, the reaction was carried out in the same manner as described in the synthesis method of polymer A-20, thereby obtaining polymer A-21. The weight-average molecular weight (Mw) of polymer A-21 is 21,000, and the amide group induction rate is 0. Furthermore, the amide group concentration U of each repeating unit of the polyamide obtained from polymer A-21 is 20.5 wt%.

[0172] Synthesis of polyimide precursor (polymer A-22): In the synthesis method of polymer A-20 described above, 58.8 g of BPDA was used instead of 62.0 g of ODPA, and 34.3 g of 4,4'-diaminodiphenyl ether (DADPE) was used instead of 36.4 g of m-TB. Otherwise, the reaction was carried out in the same manner as described in the synthesis method of polymer A-20, thereby obtaining polymer A-22. The weight-average molecular weight (Mw) of polymer A-22 is 22,000, and the amide group induction rate is 0. Furthermore, the amide group concentration U of each repeating unit of the polyamide obtained from polymer A-22 is 30.5 wt%.

[0173] Synthesis of polyimide precursor (polymer A-23): In the synthesis method of polymer A-20 described above, 81.3 g of BAPP was used instead of 36.4 g of m-TB. Otherwise, the reaction was carried out in the same manner as described in the synthesis method of polymer A-20, thereby obtaining polymer A-23. The weight-average molecular weight (Mw) of polymer A-23 is 16,000, and the amide group induction rate is 0. Furthermore, the amide group concentration U of each repeating unit of the polyamide obtained from polymer A-23 is 20.5 wt%.

[0174] Synthesis of polyimide (polymer A-24): Add 97.7 g of 6FDA (acid component), 64.1 g of TFMB (diamine component), and 529.2 g of N-methylpyrrolidone (NMP) (solvent component) to a 1-liter separable flask equipped with a Dean-Stark tube and a condenser, and dissolve them simultaneously with stirring. Then, add 126.9 g of toluene and stir, then heat to 185°C under a nitrogen atmosphere. After stirring at 185°C for 2.5 hours, remove the toluene and water generated by amide imidization from the system over a period of 1.5 hours. Finally, cool to room temperature to obtain a polyamide solution. The obtained polyimide solution was added to 1000 g of methanol to generate a precipitate containing crude polymer. The crude polymer was filtered off and washed again with methanol. The washed polymer was vacuum dried at 50°C to obtain polymer A-24 in powder form. The weight average molecular weight (Mw) of polymer A-24 was 25,000. 1H-NMR analysis of polymer A-24 was performed, comparing the peaks of polyimide derived from amide bonds with those derived from aromatic rings to confirm the amide ring-closure rate. The amide ring-closure rate was ≥99%. Furthermore, the amide group concentration U of each repeating unit of the polyimide obtained from polymer A-24 was 19.2 wt%.

[0175] <Ingredients (B)~(G)> Photopolymerization initiator B1: 3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]acetone-1-(O-acetylgoxime) (trade name: PBG-304, manufactured by Changzhou Qiangli Electronics Co., Ltd.) Photopolymerization initiator B2: 1,2-propanedione-3-cyclopentyl-1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime) (trade name: PBG-305, manufactured by Changzhou Qiangli Electronics Co., Ltd.) Photopolymerization initiator B3: 1-[4-(phenylthio)phenyl]-3-propane-1,2-dione-2-(O-acetylgoxime) (trade name: PBG-3057, manufactured by Changzhou Qiangli Electronics Co., Ltd.) Solvent C1: γ-Butyrolactone Solvent C2: Dimethyl sulfoxide (DMSO) Solvent C3: 3-Methoxy-N,N-Dimethylpropionic acid Silane coupling agent D-1: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) Silane coupling agent D-2: N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) Silane coupling agent D-3: Tributyl carbamate (3-triethoxysilylpropyl) tert-butyl ester Silane coupling agent D-4: Uretopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) Silane coupling agent D-5:X-12-1214A (manufactured by Shin-Etsu Chemical Co., Ltd., trade name) Silane coupling agent D-6: Tris(trimethoxysilylpropyl) isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd.) E-1:1,6-Hexanediol dimethacrylate, a free radical polymerizable compound (manufactured by Shin-Nakamura Chemical Co., Ltd.) Free radical polymerizable compound E-2: pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) Free radical polymerizable compound E-3: (PO (Propylene Oxide) modified) trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) Free radical polymerizable compound E-4: dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) Thermal crosslinking agent F-1: Bismaleimide compound (manufactured by Daiwa Chemical Industries, Ltd., BMI-5100) Thermal crosslinking agent F-2: Block isocyanate (manufactured by Asahi Kasei Corporation, SBB70P) Thermal crosslinking agent F-3: An alkoxymethyl compound with the following structure (manufactured by Daito Chemix, CROLIN-318). Filler G-1: Spherical silica (manufactured by Admatechs, K180SP-CY1)

[0176] <Example 1> As shown in Table 3, 100 g of polymer A-1 (component A) and 7 g of photopolymerization initiator B-1 (component B) were dissolved in a mixed solvent (weight ratio 90:10) containing γ-butyrolactone and DMSO (solvent C) to prepare a photosensitive resin composition solution. The composition was evaluated using the above method.

[0177] <Examples 2-37, Comparative Examples 1-9> Except that the types and amounts of the components were adjusted to the ratios described in Tables 3-6, a photosensitive resin composition solution was prepared using the same method as in Example 1, and then evaluated. Only in Comparative Example 8 was the prepared photosensitive resin composition solution left to stand at 40°C for 240 hours. Using the stood photosensitive resin composition, the amide content as the photosensitive resin composition layer was measured using the method described above for determining the amide structure introduction rate, and the result was 0.45. The characteristics and evaluation results are shown in Tables 7-10.

[0178] [Table 1] Table 1. diamine oligomers a:acid b: amine a / b (Morby) terminal monomers Mw W-1 BPADA m-TB 1 / 2 amine 3,000 W-2 BPADA MBAPP 2 / 3 amine 5,000 W-3 ODPA BAPP 1 / 2 amine 2,700 W-4 ODPA MBAPP 1 / 2 amine 3,000 W-5 ODPA X-1 1 / 2 amine 3,500 W-6 BPADA BAFL 1 / 2 amine 2,900 W-7 BPADA BAFL 3 / 4 amine 8,200 W-8 ODPA TFMB 1 / 2 amine 2,500 W-9 6FDA BAPP 1 / 2 amine 3,200 W-10 BPADA 1,10-Diaminodecane 2 / 3 amine 3,700

[0179] [Table 2] Table 2. (A) copolymer A:Acid B: Amine A / B (Morby) terminal monomers Mw Imine structure infusion rate Imino concentration U (wt%) Photosensitive group (first substituent introduced into the compound) Terminal modifiers (compounds with second substituents) terminal photosensitive group End structure A-1 BPADA m-TB W-2 5 / 4 acid 30,000 0.43 16.0 HEMA - - - A-2 BPADA W-1 6 / 7 amine 24,000 0.58 20.1 HEMA - - - A-3 BPADA W-1 6 / 7 amine 18,000 0.58 20.1 HEMA 2-Isocyanate Ethyl Methacrylate methacrylate Urea bond A-4 BPADA W-2 5 / 4 acid 35,000 0.53 15.2 HEMA - - - A-5 ODPA W-3 4 / 5 amine 22,000 0.63 20.5 HEMA - - - A-6 ODPA W-4 4 / 5 amine 23,000 0.63 19.6 HEMA - - - A-7 ODPA W-5 7 / 6 acid 21,000 0.43 16.7 HEMA - - - A-8 ODPA W-5 7 / 6 acid 19,000 0.43 16.7 HEMA Allylamine Allyl aceimine bond A-9 BPADA W-6 7 / 6 acid 29,000 0.43 16.8 HEMA - - - A-10 BPADA W-7 6 / 7 amine 40,000 0.88 16.8 HEMA - - - A-11 BPADA W-7 6 / 7 amine 36,000 0.88 16.8 HEMA methacrylic acid chloride methacrylate amide bond A-12 ODPA W-8 9 / 8 acid 26,000 0.58 23.6 HEMA - - - A-13 6FDA W-9 9 / 8 acid 28,000 0.44 17.1 HEMA - - - A-14 BPDA W-4 4 / 5 amine 21,000 0.63 19.8 HEMA - - - A-15 BPADA MBAPP W-6 5 / 4 acid 28,000 0.16 15.8 HEMA - - - A-16 BPADA m-TB W-10 6 / 5 acid 26,000 0.44 21.1 HEMA - - - A-17 BPADA W-1 6 / 7 amine 24,000 0.58 20.1 Glyceryl dimethacrylate - - - A-18 BPADA W-1 6 / 7 amine 24,000 0.58 20.1 2-Aminoethyl methacrylate - - - A-19 BPADA W-1 6 / 7 amine 24,000 0.58 20.1 HBMA allyl alcohol - - - A-20 ODPA m-TB 7 / 6 acid 19,000 0 28.8 HEMA - - - A-21 ODPA BAPP 7 / 6 acid 21,000 0 [[ID=4)]] 20.5 HEMA - - - A-22 BPDA DADPE 7 / 6 acid 22,000 0 30.5 HEMA - - - A-23 ODPA BAPP 6 / 7 amine 16,000 0 <( 20.5 HEMA - - - A-24 6FDA TFMB 11 / 10 acid 25,000 1 19.2 - - - -

[0180] [Table 3] Table 3. Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 (A) Polyimide precursor (g) A-1 100 100 A-2 100 100 100 A-3 100 100 A-4 100 A-5 100 A-6 100 A-7 100 (B) Photopolymerization initiator (g) B-1 7 B-2 7 B-3 7 7 6 7 7 7 8 8 7 (C) Solvent (g) C-1 270 324 324 324 270 324 324 324 324 324 270 C-2 30 36 36 36 30 36 36 36 36 36 30 (D) Sealing aid (g) D-1 2 2 2 2 2 2 2 2 (E) Free radical polymerizable compounds (g) E-1 10 10 10 10 10 10 10 Resolution C B B B A A A C B A B Dk(10 GHz) 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 3.0 2.9 3.1 [[ID=-66]] Df(10 GHz) 0.0047 0.0046 0.0047 0.0045 0.0054 0.0053 0.0055 0.0049 0.0090 0.0054 0.0071 Dk(40 GHz) 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 3.0 2.9 3.1 Df(40 GHz) 0.0055 0.0054 0.0056 0.0053 0.0064 0.0062 0.0064 0.0058 0.0098 0.0063 0.0080 Post-curing residual film rate: RFA(%) 84 81 83 81 88 86 87 90 87 88 88 Copper adhesion A A <00​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ 149.1 151.6 138.4 139.5 136.7 155.7 89.2 139.9 110.3

[0181] [Table 4] Table 4. Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 (A) Polyimide precursor (g) A-8 100 A-9 100 A-10 100 A-11 100 A-12 100 A-13 100 A-14 100 A-15 100 A-16 100 A-17 100 A-18 100 A-19 (B) Photopolymerization initiator (g) B-3 7 7 10 10 7 7 8 3 7 6 7 (C) Solvent (g) C-1 270 324 360 360 324 324 324 270 324 C-2 30 36 40 40 36 36 36 30 36 C-3 480 360 (D) Sealing aid (g) D-1 2 2 2 2 2 2 2 2 2 2 2 (E) Free radical polymerizable compounds (g) E-1 10 10 10 10 10 10 10 10 10 10 10 E-2 Resolution B B C C B B A A A A A Dk(10 GHz) 3.0 2.9 2.9 2.9 2.8 2.7 3.1 2.9 ​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​2.9 Df(40 GHz) 0.0078 0.0104 0.0092 0.0096 0.0099 0.0102 0.0064 0.0076 0.0052 0.0052 0.0052 Residual film rate after curing: RFA (%) 87 89 92 93 85 87 87 90 87 88 87 Copper tightness A B A A A A A A A A A Preservation stability B B B B B B B B A A A RFA / tanδ 40 112.1 85.9 99.5 97.3 86.3 85.5 136.5 117.8 117.8 117.8 117.8

[0182] [Table 5] Table 5. Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 Example 31 Example 32 Example 33 Example 34 Example 35 Example 36 Example 37 (A) Polyimide precursor (g) A-1 100 100 100 100 100 100 100 100 100 100 100 100 100 100 A-19 100 (B) Photopolymerization initiator (g) B-1 5 B-2 5 B-3 8 5 5 5 5 5 5 5 5 5 5 5 5 (C) Solvent (g) C-1 324 324 324 324 324 324 324 324 324 324 324 324 324 324 C-2 36 36 36 36 36 36 36 36 36 36 36 36 36 36 C-3 360 (D) Sealing aid (g) D-1 2 2 2 2 2 2 2 2 2 2 D-2 2 D-3 2 D-4 2 D-5 2 D-6 2 (E) Free radical polymerizable compounds (g) E-1 10 10 E-2 10 10 10 10 10 10 10 10 10 10 10 E-3 10 (F) Thermal crosslinking agent (g) F-1 10 F-2 10 10 10 F-3 5 (G)Storage(g) G-1 5 Connection B A A A A A A A A A A A A A C Dk(10 GHz) 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 Df(10 GHz) 0.0059 0.0053 0.0053 0.0064 0.0072 0.0064 0.0064 0.0064 0.0064 0.0069 0.0075 0.0048 0.0051 0.0072 0.0045 Dk(40 GHz) 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 Df(40 GHz) 0.0059 0.0062 0.0062 0.0074 0.0083 0.0074 0.0074 0.0074 0.0074 0.0080 0.0086 0.0055 0.0059 0.0081 0.0052 Residual film rate after curing: RFA (%) 85 85 86 88 88 88 87 87 87 88 91 89 84 89 91 Copper tightness A A A B B A A A A B B B A B B Preservation stability A A A A A A A B A B A A A A C RFA / tanδ 40 117.8 137.9 139.5 119.0 105.8 119.0 117.6 117.6 117.6 109.8 105.5 160.4 143.4 117.8 173.7

[0183] [Table 6] Table 6. Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 (A) Polyimide precursor (g) A-20 100 A-21 100 100 100 50 100 A-22 100 A-23 100 A-24 50 100 (B) Photopolymerization initiator (g) B-1 5 5 5 5 5 5 5 5 (C) Solvent (g) C-1 180 180 180 180 180 180 324 324 324 C-2 20 20 20 20 20 20 36 36 36 (D) Sealing aid (g) D-1 2 2 2 2 2 2 2 2 (E) Free radical polymerizable compounds (g) E-1 10 10 10 10 10 E-2 10 10 E-4 80 (F) Thermal crosslinking agent (g) F-2 10 resolution A A D C A A - D C Dk(10 GHz) 3.1 3.0 3.2 3.0 3.0 3.0 2.9 3.0 2.6 Df(10 GHz) 0.0140 0.012 0.018 0.011 0.0144 0.0138 0.011 0.0086 0.0134 Dk (40 GHz) 3.0 3.0 3.1 3.0 3.0 3.0 2.9 3.0 2.6 Df(40 GHz) 0.0160 0.013 0.022 0.012 0.0156 0.0150 0.012 0.0093 0.0220 Residual film rate after curing: RFA (%) 72 81 69 81 83 84 85 77 97 Copper tightness B B C B C D C B D Preservation stability B A C B A A C B C RFA / tanδ 40 45.0 62.3 31.4 67.5 53.2 56.2 70.8 83.1 44.1

[0184] As shown in Tables 1-10, in the embodiments, by introducing polyimide block structures at a specific ratio, a photosensitive resin composition with low dielectric properties, low curing shrinkage, and good storage stability can be provided. Phase separation during coating is reduced, and a high-resolution, high-copper-adhesion hardened embossed pattern can be formed. On the other hand, in Comparative Examples 1-6, which do not have a polyimide structure, the result is a higher dielectric loss factor and a lower residual film rate after curing. In Comparative Example 7, where polyimide is incorporated into a polyimide precursor with a polyimide group incorporation rate of 0, the compatibility is poor, and uniform coating is not possible, making resolution evaluation difficult. Furthermore, it is believed that phase separation leads to a higher dielectric loss factor and lower copper adhesion. In Comparative Example 8, which used a partially amide-modified polyamide precursor, although the dielectric loss factor was low, amide modification was difficult to control, resulting in a cloudy film and poor resolution after coating. In Comparative Example 9, which used 100% amide polymer, free radical polymerizable monomers were required for patterning. Although the residual film yield after curing was high, the dielectric loss factor was high and the resolution was low. These results indicate that satisfactory results were not obtained in any of the comparative examples. [Industrial Applicability]

[0185] The photosensitive resin composition of the present invention can be preferably used, for example, in the field of photosensitive materials useful for the manufacture of electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

1. A photosensitive resin composition comprising: (A) 100 parts by weight of a copolymer resin containing polyimide and a polyimide precursor; (B) 0.5 to 30 parts by weight of a photopolymerization initiator; and (C) 100 to 1000 parts by weight of a solvent; wherein the copolymer resin containing polyimide and a polyimide precursor has a structure represented by the following general formula (1). In the above formula (1), X1, X2, and X3 are independently tetravalent organic groups with 6 to 40 carbon atoms, Y1 and Y2 are independently divalent organic groups with 6 to 40 carbon atoms, n1 is an integer from 2 to 30, n2 and n3 are independently integers from 2 to 150, Z3, Z4, Z5, and Z6 are independently monovalent organic groups, and at least one of Z3, Z4, Z5, and Z6 is a photopolymerizable functional group containing reactive unsaturated bonds that are polymerized by light. The above copolymer resin containing polyimide and polyimide precursor satisfies 0.10 < n2 / (n2 + n3) < 0.

90. The structure represented by the above general formula (1) satisfies at least one of the following (a) to (c): (a) X1, X2, and X3 contain the structure represented by the following general formula (4). (In formula (4), R8 and R9 are organic groups with 1 to 10 carbon atoms, m2 and m3 are integers selected from 0 to 4, satisfying m2 + m3 ≥ 1, and Z1 is selected from any of the following groups: free single bonds, organic groups with 1 to 30 carbon atoms, and organic groups containing heteroatoms. *The two in the formula refer to the groups bonded to the main chain of the resin, and the other two refer to the groups bonded to the side chains in the above general formula (1). (b) Y1 and / or Y2 contain the structure represented by the following general formula (7), (In formula (7), R8 and R9 are organic groups with 1 to 10 carbon atoms, m2 and m3 are integers selected from 0 to 4, satisfying m2 + m3 ≥ 1, and Z1 is selected from the following groups: free single bonds, organic groups with 1 to 30 carbon atoms, and organic groups containing heteroatoms. *The two in the formula refer to the groups bonded to the main chain of the resin.) (c)Y1 and / or Y2 contain structures derived from diamines having an aliphatic chain having 6 to 20 carbon atoms.

2. The photosensitive resin composition of claim 1, wherein the photopolymerizable functional group comprises the structure represented by the following general formula (2), (in formula (2), R5, R6 and R7 are each independently hydrogen atoms or monovalent organic groups having 1 to 3 carbon atoms, and m1 is an integer from 2 to 10).

3. The photosensitive resin composition of claim 1 or 2, wherein the above n2 / (n2+n3) satisfies 0.40 < n2 / (n2+n3) < 0.

90.

4. The photosensitive resin composition of claim 1 or 2, wherein the copolymer resin comprising polyimide and polyimide precursor of (A) above is free of halogen atoms.

5. The photosensitive resin composition of claim 1 or 2, wherein the polyimide in the polyimide of the polyimide curing film obtained by heating and curing the photosensitive resin composition at 350°C has a polyimide concentration U of 12 wt% to 26 wt% as the ratio of the molecular weight of the amide group to the molecular weight of the repeating unit comprising a structure derived from tetracarboxylic dianhydride and diamine.

6. The photosensitive resin composition of claim 1 or 2, wherein the copolymer resin comprising polyimide and polyimide precursor has a reactive substituent at the resin end that is polymerizable by heat or light, different from the photopolymerizable functional group contained in the repeating unit.

7. The photosensitive resin composition of claim 1 or 2, further comprising (D) a silane coupling agent.

8. The photosensitive resin composition of claim 1 or 2, further comprising (E) a free radical polymerizable compound.

9. The photosensitive resin composition of claim 1 or 2, further comprising (F) a thermal crosslinking agent.

10. The photosensitive resin composition of claim 1 or 2, further comprising (G) filler.

11. A method for manufacturing a polyimide curable film, comprising the following steps (1) to (5): (1) coating a photosensitive resin composition as claimed in claim 1 or 2 onto a substrate to form a photosensitive resin layer on the substrate; (2) heating and drying the obtained photosensitive resin layer; (3) exposing the heated and dried photosensitive resin layer; (4) developing the exposed photosensitive resin layer; and (5) heating the developed photosensitive resin layer to form a polyimide curable film.

12. A method for manufacturing a hardened film, comprising coating a resin composition as claimed in claim 1 or 2 onto a substrate, subjecting it to exposure treatment, development treatment, and then heat treatment to obtain a hardened film, wherein the dielectric loss factor of the hardened film measured at 40 GHz by the perturbation split cylinder resonator method is 0.003 to 0.

011.

13. A method for manufacturing a copolymer resin comprising polyimide and a polyimide precursor, wherein the copolymer resin comprising polyimide and a polyimide precursor has a structure represented by the following general formula (1), wherein in the above formula (1), X1, X2 and X3 are independently tetravalent organic groups having 6 to 40 carbon atoms, Y1 and Y2 are independently divalent organic groups having 6 to 40 carbon atoms, n1 is an integer from 2 to 30, n2 and n3 are independently integers from 2 to 150, Z3, Z4, Z5 and Z6 are independently monovalent organic groups, and at least one of Z3, Z4, Z5 and Z6 is a photopolymerizable functional group comprising a reactive unsaturated bond that polymerizes by light. The copolymer resin containing polyimide and polyimide precursor satisfies 0.10 < n2 / (n2 + n3) < 0.90, and the structure represented by the above general formula (1) satisfies at least one of (a) to (c) below: (a) X1, X2 and X3 contain the structure represented by the following general formula (4), (in formula (4), R8 and R9 are independently organic groups with 1 to 10 carbon atoms, m2 and m3 are integers selected from 0 to 4, satisfying m2 + m3 ≥ 1, Z1 is selected from any of the group consisting of single bonds, organic groups with 1 to 30 carbon atoms, and organic groups containing heteroatoms, * two of which mean bonded to the main chain of the resin, and the other two mean bonded to the side chain in the above general formula (1)), (b) Y1 and / or Y2 contain the structure represented by the following general formula (7), (In formula (7), R8 and R9 are organic groups with 1 to 10 carbon atoms, m2 and m3 are integers selected from 0 to 4, satisfying m2 + m3 ≧ 1, Z1 is selected from the group consisting of single bonds, organic groups with 1 to 30 carbon atoms, and organic groups containing heteroatoms, * means bonded to the main chain of the resin), (c) Y1 and / or Y2 contain a structure derived from a diamine with an aliphatic chain having 6 to 20 carbon atoms. The above method includes the following steps: (i) condensing the first tetracarboxylic acid dianhydride or its acid / substituent adduct with the first diamine compound to perform amide imidization, thereby obtaining a diamine oligomer with repeating units having a polyamide structure; (ii) A polyimide-amide precursor moiety having a polyimide block moiety is synthesized by reacting the above-mentioned diamine oligomer with a second tetracarboxylic dianhydride or its acid / substituent adduct. (iii) A polyimide-amide precursor moiety is synthesized by reacting the above-mentioned polyimide-amide precursor moiety with a third tetracarboxylic dianhydride or its acid / substituent adduct and a second diamine compound. The first tetracarboxylic dianhydride, the second tetracarboxylic dianhydride and the third tetracarboxylic dianhydride may be the same or different from each other. At least one of the second tetracarboxylic dianhydride and the third tetracarboxylic dianhydride is in the form of an acid / substituent adduct with a photopolymerizable functional group. The first diamine compound and the second diamine compound may be the same or different from each other.

14. A method for manufacturing a photosensitive resin composition, comprising: The steps of manufacturing a copolymer resin comprising polyimide and a polyimide precursor by the method of claim 13; and the steps of mixing (A) 100 parts by weight of the above copolymer resin comprising polyimide and a polyimide precursor, (B) 0.5 to 30 parts by weight of a photopolymerization initiator, and (C) 100 to 1000 parts by weight of a solvent to obtain a photosensitive resin composition.

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