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

Abstract

According to the present invention, provided are: a photosensitive resin composition which has low dielectric properties, low curing shrinkage, good storage stability, reduced phase separation during application, and which is capable of forming a cured relief pattern having high resolution and high copper adhesion; a method for producing a cured polyimide film using the photosensitive resin composition; and a cured polyimide film. This photosensitive resin composition contains 100 parts by mass of a copolymer resin containing a polyimide and a polyimide precursor, 0.5-30 parts by mass of a photopolymerization initiator, and 100-1000 parts by mass of a solvent. The copolymer resin has a polyimide block portion having a specific structure and a polyimide precursor block portion, and the copolymer resin containing the polyimide and the polyimide precursor satisfies 0.10 < n2 / (n2 + n3) < 0.90.

Description

Technical Field

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

[0002] In the past, for insulating materials of electronic components, and passivation films, surface protection films, interlayer insulating films, etc. of semiconductor devices, polyimide resins, polybenzoxazole resins, phenolic resins, etc. with excellent heat resistance, electrical properties and mechanical properties were used. Among these resins, the material provided in the form of a photosensitive resin composition can be easily formed into a heat-resistant relief pattern film by coating, exposure, development, and closed-loop treatment (imidization, benzoxazoleization) or thermal crosslinking of the composition. This kind of photosensitive resin composition has the feature of greatly shortening the process compared to previous non-photosensitive materials, and is used for the production of semiconductor devices.

[0003] However, semiconductor devices (hereinafter also referred to as "components") are mounted on printed circuit boards by various methods depending on the purpose. In the past, components were usually made by wire bonding, which is a method of connecting wires from the external terminals (pads) of the component to the lead frame. However, as components are becoming faster and faster and the operating frequency has reached GHz, the difference in the wiring length of each terminal during installation has affected the operation of the component. Therefore, in the installation of components for high-end applications, it is necessary to accurately control the length of the installation wiring, and wire bonding is difficult to meet this requirement.

[0004] Therefore, a flip chip installation is proposed, which is to form a redistribution layer on the surface of a semiconductor chip and form bumps (electrodes) thereon, and then the chip is turned upside down (flipped) and directly installed on a printed circuit board. Since the flip chip installation can accurately control the wiring distance, it is used for high-end components that process high-speed signals, or, because the installation size is small, it is used in mobile phones, etc., and the demand is rapidly expanding. Furthermore, a semiconductor chip installation technology called fan-out wafer-level packaging (FOWLP) has recently been proposed, which is to cut the wafer that has completed the previous process to manufacture a single chip, reconstruct the single chip on a support body and seal it with a molded resin, and form a redistribution layer after the support body is peeled off (for example, Patent Document 1). In the fan-out wafer-level packaging, the redistribution layer is formed with a thinner film thickness, so it has the advantages of being able to make the package highly thin, and achieving high-speed transmission and low cost.

[0005] In recent years, with the significant increase in the amount of information communication, it is necessary to seek higher-speed communication than the previous level, and it is necessary to shift to the fifth generation communication (5G) using a frequency of more than 3GHz, or the communication in the ultra-high frequency band of the quasi-millimeter wave band (20GHz to 30GHz) to the millimeter wave band (30GHz and above) which is easy to ensure a wider bandwidth. Not only in the printed circuit board, but also in the semiconductor chip mounted on the substrate, it is required to cope with high frequency. Therefore, in order to reduce the transmission loss, a packaged antenna (AiP) has been developed that integrates the front-end module (FEM) for transmitting and receiving radio waves with the antenna (for example, refer to the following patent document 2). In AiP, the wiring length is short, so the transmission loss that increases in proportion to the wiring length can be suppressed, but as the communication frequency band increases, low dielectric properties are required for the rewiring material. In addition, AiP requires a multi-layer rewiring layer like the previous FOWLP, so the flattening of the rewiring layer is also required.

[0006] As a method for solving the above-mentioned problem, in order to reduce the transmission loss under the high frequency band, it is considered that there are two methods of reducing dielectric loss and reducing conductor loss. Regarding the former, low dielectric properties (low dielectric loss tangent, low dielectric constant) are required for the photosensitive resin composition, and Patent Document 3, Patent Document 4, and Patent Document 5 are cited as examples. However, in Patent Document 3, since the measurement frequency is as low as 1GHz, it is not sufficient as the rewiring layer of AiP for high-frequency purposes. In Patent Document 4, since the polyimide precursor resin is blended with the polyimide resin, there is concern about the storage stability of the photosensitive resin composition or the phase separation during coating. In Patent Document 5, a partially imidized polyimide precursor is prepared in the varnish by heating and aging a varnish containing a polyimide precursor resin. However, since it is difficult to control the imidization rate, there are problems with the uniformity during spin coating, and it is difficult to achieve high resolution.

[0007] As a method for flattening the redistribution layer, a method for suppressing the curing shrinkage of the redistribution layer is considered, and Patent Document 6 is cited as an example. In Patent Document 6, high flattening is achieved by using a multifunctional (meth)acrylate for a polyimide resin. However, there is no record about the dielectric properties, and there is concern that the dielectric properties may deteriorate at high frequencies due to the influence of a large amount of multifunctional (meth)acrylate.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Publication No. 2005-167191

[0011] Patent Document 2: U.S. Patent Application Publication No. 2016 / 0104940

[0012] Patent Document 3: International Publication No. 2019 / 044874

[0013] Patent Document 4: Taiwan Publication No. 2020 / 026762

[0014] Patent Document 5: Japanese Patent Application Publication No. 2022-54416

[0015] Patent Document 6: Japanese Patent Application Publication No. 2021-152634 Summary of the invention

[0016] Problem that the invention aims to solve

[0017] In recent years, the packaging installation technology has been diversified, and the types of supports have been diversified, and the rewiring layer has been multilayered. Therefore, the dielectric constant or dielectric loss tangent (tan δ) of the insulating material used to form the wiring has increased. In the case where the dielectric constant or dielectric loss tangent is high, the increase in dielectric loss will cause the transmission loss to increase. Polyimide resin has high material reliability due to its excellent insulation performance and thermomechanical properties. On the other hand, the influence of polar functional groups derived from imide groups, polar functional groups added for photosensitization, and additives, etc., will cause dielectric constants or dielectric loss tangents to be high, which is considered a problem. In addition, there is a situation where the multilayering of the rewiring layer causes problems with the flatness of the rewiring layer due to low curing shrinkage.

[0018] The object of the present invention is to provide a photosensitive resin composition having low dielectric properties, low curing shrinkage, good storage stability, reduced phase separation during coating, and capable of forming a cured relief pattern with high resolution and high copper adhesion, as well as a method for producing a polyimide cured film using the same and the polyimide cured film.

[0019] Solutions for solving problems

[0020] The following items [1] to

[16] are listed as examples of embodiments of the present invention. [1]

[0022] A photosensitive resin composition, comprising:

[0023] (A) 100 parts by mass of a copolymer resin comprising polyimide and a polyimide precursor;

[0024] (B) 0.5 to 30 parts by mass of a photopolymerization initiator; and

[0025] (C) 100 to 1000 parts by mass of a solvent, and

[0026] The copolymer resin comprising polyimide and polyimide precursor has a structure represented by the following general formula (1):

[0027]

[0028] In the above formula (1), X1, X2 and X3 are each independently a tetravalent organic group having 6 to 40 carbon atoms, Y1 and Y2 are each independently a divalent organic group having 6 to 40 carbon atoms, n1 is an integer of 2 to 30, n2 and n3 are each independently an integer of 2 to 150, Z3, Z4, Z5 and Z6 are each independently a monovalent organic group, and at least one of Z3, Z4, Z5 and Z6 is a photopolymerizable functional group,

[0029] The copolymer resin including the polyimide and the polyimide precursor satisfies 0.10<n2 / (n2+n3)<0.90. [2]

[0031] The photosensitive resin composition according to item 1, wherein the photopolymerizable functional group includes a structure represented by the following general formula (2).

[0032]

[0033] (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.) [3]

[0035] The photosensitive resin composition according to item 1 or 2, wherein n2 / (n2+n3) satisfies 0.40<n2 / (n2+n3)<0.90. [4]

[0037] The photosensitive resin composition according to any one of items 1 to 3, wherein the copolymer resin (A) containing a polyimide and a polyimide precursor does not contain a halogen atom. [5]

[0039] The photosensitive resin composition according to any one of items 1 to 4, wherein in the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350° C., the ratio of the molecular weight of the imide group to the molecular weight of the repeating unit containing the structure derived from tetracarboxylic dianhydride and diamine, i.e., the imide group concentration U, is 12 wt % to 26 wt %. [6]

[0041] The photosensitive resin composition according to any one of items 1 to 5, wherein X1, X2 and X3 of the copolymer resin (A) comprising polyimide and a polyimide precursor comprise a structure represented by the following general formula (4),

[0042]

[0043] In formula (4), R8 and R9 are each independently an organic group having 1 to 10 carbon atoms, m2 and m3 are integers selected from 0 to 4, satisfying m2+m3≥1, Z1 is selected from any one of the group consisting of a single bond, an organic group having 1 to 30 carbon atoms, and an organic group containing a heteroatom, two of the * represent bonds bonded to the main chain of the resin, and the other two represent bonds bonded to the side chain in the above general formula (1); and / or,

[0044] Y1 and / or Y2 include a structure represented by the following general formula (7),

[0045]

[0046] In formula (7), R8 and R9 are each independently an organic group having 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 a single bond, an organic group having 1 to 30 carbon atoms, and an organic group containing a heteroatom, and * indicates bonding to the main chain of the resin. [7]

[0048] The photosensitive resin composition according to any one of items 1 to 6, wherein the copolymer resin (A) comprising a polyimide and a polyimide precursor has other reactive substituents polymerized by heat or light, different from the photopolymerizable functional groups contained in the repeating units, at the resin terminals. [8]

[0050] The photosensitive resin composition according to any one of items 1 to 7, further comprising (D) a silane coupling agent. [9]

[0052] The photosensitive resin composition according to any one of items 1 to 8, further comprising (E) a radical polymerizable compound.

[10]

[0054] The photosensitive resin composition according to any one of items 1 to 9, further comprising (F) a thermal crosslinking agent.

[11]

[0056] The photosensitive resin composition according to any one of items 1 to 10, further comprising (G) a filler.

[12]

[0058] A method for producing a polyimide cured film, comprising the following steps (1) to (5):

[0059] (1) a step of applying the photosensitive resin composition according to any one of items 1 to 11 onto a substrate to form a photosensitive resin layer on the substrate;

[0060] (2) a step of heating and drying the obtained photosensitive resin layer;

[0061] (3) exposing the heated and dried photosensitive resin layer to light;

[0062] (4) a step of developing the exposed photosensitive resin layer; and

[0063] (5) A step of heat-treating the developed photosensitive resin layer to form a polyimide cured film.

[13]

[0065] A method for producing a cured film, comprising applying the resin composition described in any one of items 1 to 11 onto a substrate, performing an exposure treatment, a development treatment, and then performing a heat treatment to obtain a cured film, wherein the dielectric loss tangent of the cured film measured at 40 GHz by a perturbation split cylindrical resonant cavity method is 0.003 to 0.011.

[14]

[0067] A polyimide cured film, wherein the dielectric loss tangent at a frequency of 40 GHz measured by a perturbation split cylindrical resonant cavity method is 0.003 to 0.011, the RFA is 0.81 to 0.93, and the film satisfies the following formula:

[0068] 85<RFA / tanδ 40 <175

[0069] {where RFA represents the residual film rate (ratio) after thermal curing, tanδ 40 It represents the dielectric loss tangent at a frequency of 40 GHz measured by the perturbation split cylindrical resonator method.}

[15]

[0071] A method for producing a copolymer, which is a method for producing a copolymer comprising polyimide and a polyimide precursor, the method comprising the following steps:

[0072] (i) subjecting a first tetracarboxylic dianhydride or its acid / substituent adduct to a condensation reaction with a first diamine compound to perform imidization, thereby obtaining a diamine oligomer having a repeating unit of a polyimide structure;

[0073] (ii) subjecting the diamine oligomer to a condensation reaction with a second tetracarboxylic dianhydride or an acid / substituent adduct thereof to synthesize a polyimide-imide precursor portion having a polyimide block portion; and

[0074] (iii) synthesizing a polyimide precursor by condensing the polyimide-imide precursor with a third tetracarboxylic dianhydride or an acid / substituent adduct thereof and a second diamine compound,

[0075] 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 having a photopolymerizable functional group, and the first diamine compound and the second diamine compound may be the same or different from each other.

[16]

[0077] A method for producing a photosensitive resin composition, comprising:

[0078] Producing a copolymer resin comprising polyimide and a polyimide precursor by the method described in item 15; and

[0079] A step of mixing (A) 100 parts by mass of the copolymer resin containing the polyimide and the polyimide precursor, (B) 0.5 to 30 parts by mass of a photopolymerization initiator, and (C) 100 to 1000 parts by mass of a solvent to obtain a photosensitive resin composition.

[0080] Effects of the Invention

[0081] According to the present invention, there can be provided a photosensitive resin composition having low dielectric properties, low curing shrinkage, good storage stability, reduced phase separation during coating, capable of forming a cured relief pattern with high resolution and high copper adhesion, and a method for producing a polyimide cured film using the same and a polyimide cured film. DETAILED DESCRIPTION

[0082] Hereinafter, embodiments of the present invention will be described in detail. In this specification, when there are multiple structures represented by the same symbol in the general formula in a molecule, as long as it is not specified otherwise, they are selected independently and may be the same or different from each other. In addition, the structures represented by the common symbol in different general formulas are also the same, as long as it is not specified otherwise, they are selected independently and may be the same or different from each other.

[0083] <Photosensitive resin composition>

[0084] The photosensitive resin composition of the present invention contains: (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 contain (D) a silane coupling agent, (E) a radical polymerizable compound, (F) a thermal crosslinking agent, (G) a filler, and other components in addition to the above components as needed.

[0085] (A) Copolymer resin containing polyimide and polyimide precursor

[0086] The copolymer resin containing a polyimide and a polyimide precursor (hereinafter, simply referred to as a "copolymer resin") preferably contains a structure represented by the following general formula (1).

[0087] General formula (1):

[0088]

[0089] In formula (1), X1, X2 and X3 are each independently a tetravalent organic group having 6 to 40 carbon atoms, and Y1 and Y2 are each independently a divalent organic group having 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 of 2 to 30. n2 and n3 are each independently an integer of 2 to 150. In the present invention, the unit of n1 in formula (1) is referred to as a "polyimide block portion", the unit of n2 is referred to as a "polyimide-imide precursor portion", and the unit of n3 is referred to as a "polyimide precursor portion". In formula (1), for the sake of simplicity, only one polyimide-imide precursor portion and one polyimide precursor portion are described, but the copolymer resin may have a plurality of polyimide-imide precursor portions and a plurality of polyimide precursor portions randomly.

[0090] In formula (1), Z3, Z4, Z5, and Z6 are independently monovalent organic groups, but at least one of them is a photopolymerizable functional group. The photopolymerizable functional group preferably includes a reactive unsaturated bond that is polymerized by light. Z3, Z4, Z5, and Z6 more preferably form an ester bond (hereinafter referred to as "ester bond type") or an amide bond (hereinafter referred to as "amide bond type") together with the carbonyl group (-C(=O)-) directly bonded thereto. When Z3, Z4, Z5, and Z6 are ester bond type side chains, they can be represented as R1O-, R2O-, R3O-, and R4O-, respectively, and when Z3, Z4, Z5, and Z6 are amide bond type side chains, they can be represented as R1NH-, R2NH-, R3NH-, and R4NH-, respectively. Z3, Z4, Z5, and Z6 may all be of ester bond type, may all be of amide bond type, or may be a combination of ester bond type and amide bond type.

[0091] 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, and examples thereof include at least one group selected from (meth)acryloyloxyalkyl, allyl, ethynyl, and styryl, among which (meth)acryloyloxyalkyl is more preferred. Z3, Z4, Z5, and Z6 are further preferably photopolymerizable functional groups represented by the following general formula (2).

[0092] General formula (2):

[0093]

[0094] 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, preferably methyl. R5 is preferably a hydrogen atom or a methyl group, and R6 and R7 are preferably hydrogen atoms or methyl groups, more preferably hydrogen atoms. m1 is preferably an integer of 2 to 5, 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).

[0095] In the copolymer resin containing polyimide and polyimide precursor, the ratio of the molar number of polyimide-imide precursor part (n2 unit) to the total molar number of polyimide-imide precursor part (n2 unit) and polyimide precursor part (n3 unit) (hereinafter also referred to as "imide structure introduction rate") satisfies 0.10<n2 / (n2+n3)<0.90. Thus, 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 relief pattern with high resolution.

[0096] By including the structure represented by the above-mentioned general formula (1), a cured film with good resolution of relief pattern and low dielectric properties and low curing shrinkage can be obtained. Although not subject to theoretical constraints, it is believed that by having a polyimide block portion (n1 unit) and a polyimide precursor structure (i.e., the imide precursor structure in the unit of n2 and n3) in the same molecule, and making the polyimide-imide precursor part exist at a specific ratio, the swelling of the exposure part is suppressed, and it is easy to ensure the contrast with the unexposed part, so the resolution of the relief pattern is improved. In addition, it is believed that since a part of the copolymer resin has a polyimide block portion, the detached part of the side chain structure during the closed loop is reduced, and thus, curing shrinkage is suppressed, and low dielectric properties can be shown. 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 a photosensitive resin composition solution (hereinafter, also referred to as "varnish"). It is believed that the storage stability of the varnish will not be impaired. On the other hand, when an imide structure is formed by heating a varnish containing a polyimide precursor resin, since a photosensitive group separated from the side chain structure remains in the varnish, the curing shrinkage becomes large.

[0097] Based on the viewpoints of resolution, low dielectric properties, and low curing shrinkage, the imide structure introduction rate is preferably 0.10 to 0.90. Based on the viewpoint of resolution, it is preferred that the imide structure introduction rate is low, and based on the viewpoints of low dielectric properties and low curing shrinkage, a high n2 / (n2+n3) is preferred. Therefore, the imide structure introduction rate is more preferably 0.20 to 0.90, further preferably 0.30 to 0.90, further preferably 0.40 to 0.90, particularly preferably 0.43 to 0.80, and particularly preferably 0.45 to 0.75.

[0098] From the viewpoints of resolution, low dielectric properties, and low cure shrinkage, the ratio of the copolymer resin represented by the general formula (1) relative to the total mass of the copolymer (A) comprising polyimide and a polyimide precursor is preferably 25 mass % or more, more preferably 35 mass % or more, further preferably 50 mass % or more, particularly preferably 75 mass % or more, particularly preferably 90 mass % or more, particularly preferably 95 mass % or more, and most preferably 100 mass %.

[0099] Based on the viewpoint of the photosensitivity and mechanical properties of the photosensitive resin composition, n2 in the above general formula (1) is preferably an integer of 3 to 100, and more preferably an integer of 5 to 70. Based on the viewpoint of photosensitivity and mechanical properties, n3 is preferably an integer of 3 to 100, and more preferably an integer of 5 to 70. Based on the viewpoint of coating properties and dielectric loss tangent, n1 is preferably an integer of 2 to 30, and more preferably an integer of 5 to 20. The larger n1 is, the higher the imide structure introduction rate is, and the better the dielectric loss tangent is. On the other hand, if n1 is too large, the coating properties will be impaired, so the balance is important.

[0100] In the above general formula (1), based on the consideration of both heat resistance and photosensitivity, the tetravalent organic groups represented by X1, X2 and X3 are preferably organic groups with 6 to 40 carbon atoms, and more preferably aromatic groups or alicyclic aliphatic groups in which -COOR1 and -COOR2 are ortho to -CONH-. As the tetravalent organic groups represented by X1, X2 and X3, specifically, organic groups with 6 to 40 carbon atoms containing aromatic rings can be listed, such as groups having a structure represented by the following general formula (3), but are not limited to these. The tetravalent organic groups represented by X1, X2 and X3 may be one kind or a combination of two or more kinds. The X1, X2 and X3 groups having a structure represented by the above formula (3) are particularly preferred in terms of both heat resistance and photosensitivity.

[0101]

[0102] {In formula (3), R 11 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 hydrocarbon group, and a C1-C10 fluorine-containing hydrocarbon group, m5 is an integer of 1 to 2, m6 is an integer of 1 to 3, and m7 is an integer of 1 to 4.}

[0103] From the viewpoint of resolution and low dielectric properties, X1, X2 and X3 in the above general formula (1) preferably include a structure represented by the following general formula (4).

[0104] General formula (4):

[0105]

[0106] {In the formula, R8 and R9 are independently an organic group having 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 one of the group consisting of a single bond, an organic group having 1 to 30 carbon atoms, and an organic group containing a heteroatom; two of the * represent bonds bonded to the main chain of the resin, and the other two represent 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)-).}

[0107]

[0108] {In the formula, Z2 is any one selected from the group consisting of a single bond, an organic group having 1 to 30 carbon atoms, and an organic group containing a heteroatom; two of the * represent bonds to the main chain of the resin, and the other two represent bonds to the side chain in the above general formula (1).}

[0109] The organic groups having 1 to 10 carbon atoms represented by R8 and R9 in the general formula (4) are preferably linear or branched alkyl groups. By introducing the alkyl group into the aromatic ring, the solubility of the copolymer resin (A) in the developer is improved, and the contrast with the exposed part is easily ensured, thereby improving the resolution of the relief pattern. In addition, by introducing the alkyl group into the aromatic ring, the polarizability is reduced, thereby achieving low dielectric properties.

[0110] From the viewpoint of chemical resistance, R8 and R9 in the general formula (4) are preferably organic groups having 1 to 4 carbon atoms, more preferably alkyl groups having 1 to 4 carbon atoms, for example, methyl, ethyl, propyl and butyl groups, and particularly preferably methyl groups.

[0111] In the above general formula (1), the structure represented by X1, X2 and X3 more preferably includes at least one structure selected from the group consisting of the following general formula (5). 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). The above structures may be one or a combination of two or more.

[0112] General formula (5):

[0113]

[0114] {Two of the * represent bonds to the main chain of the resin, and the other two represent bonds to the side chain in the above general formula (1).}

[0115] In the above general formula (1), the divalent organic groups represented by Y1 and Y2 are aliphatic chains (alkylene groups) having 6 to 40 carbon atoms, preferably 6 to 20 carbon atoms, such as heptylene, octylene, nonylene, decylene, and undecylene; and aromatic groups having 6 to 40 carbon atoms. In view of the balance between heat resistance and photosensitivity, aromatic groups are preferred, and aromatic groups having 6 to 40 carbon atoms are more preferred, such as groups having a structure represented by the following general formula (6), but not limited thereto. The divalent organic groups represented by Y1 and Y2 may be one or a combination of two or more. The Y1 and Y2 groups having the structure represented by the above formula (6) are particularly preferred in terms of balance between heat resistance and photosensitivity.

[0116]

[0117] {In formula (6), R 11 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 hydrocarbon group, and a C1-C10 fluorine-containing hydrocarbon group, m6 is an integer of 1 to 3, and m7 is an integer of 1 to 4.}

[0118] From the viewpoint of resolution and low dielectric properties, Y1 and / or Y2 in the above general formula (1) preferably includes a structure represented by the following general formula (7).

[0119] General formula (7):

[0120]

[0121] {In the formula, R8 and R9 are independently an organic group having 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 one of the group consisting of a single bond, an organic group having 1 to 30 carbon atoms, and an organic group containing a heteroatom; * indicates bonding to the main chain of the resin.}

[0122] The organic groups having 1 to 10 carbon atoms represented by R8 and R9 in the general formula (7) are preferably linear or branched alkyl groups. By introducing an alkyl group into the aromatic ring, the solubility of the copolymer resin (A) in the developer is improved, and the contrast with the exposed part is easily ensured, thereby improving the resolution of the relief pattern. In addition, by introducing an alkyl group into the aromatic ring, the polarizability is reduced, thereby achieving low dielectric properties.

[0123] From the viewpoint of chemical resistance, R8 and R9 in the 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 particularly preferably methyl. As an example of the general formula (7), it is preferred to include at least one structure selected from the group consisting of the following general formula (8).

[0124] General formula (8):

[0125]

[0126] *Indicates bonding to the main chain of the resin.

[0127] In the above general formula (1), the structures represented by Y1 and Y2 preferably include at least one structure selected from the group consisting of the following general formula (9).

[0128] General formula (9):

[0129]

[0130] * indicates bonding to the main chain of the resin. The structures of Y1 and Y2 in the general formula (1) are not limited to the structures listed in (6) to (9) above. The above structures may be one or a combination of two or more.

[0131] From the viewpoint of suppressing copper corrosion in the thermal curing step, it is preferred that at least one or all of X1, X2, X3, Y1, and Y2 in the general formula (1) contain no halogen atom. That is, the copolymer resin (A) more preferably contains no halogen atom.

[0132] In the (A) copolymer resin, it is preferred that at least any one of X1, X2 and X3 as the skeleton components derived from the tetracarboxylic acid compound and Y1 and Y2 as the skeleton components derived from the diamine compound has more than 2 benzene rings. More than 2 benzene rings can be bonded to each other directly or by means of divalent or more organic groups. The number of benzene rings can be more than 3 or more than 4, less than 6, less than 5 or less than 4, more preferably 4. It is further preferred that the sum of the carbon atoms of X1, X2 and X3 constituting the structure derived from the tetracarboxylic acid compound and Y1 and Y2 representing the structure derived from the diamine compound is greater than 39. By making the (A) copolymer resin have such a structure, there is a tendency to maintain the resolution of the negative photosensitive resin composition and achieve low dielectric properties in the obtained cured relief pattern.

[0133] In the photosensitive resin composition of the present invention, the imide group concentration U in the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition is 12wt% to 26wt%. In the specification of the present application, "imide group concentration U" refers to the ratio of the molecular weight of the imide group to the molecular weight of the repeating unit containing the structure derived from the tetracarboxylic dianhydride and the diamine compound in the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350°C. The reason for heating and curing at 350°C as a condition is that by using the state in which the (A) copolymer resin is imidized approximately 100% as a reference, the reference of the aliphatic hydrocarbon group concentration T becomes clear, and it is not intended to heat and cure the photosensitive resin composition at 350°C in actual use.

[0134] If the imide group concentration U is 12.0wt% or more, the resolution of the relief pattern tends to be good. The imide group concentration U is preferably 15wt% or more, and more preferably 17.5wt% or more. On the other hand, by making the imide group concentration U 26wt% or less, the dielectric loss tangent of the obtained polyimide cured film tends to be good. The imide group concentration U is more preferably 23.0wt% or less, and further preferably 20.5wt% or less.

[0135] The imide group concentration U in the repeating unit of the polyimide cured film is represented by the following formula (I) using the molecular weight of the tetracarboxylic dianhydride used when preparing the copolymer resin (A) and the molecular weight of the diamine compound. It should be noted that, when using more than two tetracarboxylic dianhydrides and / or diamine compounds, for example, when two tetracarboxylic dianhydrides and / or diamines are used for preparation, it is represented by the following formula (II). When using more than three tetracarboxylic dianhydrides and / or diamines, it is also obtained in the same way. When using tetracarboxylic acids and / or tetracarboxylic acid dichlorides as raw materials, the mass of the corresponding tetracarboxylic dianhydride is used for calculation.

[0136] 70.02×2 / [Mw(A)+Mw(B)-36]×100(I)

[0137] {In formula (I), Mw(A) represents the molecular weight of tetracarboxylic dianhydride, and Mw(B) represents the molecular weight of diamine.}

[0138] 70.02×2 / [Mw(A1)×a1+Mw(A2)×a2+Mw(B1)×b1+Mw(B2)×b2-36]×100(II)

[0139] {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.}

[0140] The copolymer resin (A) may also have other reactive substituents at the end of the main chain that are different from the photopolymerizable functional groups contained in the repeating units and that are cross-linked by heat or light. The reactive substituents at the end are preferably groups having reactive unsaturated bonds that can react with each other by heat or light and cross-link. The copolymer resin (A) preferably has at least one of the structures represented by the following general formulas (E1) and (E2) at the end of the main chain. By allowing the copolymer resin (A) to have these reactive substituents at the end of the main chain, a high-resolution negative photosensitive resin composition with further improved residual film rate after curing or dielectric properties can be obtained.

[0141] General formula (E1):

[0142]

[0143] In formula (E1), a1 includes at least one of an amide bond, an imide bond, a urea bond, and a urethane bond, b1 is a reactive substituent that undergoes crosslinking by heat or light, and e1 is a monovalent organic group having 1 to 30 carbon atoms. 12 , R 15 are each independently a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, R 13 , R 14 are each independently a hydrogen atom, a monovalent or divalent organic group having 1 to 30 carbon atoms, or a part of an aromatic ring or an aliphatic ring. 13 With R 14 are not hydrogen atoms at the same time, and R 13 and / or R 14 Connected to the main chain structure.

[0144] General formula (E2):

[0145]

[0146] In formula (E2), f1 includes at least one of an amide bond, an imide bond, a urea bond, a urethane bond, and an ester bond, g1 is a reactive substituent that is cross-linked by heat or light, and R 16 ~R 20are independently a hydrogen atom, a monovalent or divalent organic group having 1 to 30 carbon atoms, or together form an aromatic ring or an aliphatic ring. 17 , R 18 , R 19 are not hydrogen atoms at the same time, and R 17 , R 18 and R 19 In view of the ease of cross-linking and the high chemical resistance due to the difficulty in hydrolysis, f1 preferably contains at least one of an amide group, an imide bond, a urea group and a urethane group.

[0147] The reactive substituent b1 that is cross-linked by heat or light is preferably selected from, for example, an acrylic group, a methacrylic group, a vinyl group, an alkenyl group, a cycloalkenyl group, an alkadienyl group, a cycloalkenyl group, a styryl group, an ethynyl group, an imino group, an isocyanate group, a cyanato group, a cycloalkyl group, an epoxy group, an oxetane group, a carbonate group, a hydroxyl group, a mercapto group, a hydroxymethyl group, and at least one of an alkoxyalkyl group. From the perspective of film thickness uniformity, b1 is preferably selected from at least one of an acrylic group, a methacrylic group, a vinyl group, an alkenyl group, a cycloalkenyl group, an alkadienyl group, a cycloalkenyl group, a styryl group, and an ethynyl group. A methacrylic group is particularly preferred.

[0148] The reactive substituent g1 that is cross-linked by heat or light is, for example, at least one selected from acrylic, methacrylic, vinyl, alkenyl, cycloalkenyl, alkadienyl, cycloalkadienyl, styryl, ethynyl, imino, isocyanate, cyanato, cycloalkyl, epoxy, oxetane, carbonate, hydroxyl, mercapto, methylol, and alkoxyalkyl. From the perspective of film thickness uniformity, g1 is preferably at least one selected from acrylic, methacrylic, vinyl, alkenyl, cycloalkenyl, alkadienyl, cycloalkadienyl, styryl, and ethynyl. g1 is particularly preferably methacrylic.

[0149] Specific examples of the compound having a reactive substituent that reacts by heat or light and having a site that also reacts with a carboxyl group, and the main chain terminal of the polyimide precursor modified by the reactive substituent are shown below.

[0150]

[0151] (A) Method for producing a copolymer comprising a polyimide and a polyimide precursor

[0152] The method for producing a copolymer comprising polyimide and a polyimide precursor of the present invention comprises the following steps:

[0153] (i) subjecting a first tetracarboxylic dianhydride or its acid / substituent adduct to a condensation reaction with a first diamine compound to perform imidization, thereby obtaining a diamine oligomer having a repeating unit of a polyimide structure;

[0154] (ii) synthesizing a polyimide-imide precursor portion having a polyimide block portion by condensing the diamine oligomer with a second tetracarboxylic dianhydride or an acid / substituent adduct thereof; and

[0155] (iii) synthesizing a polyimide precursor by subjecting the polyimide-imide precursor to a condensation reaction with a third tetracarboxylic dianhydride or an acid / substituent adduct thereof, 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 may be in the form of an acid / substituent adduct having a photopolymerizable functional group, and the first diamine compound and the second diamine compound may be the same or different from each other.

[0156] (Preparation of Acid / Substituent Adducts)

[0157] The first tetracarboxylic dianhydride, the second tetracarboxylic dianhydride and the third tetracarboxylic dianhydride used in steps (i), (ii) and (iii) may be in the form of an acid dianhydride, or may be in the form of an acid portion (HO-C(=O)-) and a substituent addition portion (ZC(=O)-, Z corresponds to Z3 to Z6 in the general formula (1)) obtained by adding a side chain substituent to the acid dianhydride in advance (also referred to as "acid / substituent adduct" in the present invention). Among them, at least one of the second tetracarboxylic dianhydride and the third tetracarboxylic dianhydride is in the form of an acid / substituent adduct having a photopolymerizable functional group. Z3, Z4, Z5, and Z6 may be of an ester bond type (hereinafter referred to as "acid / ester body") or an amide bond type (hereinafter referred to as "acid / amide body") as described above, and by using such an acid / ester body or an acid / amide body, an ester bond type or amide bond type polyimide precursor may be prepared. The tetracarboxylic dianhydride having a tetravalent organic group X1 having 6 to 40 carbon atoms which can be preferably used for preparing an ester bond type or amide bond type polyimide precursor is not limited except for the tetracarboxylic dianhydride derived from the above-mentioned structure, and examples thereof include pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenyl sulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, 4,4'-(4,4'-isopropylidene diphenyloxy) diphthalic anhydride, 4,4'-bis(3,4-dicarboxyphenoxy) benzophenone dianhydride, etc. Tetracarboxylic dianhydride may be used alone or in combination of two or more.

[0158] By using these tetracarboxylic dianhydrides containing a tetravalent organic group X1 having 6 to 40 carbon atoms and reacting them with a compound having a reactive substituent (photopolymerizable functional group) that reacts by light (also referred to as a "substituent-introducing compound" in the present invention), esterified or amidated tetracarboxylic acids (acid / ester or acid / amide) can be obtained. In addition, the above-mentioned substituent-introducing compound can also be used to introduce a reactive substituent into the terminal of the main chain of the copolymer (A). The reaction order varies depending on the introduction method.

[0159] As the substituent-introducing compound (also referred to as "first substituent-introducing compound" in the present invention) which can be preferably used for synthesizing the esterified tetracarboxylic acid (acid / ester), alcohols having a photopolymerizable functional group can be cited. As the alcohols having a photopolymerizable functional group, alcohols having a structure of the general formula (2) can be preferably cited, for example, 2-hydroxyethyl methacrylate (HEMA), 2-acryloyloxyethanol, 1-acryloyloxy-3-propanol, 2-acrylamideethanol, 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-tert-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethanol, 1-methacryloyloxy-3-propanol, 2-methacrylamideethanol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

[0160] As the saturated aliphatic alcohols which can be optionally used together with the alcohols having a photopolymerizable functional group, preferably saturated aliphatic alcohols having 1 to 4 carbon atoms are used. Specific examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and the like.

[0161] As the substituent-introducing compound (also referred to as "first substituent-introducing compound" in the present invention) which can be preferably used for synthesizing the amidated tetracarboxylic acid (acid / amide), amines having a photopolymerizable functional group can be cited. As the amines having a photopolymerizable functional group, amines having a structure of the general formula (2), such as 2-aminoethyl methacrylate, 2-aminoethyl acrylate, 2-(tert-butylamino)ethyl methacrylate, etc. can be preferably cited.

[0162] By mixing the above-mentioned tetracarboxylic dianhydride and the first substituent-introducing compound, preferably in the presence of a basic catalyst such as pyridine, preferably in an appropriate reaction solvent, and stirring at a temperature of 20 to 50° C. for 4 to 10 hours, addition of the substituent to the acid anhydride (for example, esterification or amidation reaction) can be carried out, thereby obtaining the desired acid / substituent addition product.

[0163] As the above-mentioned reaction solvent, it is preferred that the tetracarboxylic dianhydride and the first substituent introduction compound as raw materials, and the acid / substituent adduct as the product are completely dissolved in the solvent. More preferably, it is a solvent that completely dissolves the polyimide precursor as the amide polycondensation product of the acid / substituent adduct and the diamine. For example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, etc. As specific examples of these, as ketones, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. can be listed. As esters, for example, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, etc. can be listed. As lactones, for example, γ-butyrolactone, etc. can be listed. As ethers, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, etc. can be listed. Examples of halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, etc. Examples of hydrocarbons include hexane, heptane, benzene, toluene, xylene, etc. These may be used alone or in combination of two or more, as required.

[0164] (Preparation of diamine oligomer)

[0165] Step (i):

[0166] By imidizing the first tetracarboxylic dianhydride or its acid / substituent adduct with the first diamine compound through a condensation reaction, a diamine oligomer having a repeating unit of a polyimide structure can be obtained. Based on the viewpoint of increasing the imide ring closure rate, the first tetracarboxylic dianhydride used for the condensation reaction is preferably in the form of an acid dianhydride rather than an acid / substituent adduct. For example, the first tetracarboxylic dianhydride containing 6 to 40 4-valent organic groups X1 and an excess of the first diamine compound containing 6 to 40 carbon atoms can be condensed and heated to close the ring. There is no limitation on the conditions for imidization, for example, heating at a temperature of 160°C or more and 300°C or less for 1 to 10 hours is sufficient. The higher the imide ring closure rate, the more preferred it is, and there is no limitation, for example, it is 90% or more, preferably 95% or more, and more preferably 99% or more or 100%.

[0167] Regarding the first diamine compound having a divalent organic group Y1 having 6 to 40 carbon atoms as a raw material of a diamine oligomer having a polyimide structure, examples include diamines having an aliphatic chain (alkylene group) having 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 having 6 to 40 carbon atoms. Examples of the diamine having an aromatic group include, in addition to the diamines derived from the structures listed above, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl sulfone, 3,4'-diaminobiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl sulfone, 3,4'-diaminobiphenyl sulfone, 3,3'-diaminobiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl sulfone ... benzene, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4- Bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenyl)hexafluoropropane

[0043] The invention relates to diamine compounds, for example, hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, o-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, and bis{4-(4-aminophenoxy)phenyl}ketone, and those in which a part of the hydrogen atoms on the benzene rings thereof are substituted by alkyl chains such as methyl and ethyl, for example, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof. However, the diamine compound is not limited to these. These diamine compounds may be used alone or in combination of two or more thereof. These diamine compounds may also be used as the second diamine compound.

[0168] (Preparation of Copolymer Containing Polyimide and Polyimide Precursor)

[0169] Step (ii):

[0170] The diamine oligomer obtained by the above method can be used as a diamine, and a condensation reaction is carried out with the second tetracarboxylic dianhydride or its acid / substituent adduct to synthesize a polyimide-imide precursor part (n2 unit) having a polyimide block part (n1 unit). The second tetracarboxylic dianhydride is preferably in the form of an acid / substituent adduct having a photopolymerizable functional group. The acid / substituent adduct is typically in a solution state dissolved in a reaction solvent after the acid / substituent adduct is prepared by the above method. It is preferred to add and mix a suitable dehydration condensation agent under ice bath cooling to make the acid / substituent adduct a polyanhydride. Then, a solvent in which the diamine oligomer obtained by the above method is dissolved or dispersed is added dropwise thereto, and the two are subjected to amide polycondensation, thereby obtaining a polyimide-imide precursor part (n2 unit). Diaminosiloxanes can also be used in combination with the above-mentioned diamines having a divalent organic group Y1, which are raw materials for diamine oligomers having a polyimide structure. Examples of the dehydration condensation agent include dicyclohexylcarbodiimide (DCC), 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, and N,N′-disuccinimidyl carbonate. A polyanhydride as an intermediate is obtained in the above manner.

[0171] Step (iii):

[0172] The obtained polyimide-imide precursor part can be further subjected to a condensation reaction with the third tetracarboxylic dianhydride or its acid / substituent adduct, and the second diamine compound to synthesize the polyimide precursor part (unit of n3). When the second tetracarboxylic dianhydride (or its acid / substituent adduct) and the third tetracarboxylic dianhydride (or its acid / substituent adduct) are the same, the excess second tetracarboxylic dianhydride (or its acid / substituent adduct) present in the reaction solvent after the synthesis of the polyimide-imide precursor part can be directly used as the third tetracarboxylic dianhydride (or its acid / substituent adduct). The required tetracarboxylic dianhydride (or its acid / substituent adduct) can also be added to the system. When the first diamine compound and the second diamine compound are the same, the 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 required diamine compound can also be added to the system.

[0173] (Reactive resin end formation)

[0174] Different from the photopolymerizable functional group contained in the repeating unit of the copolymer (A), another reactive substituent that is polymerized by heat or light can be introduced into the terminal of the main chain by the following method.

[0175] (1) preparing an acid / substituent adduct having a photopolymerizable functional group and a reactive substituent by reacting a second tetracarboxylic dianhydride and / or a third tetracarboxylic dianhydride with a first substituent-introducing compound having a photopolymerizable functional group, and then reacting a second substituent-introducing compound having a reactive substituent that reacts by heat or light, which is different from the first substituent-introducing compound, or obtaining an acid / substituent adduct having a photopolymerizable functional group and a reactive substituent by reacting the second tetracarboxylic dianhydride and / or the third tetracarboxylic dianhydride with a second substituent-introducing compound, and then reacting the first substituent-introducing compound; and / or

[0176] (2) preparing a diamine oligomer having a second reactive substituent by reacting the diamine oligomer with a second substituent-introducing compound;

[0177] (3) Using the acid / substituent adduct having a photopolymerizable functional group and a reactive substituent obtained by the above (1) and / or the diamine oligomer having a reactive substituent obtained by the above (2), steps (ii) and (iii) in the method for producing the copolymer (A) are carried out, thereby introducing a reactive substituent derived from the second substituent-introducing compound into the acid terminal and / or amine terminal of the main chain of the copolymer (A).

[0178] The compound introduced as the second substituent is preferably a compound into which the structure represented by the above-mentioned general formula (E1) and (E2) is introduced, and examples thereof include, but are not limited to, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 2-(2-methacryloyloxyethoxy)ethyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, allylamine, and methacryloyl chloride.

[0179] In order to improve the adhesion between the photosensitive resin layer formed on the substrate by applying the photosensitive resin composition on the substrate and various substrates, when preparing (A) a copolymer containing a polyimide and a polyimide precursor, diaminosiloxanes such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane may be copolymerized.

[0180] After the amide polycondensation reaction is completed, the water absorption byproduct of the dehydration condensation agent coexisting in the reaction solution is filtered and separated as needed, and then a suitable poor solvent, such as water, aliphatic lower alcohol, or a mixed solution thereof, is added to the solution containing the polymer component to precipitate the polymer component, and then, as needed, operations such as redissolution and reprecipitation are repeated to purify the polymer, and then vacuum drying is performed to separate the target copolymer containing polyimide and polyimide precursor. In order to improve the purification degree, the polymer solution can also be passed through a column filled with an anion and / or cation exchange resin swollen with a suitable organic solvent to remove ionic impurities.

[0181] From the viewpoint of heat resistance and mechanical properties of the film obtained after heat treatment, the weight average molecular weight of the copolymer (A) containing polyimide and polyimide precursor is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, and particularly preferably 18,000 to 40,000 when measured by polystyrene conversion weight average molecular weight using gel permeation chromatography (GPC). If the weight average molecular weight is 8,000 or more, the mechanical properties are good, so it is preferred. On the other hand, if it is 150,000 or less, the dispersibility in the developer and the resolution of the relief pattern are good, so it is preferred. As the developing solvent of gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. In addition, the molecular weight is obtained based on a standard curve made using standard monodisperse polystyrene. As a standard monodisperse polystyrene, it is recommended to select from the organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko K.K.

[0182] (B) Photopolymerization initiator

[0183] (B) A photopolymerization initiator is a compound that can generate free radicals by active light and polymerize compounds containing ethylenically unsaturated groups. Examples of initiators that generate free radicals by active light include compounds containing structures such as benzophenone, N-alkylaminoacetophenone, oxime esters, acridine, and phosphine oxide. Examples thereof include benzophenone, N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-acetone-1, acrylated benzophenone, and the like. Aromatic ketones such as 4-benzoyl-4'-methyldiphenyl sulfide; benzoin ether compounds such as 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)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime) (BASF Japan Co., Ltd., Irgacure Oxe02), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(o-benzoyl oxime) (Jishu Strong Electronic Materials Co., Ltd., PBG305), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3-yl]-, 2-(O-acetyl oxime) (Nikko TR-PBG-326 (product name) manufactured by Chemtech Co., Ltd.) and other oxime ester compounds; benzyl derivatives such as benzyl dimethyl ketal; acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; N-phenylglycine derivatives such as N-phenylglycine; coumarin compounds; oxazole compounds; phosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, but are not limited to these. The (C) polymerization initiator described above can be used alone, or two or more types can be mixed and used. In particular, from the perspective of resolution, the above-mentioned photopolymerization initiator is more preferably an oxime ester compound.

[0184] in,

[0185] The amount of the photopolymerization initiator is 0.5 to 30 parts by mass, preferably 3 to 15 parts by mass, relative to 100 parts by mass of the copolymer (A) comprising polyimide and a polyimide precursor. Based on the viewpoint of sensitivity or patterning performance, the above-mentioned amount is 0.5 parts by mass or more, and on the other hand, based on the viewpoint of the physical properties of the photosensitive resin layer after curing of the photosensitive resin composition, the above-mentioned amount is preferably 30 parts by mass or less.

[0186] (C) Solvent

[0187] (C) The solvent is not limited as long as it can make (A) the copolymer containing polyimide and polyimide precursor, (B) the photopolymerization initiator uniformly dissolve or suspend the solvent. As such a solvent, γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, N,N-dimethylacetoacetamide, ε-caprolactone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, etc. These solvents can be used alone or in combination.

[0188] According to the coating film thickness and viscosity required for the photosensitive resin composition, the above-mentioned solvent can be used in a range of, for example, 30 to 1500 parts by mass, preferably 100 to 1,000 parts by mass, relative to 100 parts by mass of the copolymer (A) containing polyimide and polyimide precursor. In the case where the solvent contains an alcohol without an olefinic double bond, the content of the alcohol without an olefinic double bond in the total solvent is preferably 5 to 50% by mass, and more preferably 10 to 30% by mass. When the above-mentioned content of the alcohol without an olefinic double bond is 5% by mass or more, the storage stability of the photosensitive resin composition becomes good, and when its content is 50% by mass or less, the solubility of the copolymer (A) containing polyimide and polyimide precursor becomes good.

[0189] (D) Silane coupling agent

[0190] The photosensitive resin composition may optionally contain (D) a silane coupling agent in order to improve the adhesiveness of the relief pattern. The (D) silane coupling agent preferably has a structure represented by the following general formula (9).

[0191] General formula (9):

[0192]

[0193] In formula (9), R 21 is at least one selected from the group consisting of substituents including an epoxy group, a phenylamino group, and a urea group, and R22 are 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 of 1 to 3, and m4 is an integer of 1 to 6.

[0194] In the general formula (9), d may be an integer of 1 to 3 without limitation, and is preferably 2 or 3, more preferably 3, from the viewpoint of adhesion to the metal redistribution layer. m4 may be an integer of 1 to 6 without limitation, and is preferably 1 to 4 from the viewpoint of adhesion to the metal redistribution layer. From the viewpoint of developability, it is preferably 2 to 5.

[0195] R 21 The substituent may be any one of the structures selected from the group consisting of an epoxy group, a phenylamino group, a urea group, an isocyanate group, and an isocyanurate group. Among them, from the viewpoint of developability or adhesion to the metal redistribution layer, it is preferably at least one selected from the group consisting of a substituent comprising a phenylamino group and a substituent comprising a urea group, and more preferably a substituent comprising a phenylamino group. 22 There is no limitation as long as it is an alkyl group having 1 to 4 carbon atoms. Examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl. 23 There is no limitation as long as it is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include 22 Same alkyl group.

[0196] As the silane coupling agent containing epoxy group, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. can be illustrated. As the silane coupling agent containing phenylamino group, N-phenyl-3-aminopropyltrimethoxysilane can be illustrated. As the silane coupling agent containing urea group, 3-ureapropyltrialkoxysilane can be illustrated. As the silane coupling agent containing isocyanate group, 3-isocyanatepropyltriethoxysilane can be illustrated.

[0197] The content of the silane coupling (D) in the resin composition is 0.2 to 10% by mass relative to 100 parts by mass of the copolymer (A) containing a polyimide and a polyimide precursor, more preferably 1 to 8% by mass, and even more preferably 2 to 6% by mass from the viewpoint of copper adhesion.

[0198] (E) Radical polymerizable compound

[0199] In order to improve the resolution of the relief pattern and suppress the shrinkage during curing during heat curing, the photosensitive resin composition may optionally contain (E) a radical polymerizable compound. As such a compound, a (meth) acrylic compound that undergoes a radical polymerization reaction by a photopolymerization initiator is preferred, and although not particularly limited to the following, examples thereof include: di(meth)acrylates of ethylene glycol or polyethylene glycol represented by 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, 1,4-butanediol Compounds such as di(meth)acrylate, di(meth)acrylate of 1,6-hexanediol, di(meth)acrylate of neopentyl glycol, di(meth)acrylate of bisphenol A, (meth)acrylamide, derivatives thereof, trimethylolpropane tri(meth)acrylate, di(meth)acrylate or tri(meth)acrylate of glycerol, di(meth)acrylate, tri(meth)acrylate or tetra(meth)acrylate of pentaerythritol, ethylene oxide or propylene oxide adducts of these compounds. Among these free radical polymerizable compounds, it is preferred to have three or more free radical polymerizable groups based on the viewpoint of suppressing cure shrinkage. In addition, these monomers can be used alone or as a mixture of two or more.

[0200] The content of the radically polymerizable compound (E) in the resin composition is 0.5% to 50% by mass relative to 100 parts by mass of the copolymer (A) comprising a polyimide and a polyimide precursor, and is more preferably 5% to 40% by mass, and further preferably 10% to 30% by mass, from the viewpoint of resolution and suppression of cure shrinkage.

[0201] (F) Thermal crosslinking agent

[0202] The photosensitive resin composition may optionally contain (F) a thermal crosslinking agent in order to suppress cure shrinkage of the film after curing.

[0203] (F) The thermal crosslinking agent refers to a compound that causes an addition reaction or a polycondensation reaction by heat. These reactions occur between the copolymer resin (A) containing polyimide and polyimide precursor and the thermal crosslinking agent (F), between the thermal crosslinking agents (F), and between the thermal crosslinking agents (F) and the combination of the thermal crosslinking agent and the following other components, and the reaction temperature is preferably 150° C. or higher.

[0204] Examples of the (F) thermal crosslinking agent include alkoxymethyl compounds, epoxy compounds, oxetane compounds, bismaleimide compounds, allyl compounds, and blocked isocyanate compounds. From the viewpoint of suppressing cure shrinkage, the (F) thermal crosslinking agent preferably contains a nitrogen atom.

[0205] Examples of the alkoxymethyl compound include the following compounds, but are not limited to these.

[0206]

[0207]

[0208] Examples of epoxy compounds include epoxy compounds containing bisphenol A type groups, hydrogenated bisphenol A diglycidyl ether (e.g., Epolight 4000 manufactured by Kyoeisha Chemical Co., Ltd.), etc. Examples of oxetane compounds include: 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, bis[1-ethyl(3-oxetanyl)methyl ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methyl]biphenyl, 4,4'-bis(3-ethyl-3-oxetanylmethoxy)biphenyl, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, diethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, bis(3-ethyl-3-oxetanylmethyl)ether, methyl) diphenol ester, trimethylolpropane tris(3-ethyl-3-oxetanyl methyl) ether, pentaerythritol tetra(3-ethyl-3-oxetanyl methyl) ether, poly[[3-[(3-ethyl-3-oxetanyl)methoxy]propyl]silsesquioxane] derivative, silicate oxetanyl ester, novolac type oxetane, 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene, OXT121 (manufactured by Toa Gosei, trade name), OXT221 (manufactured by Toa Gosei, trade name), etc. Examples of the bismaleimide compound include 1,2-bis(maleimide)ethane, 1,3-bis(maleimide)propane, 1,4-bis(maleimide)butane, 1,5-bis(maleimide)pentane, 1,6-bis(maleimide)hexane, 2,2,4-trimethyl-1,6-bis(maleimide)hexane, N,N'-1,3-phenylenebis(maleimide), 4-methyl-N,N'-1,3-phenylenebis(maleimide), -1,3-phenylenebis(maleimide), N,N'-1,4-phenylenebis(maleimide), 3-methyl-N,N'-1,4-phenylenebis(maleimide), 4,4'-bis(maleimide)diphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-bis(maleimide)diphenylmethane or 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane. Examples of the allyl compound include allyl alcohol, allyl anisole, allyl benzoate, allyl cinnamate, N-allyloxyphthalimide, allyl phenol, allyl phenyl sulfone, allyl urea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl isocyanurate, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallylamine, triallyl 1,3,5-benzenetricarboxylate, triallyl trimellitate, triallyl phosphate, triallyl phosphite, and triallyl citrate.Examples of the blocked isocyanate compound include hexamethylene diisocyanate-based blocked isocyanates (e.g., Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B, and WM44-L70G manufactured by Asahi Kasei Corporation, Takenate B-882N manufactured by Mitsui Chemicals, Inc., 7960, 7961, 7982, 7991, and 7992 manufactured by Baxenden, etc.), toluene diisocyanate-based blocked isocyanates (e.g., Takenate B-830 manufactured by Mitsui Chemicals, Inc.), 4,4′-diphenylmethane diisocyanate-based blocked isocyanates (e.g., Takenate B-106 manufactured by Mitsui Chemicals, Inc.), and 4,4′-diphenylmethane diisocyanate-based blocked isocyanates. B-815N, Blonate PMD-OA01 and PMD-MA01 manufactured by Daiei Sangyo Co., Ltd., etc.), 1,3-bis(isocyanatomethyl)cyclohexane-based blocked isocyanates (e.g. Takenate B-846N manufactured by Mitsui Chemicals, Inc., Coronate BI-301, 2507, and 2554 manufactured by Tosoh Co., Ltd., etc.), isophorone diisocyanate-based blocked isocyanates (e.g. 7950, 7951, and 7990 manufactured by Baxenden Co., Ltd., etc.). Among them, blocked isocyanates or bismaleimide compounds are preferred from the viewpoint of storage stability. (F) The thermal crosslinking agent may be used alone or in combination of two or more.

[0209] The content of the (F) thermal crosslinking agent in the resin composition is 0.2% to 40% by mass relative to 100 parts by mass of the (A) copolymer containing a polyimide and a polyimide precursor. From the viewpoint of low dielectric properties and suppression of cure shrinkage, it is more preferably 1% to 20% by mass, and even more preferably 2% to 10% by mass.

[0210] (G) Filler

[0211] The photosensitive resin composition may optionally contain (G) a filler in order to suppress the cure shrinkage of the cured film. The filler is not limited as long as it is an inactive substance added to improve strength or various properties.

[0212] From the viewpoint of suppressing the increase in viscosity when the resin composition is prepared, the filler is preferably in a granular form. Examples of granular forms include needle-shaped, plate-shaped, spherical, etc. From the viewpoint of suppressing the increase in viscosity when the resin composition is prepared, the filler is preferably in a spherical form.

[0213] Examples of the needle-like filler include wollastonite, potassium titanate, xonotlite, aluminum borate, and needle-like calcium carbonate.

[0214] Examples of the plate-like filler include talc, mica, sericite, glass flakes, montmorillonite, boron nitride, and plate-like calcium carbonate.

[0215] Examples of the spherical filler include calcium carbonate, silica, alumina, titanium oxide, clay, hydrotalcite, magnesium hydroxide, zinc oxide, barium titanate, etc. Among them, silica, alumina, titanium oxide, and barium titanate are preferred from the viewpoint of electrical properties or storage stability when the resin composition is prepared, and silica and alumina are more preferred.

[0216] As the size of the filler, the primary particle size is defined as the size in the case of a sphere, and the length of the long side is defined as the size in the case of a plate or needle, preferably 5nm to 1000nm, more preferably 10nm to 1000nm. If it is more than 10nm, when a resin composition is made, there is a tendency to become fully uniform, and if it is less than 1000nm, photosensitivity can be imparted. Based on the viewpoint of imparting photosensitivity, it is preferably less than 800nm, more preferably less than 600nm, and particularly preferably less than 300nm. Based on the viewpoint of adhesion or uniformity of the resin composition, it is preferably more than 15nm, more preferably more than 30nm, and particularly preferably more than 50nm.

[0217] The content of the filler (G) in the resin composition is 1 vol% to 20 vol% relative to 100 parts by mass of the copolymer (A) comprising polyimide and a polyimide precursor, preferably 5 vol% to 20 vol% from the viewpoint of dielectric properties, and more preferably 5 vol% to 10 vol% from the viewpoint of resolution.

[0218] (H) Other ingredients

[0219] The photosensitive resin composition may further contain components other than the above-mentioned components (A) to (G). Examples of other components include: resin components other than the copolymer (A) containing polyimide and polyimide precursor; organic compounds containing metal elements, sensitizers, thermal inhibitors, azole compounds, and hindered phenol compounds.

[0220] The photosensitive resin composition may further contain resin components other than the copolymer (A) containing polyimide and polyimide precursor. As the resin components that may be contained in the photosensitive resin composition, for example, polyimide, polyoxazole, polyoxazole precursor, phenolic resin, polyamide, epoxy resin, siloxane resin, acrylic resin, etc. are listed. The compounding amount of these resin components is preferably in the range of 0.01 to 20 parts by mass relative to 100 parts by mass of the copolymer (A) containing polyimide and polyimide precursor.

[0221] The photosensitive resin composition may contain an organic compound containing a metal element. The organic compound containing a metal element preferably contains at least one metal element selected from the group consisting of titanium and zirconium in one molecule. As an organic group, it is preferred to contain a hydrocarbon group containing a hydrocarbon group and a heteroatom. By containing an organic compound, the imidization rate of the polyimide precursor contained in the photosensitive resin composition increases, and the dielectric loss tangent of the cured film decreases. As usable organic titanium or zirconium compounds, for example, substances to which an organic group is bonded to a titanium atom or a zirconium atom via a covalent bond or an ionic bond can be cited.

[0222] Specific examples of organic titanium or zirconium compounds are shown in the following I) to VII):

[0223] As I) chelate compound, based on the storage stability of the photosensitive resin composition and the aspect that a good pattern can be obtained, a compound having two or more alkoxy groups is more preferably used. Specific examples of chelate compounds include: bis(triethanolamine)diisopropyl titanate, di(n-butoxy)bis(2,4-pentanedione)titanium, diisopropoxybis(2,4-pentanedione)titanium, diisopropoxybis(tetramethylheptanedione)titanium, diisopropoxybis(ethyl acetoacetate)titanium, and compounds obtained by replacing the titanium atom of these compounds with a zirconium atom, but are not limited to these.

[0224] Examples of II) tetraalkoxy compounds include titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenol, titanium tetra(n-nonoxide), titanium tetra(n-propoxide), titanium tetrastearylate, titanium tetra[bis{2,2-(allyloxymethyl)butoxide}], and compounds obtained by replacing the titanium atom of these compounds with a zirconium atom, but the present invention is not limited thereto.

[0225] Examples of the titanocene or zirconocene compound (III) include pentamethylcyclopentadienyltrimethoxytitanium, bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and compounds in which the titanium atom of these compounds is replaced with a zirconium atom, but the present invention is not limited to these.

[0226] Examples of the monoalkoxy compound IV include titanium tris(dioctylphosphate)isopropoxide, titanium tris(dodecylbenzenesulfonate)isopropoxide, and compounds obtained by replacing the titanium atom of these compounds with a zirconium atom, but the present invention is not limited thereto.

[0227] Examples of V) the titanyl or zirconyl compound include bis(pentanedione)titania, bis(tetramethylheptanedione)titania, titanylphthalocyanine, and compounds obtained by replacing the titanium atom of these compounds with a zirconium atom, but the present invention is not limited thereto.

[0228] Examples of VI) titanium tetraacetylacetonate or zirconium tetraacetylacetonate compounds include titanium tetraacetylacetonate and compounds obtained by replacing the titanium atom of these compounds with a zirconium atom, but are not limited thereto.

[0229] Examples of the titanate coupling agent (VII) include, but are not limited to, isopropyl tri(dodecylbenzenesulfonyl) titanate.

[0230] In the above I) to VII), from the viewpoint of achieving a better dielectric loss tangent, the organic titanium compound is preferably at least one compound selected from the group consisting of the above I) titanium chelate compound, II) tetraalkoxy titanium compound, and III) titanocene compound. Particularly preferred are diisopropoxybis(ethyl acetoacetate)titanium, tetra(n-butoxide)titanium, and bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium.

[0231] The amount of the organic titanium or zirconium compound mixed with the copolymer containing polyimide and polyimide precursor (A) 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, the imidization rate of the resin composition and the dielectric loss tangent of the cured film are good. On the other hand, if it is 10 parts by mass or less, the storage stability is excellent, so it is preferred.

[0232] By making the photosensitive resin composition contain the above-mentioned organic compound containing a metal element, the imidization rate of the polyimide precursor contained in the resin composition can be increased, and the dielectric loss tangent of the cured film obtained by using the resin composition can be reduced. Although not limited by theory, it is believed that the reason why the imidization rate of the polyimide precursor can be increased is that the metal element contained in the organic compound containing a metal element is coordinated to the carbonyl group derived from the ester group, amide group and / or carboxyl group of the polyimide precursor, which can reduce the electron density of the carbon atom of the carbonyl group and promote the ring closing reaction.

[0233] In order to improve the sensitivity, the photosensitive resin composition may optionally contain a sensitizer. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylamino Cinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenyl biphenylene)-benzothiazole, 2-(p-dimethylaminophenyl vinylidene)benzothiazole, 2-(p-dimethylaminophenyl vinylidene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin ), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isopentyl dimethylaminobenzoate, isopentyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminophenylvinyl)benzoxazole, 2-(p-dimethylaminophenylvinyl)benzothiazole, 2-(p-dimethylaminophenylvinyl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, etc. These can be used alone or in combination of two or more (for example, 2 to 5 kinds). The amount of the sensitizer to be added is preferably 0.1 to 25 parts by mass based on 100 parts by mass of the copolymer (A) containing a polyimide and a polyimide precursor.

[0234] In order to improve the stability of the viscosity and sensitivity of the photosensitive resin composition when the solution containing the solvent is stored, the photosensitive resin composition may optionally contain a thermal polymerization inhibitor. As a thermal polymerization inhibitor, for example, hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt, etc. can be used. In addition, these thermal polymerization inhibitors can use one kind, and a mixture of two or more kinds can also be used. The amount of the thermal polymerization inhibitor to be added is preferably in the range of 0.005 to 12 parts by mass relative to 100 parts by mass of the copolymer containing the (A) polyimide and the polyimide precursor.

[0235] In the case of using a substrate containing copper or a copper alloy, in order to suppress discoloration of the substrate, the photosensitive resin composition may optionally contain an azole compound. 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)

[0063] In some embodiments, the present invention includes benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-tert-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxyl-1H-benzotriazole, 5-carboxyl-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. These azole compounds may be used alone or in combination of two or more.

[0236] The amount of the azole compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the copolymer (A) comprising polyimide and a polyimide precursor, and more preferably 0.5 to 5 parts by mass based on the viewpoint of sensitivity characteristics. If the amount of the azole compound is 0.1 parts by mass or more relative to 100 parts by mass of the copolymer (A) comprising polyimide and a polyimide precursor, when the photosensitive resin composition is formed on copper or a copper alloy, discoloration of the surface of the copper or copper alloy can be suppressed. On the other hand, if it is 20 parts by mass or less, the sensitivity is excellent, so it is preferred.

[0237] When a substrate containing copper or a copper alloy is used, the photosensitive resin composition may contain a hindered phenol compound in order to suppress discoloration of the substrate. Examples of the hindered phenol compound 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'-thio-bis(3-methyl-6-tert-butylphenol), 4,4'-butylene-bis(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], and the like. propionate], 2,2-thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(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)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-sec-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione,5-Tris(4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, etc., but not limited to these. Among them, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione is particularly preferred. ,

[0238] The amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the copolymer (A) comprising a polyimide and a polyimide precursor, and more preferably 0.5 to 10 parts by mass from the viewpoint of sensitivity characteristics. If the amount of the hindered phenol compound is 0.1 parts by mass or more relative to 100 parts by mass of the copolymer (A) comprising a polyimide and a polyimide precursor, for example, when the photosensitive resin composition is formed on copper or a copper alloy, discoloration and corrosion of the copper or the copper alloy can be prevented, while if it is 20 parts by mass or less, the sensitivity is excellent, which is preferred.

[0239] <Polyimide cured film and method for producing the same>

[0240] In addition, the present invention also provides a method for producing a cured polyimide film, which includes the step of converting a photosensitive resin composition into a polyimide. The method for producing a cured polyimide film of the present invention includes, for example, the following steps (1) to (5):

[0241] (1) a step of applying the photosensitive resin composition of the present invention onto a substrate to form a photosensitive resin layer on the substrate;

[0242] (2) a step of heating and drying the obtained photosensitive resin layer;

[0243] (3) exposing the heated and dried photosensitive resin layer to light;

[0244] (4) a step of developing the exposed photosensitive resin layer; and

[0245] (5) A step of heat-treating the developed photosensitive resin layer to form a polyimide cured film.

[0246] The photosensitive resin composition used in the method for producing a cured film preferably contains: 100 parts by mass of a copolymer containing a polyimide and a polyimide precursor, 0.5 to 30 parts by mass of a photosensitizer, and 100 to 1000 parts by mass of a solvent. It is more preferred to contain a photoradical polymerization initiator as the photosensitizer, and it is further preferred that the photosensitive resin composition is a negative type.

[0247] The specific steps in the method for producing a cured film can be carried out in accordance with the steps (1) to (5) of the method for producing a cured film described above. Hereinafter, a typical embodiment of each step will be described.

[0248] (1) Photosensitive resin layer forming step

[0249] In this step, the photosensitive resin composition of the present invention is applied to a substrate, and then dried as needed to form a photosensitive resin layer. As a coating method, a conventional method for coating a photosensitive resin composition, such as a method of coating by a spin coater, a bar coater, a knife coater, a curtain coater, a screen printer, etc., a method of spray coating by a spray coater, etc. can be used.

[0250] (2) Heating and drying process

[0251] The photosensitive resin composition film can be heated and dried as needed. As a drying method, air drying, heating drying using an oven or a hot plate, vacuum drying and the like can be used. In addition, it is desirable that the coating film is dried under conditions that do not cause imidization of the polyimide precursor portion (polyamic acid ester) of the (A) copolymer in the photosensitive resin composition. Specifically, in the case of air drying or heating drying, drying can be performed under the conditions of 20°C to 140°C for 1 minute to 1 hour. In the above manner, a photosensitive resin layer can be formed on a substrate.

[0252] (3) Exposure process

[0253] In this process, the photosensitive resin layer formed by the above method is exposed. As an exposure device, for example, a contact aligner, a mirror projection, a stepper exposure device, etc. can be used. The exposure can be performed with a photomask or a reticle having a pattern at intervals, or directly. The light used for exposure is, for example, an ultraviolet light source.

[0254] After exposure, a post-exposure bake (PEB) and / or a pre-development bake may be performed at any temperature and time combination as required for the purpose of improving sensitivity, etc. Regarding the range of baking conditions, the temperature is preferably 40 to 120° C., and the time is preferably 10 seconds to 240 seconds, but it is not limited to this range as long as it does not hinder the various properties of the negative photosensitive resin composition of this embodiment.

[0255] (4) Development process

[0256] In this process, the photosensitive resin layer after exposure is developed to form a relief pattern. In the case where the photosensitive resin composition is a negative type, the unexposed portion in the photosensitive resin layer after exposure is developed and removed. As a developing method for developing the photosensitive resin layer after exposure (irradiation), any method can be selected from the previously known developing methods of photoresists, such as a spin spray method, a paddle method, an immersion method accompanied by ultrasonic treatment, etc. to use. In addition, after development, it is also possible to implement post-development baking with any combination of temperature and time as needed for the purpose of adjusting the shape of the relief pattern. As a developer for development, for example, it is preferably a good solvent for a negative photosensitive resin composition, or a combination of the good solvent and a poor solvent. As a good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. are preferred. As the poor solvent, for example, toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate and water are preferred. When a good solvent and a poor solvent are mixed for use, it is preferred to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the negative photosensitive resin composition. In addition, two or more, for example, multiple solvents can also be used in combination. In the process of developing the photosensitive resin layer after exposure, it is preferred to perform the above-mentioned coating-development process in a manner to obtain a photosensitive resin layer with a film thickness of 10μm to 15μm.

[0257] (5) Polyimide Cured Film Formation Step

[0258] In this process, the relief pattern obtained by the above-mentioned development is heated to volatilize the photosensitive component, and the (A) copolymer is imidized and converted into a cured relief pattern containing polyimide. As a method for heat curing, various methods such as a method using a hot plate, a method using an oven, and a method using a temperature-raising oven with a settable temperature program can be selected. Heating can be carried out, for example, at 160°C to 400°C for 30 minutes to 5 hours. As the ambient gas during heat curing, air can be used, and inert gases such as nitrogen and argon can also be used. In the manner described above, a cured relief pattern (polyimide cured film) can be manufactured.

[0259] The method for producing a polyimide cured film of the present invention is, for example, a method for producing a cured film comprising the steps of applying the photosensitive resin composition of the present invention on a substrate, performing an exposure treatment, a development treatment, and then performing a heat treatment, wherein the dielectric loss tangent of the cured film when measured at 40 GHz by a perturbation-type separated cylindrical resonant cavity method is preferably 0.003 to 0.011. It should be noted that the dielectric loss tangent can be measured by the perturbation-type separated cylindrical resonant cavity method shown in the following examples.

[0260] In addition, the present invention also provides a polyimide cured film obtained from the photosensitive resin composition described above. Based on the viewpoint of transmission loss caused by dielectric, the dielectric loss tangent of the cured film at a frequency of 40 GHz measured by the perturbation-type separated cylindrical resonant cavity method is preferably 0.003 to 0.011, and the lower the better. In addition, based on the viewpoint of multilayering of the redistribution layer, the cured film is preferably 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 deformation of the redistribution layer caused by copper wiring during redistribution will become slight. As a redistribution material for copper wiring for high-speed transmission, it is preferred that the residual film rate after curing (RFA) and the dielectric loss tangent (tanδ 40 ) quotient (RFA / tanδ 40 ) is within a certain range, preferably the value of the dielectric loss tangent 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 (81%<RFA<93% in terms of percentage), and satisfies the following formula:

[0261] 85<RFA(ratio) / tanδ 40 <175

[0262] By making RFA(ratio) / tanδ 40 When the ratio is within the range of greater than 85 and less than 175, a polyimide cured product can be obtained as a rewiring material preferably used for copper wiring for high-speed transmission. RFA (ratio) / tan δ 40 More preferably, it is greater than 100 and less than 170.

[0263] <Semiconductor devices>

[0264] The present invention may also provide a semiconductor device having a cured relief pattern obtained by the above-mentioned method for manufacturing a cured relief pattern using the photosensitive resin composition of the present invention. Therefore, the present invention provides a semiconductor device having: a semiconductor element, i.e., a substrate, and a cured relief pattern of polyimide formed on the substrate by the above-mentioned method for manufacturing a cured relief pattern. In addition, the present invention may also be applied to a method for manufacturing a semiconductor device using a semiconductor element as a substrate and including the above-mentioned method for manufacturing a cured relief pattern as part of the process. The semiconductor device may be manufactured by forming a cured relief pattern formed by the above-mentioned method for manufacturing a cured relief pattern as a surface protective film, an interlayer insulating film, an insulating film for redistribution, a protective film for a flip chip, or a protective film for a semiconductor device having a bump structure, and combining it with a known method for manufacturing a semiconductor device.

[0265] The polyimide contained in the cured relief pattern (polyimide cured film) formed from the photosensitive resin composition preferably has a structure represented by the following general formula (10).

[0266]

[0267] {In the general formula (10), X1, X2, X3, Y1, and Y2 are the same as X1, X2, X3, Y1, and Y2 in the above general formula (1), n1 is an integer of 2 to 30, and n2 and n3 are integers of 2 to 150.}

[0268] <Display device>

[0269] The present invention may also provide a display device, which is a display device using the photosensitive resin composition of the present invention, having a display element, and a cured film disposed on the upper portion of the display element, and the cured film is the above-mentioned cured relief pattern. Here, the cured relief pattern may be directly stacked with the display element, or may be stacked with other layers. For example, as the cured film, there may be listed: surface protective films, insulating films, and flattening films of TFT liquid crystal display elements and color filter elements, protrusions for MVA type liquid crystal display devices, and partition walls for cathodes of organic EL (Electroluminescence) elements.

[0270] The photosensitive resin composition of the present invention can be used for applications other than the semiconductor device described above, such as interlayer insulation of multilayer circuits, cover coating of flexible copper-clad laminates, solder resist films, and liquid crystal alignment films.

[0271] <Method for producing photosensitive resin composition>

[0272] The method for producing a photosensitive resin composition of the present invention comprises: a step of producing (A) a copolymer resin by the method of the present invention as described in the above "(A) method for producing a copolymer resin containing a polyimide and a polyimide precursor"; and a step of mixing (A) 100 parts by mass of the copolymer resin, (B) 0.5 to 30 parts by mass of a photopolymerization initiator, and (C) 100 to 1000 parts by mass of a solvent to obtain a photosensitive resin composition. The above-described (D) silane coupling agent, (E) free radical polymerizable compound, (F) thermal crosslinking agent, (G) filler, and (H) other components may also be optionally mixed.

[0273] Example

[0274] The physical properties of the photosensitive resin compositions in Examples, Comparative Examples, and Production Examples of the present invention were measured and evaluated according to the following methods.

[0275] <Measurement and evaluation methods>

[0276] (1) Weight average molecular weight

[0277] The weight average molecular weight (Mw) of the diamine oligomer and copolymer resin was measured by gel permeation chromatography (standard polystyrene conversion). The columns used for the measurement were Shodex805M / 806M series manufactured by Showa Denko K.K., the standard monodisperse polystyrene was Shodex STANDARD SM-105 manufactured by Showa Denko K.K., the developing solvent was N-methyl-2-pyrrolidone, and the detector was Shodex RI-930 manufactured by Showa Denko K.K.

[0278] (2) Determination of the imide structure introduction rate of copolymer resin

[0279] 10 g of the copolymer resin was dissolved in a mixed solvent containing γ-butyrolactone and DMSO (weight ratio 90:10), and the amount of the solvent was adjusted so that the viscosity became about 25 poise, thereby preparing a polymer solution. The polymer solution was spin-coated on a 6-inch silicon wafer (manufactured by Fujimi Electronics Industry Co., Ltd., thickness 625±25 μm) using a coating and developing device (D-Spin 60A model, manufactured by SOKUDO), and heated and dried on a hot plate at 110°C for 3 minutes, thereby forming a photosensitive resin layer with a thickness of about 10 μm. An ATR-FTIR measuring device (Nicolet Continuum, manufactured by Thermo Fisher Scientific) was used with a Si prism and a measuring range of 4000 cm -1 ~700cm -1 The photosensitive resin layer was measured 50 times. The cured film was measured at 1380 cm -1Nearby (1350cm -1 ~1450cm -1 (in the case of multiple peaks, the peak with the largest peak intensity) divided by 1500 cm -1 Nearby (1460cm -1 ~1550cm -1 The value obtained by measuring the peak height (in the case of multiple peaks, the peak with the largest peak intensity) was taken as the imidization index 1. The imidization index 1 was divided by the imidization index 2 of a cured film cured at 350° C. under the same conditions to calculate the imide structure introduction rate.

[0280] (3) Resolution and development time of the cured relief pattern on the Cu substrate

[0281] On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industry Co., Ltd., thickness 625±25μm), a sputtering device (L-440S-FHL type, manufactured by CANON ANELVA) was used to sputter Ti with a thickness of 200nm and Cu with a thickness of 400nm in sequence. Next, on the wafer, a photosensitive resin composition prepared by the following method was spin-coated using a coating and developing device (D-Spin60A type, manufactured by SOKUDO) and heated and dried on a hot plate at 110°C for 3 minutes, thereby forming a photosensitive resin layer with a thickness of about 13.5μm. Using a mask with a test pattern, the photosensitive resin layer was irradiated with 600mJ / cm using a Prisma GHI (manufactured by Ultratech) equipped with an i-ray filter. 2 energy. Next, using cyclopentanone as a developer, the photosensitive resin layer is spray-developed using a coating development device (D-Spin60A, manufactured by SOKUDO), and rinsed with propylene glycol methyl ether acetate, thereby obtaining a relief pattern on Cu. The spray development time at this time is taken as the development time. Using a temperature-rising program curing furnace (VF-2000, manufactured by Koyo Lindberg), the wafer with the relief pattern formed on Cu is heated at 230°C for 2 hours in a nitrogen environment, thereby obtaining a cured relief pattern containing resin with a thickness of about 10 μm on Cu. The produced relief pattern is observed under an optical microscope to find the size of the minimum opening pattern. At this time, if the area of ​​the opening portion of the obtained pattern is more than 1 / 2 of the corresponding pattern mask opening area, it is considered to be resolvable, and the resolution is determined according to the following evaluation criteria based on the length of the photomask opening edge corresponding to the opening portion with the smallest area that can be resolved (the size of the opening pattern).

[0282] (Evaluation Criteria)

[0283] A: The minimum opening pattern size is less than 10μm

[0284] B: The minimum opening pattern size is 10 μm or more and less than 15 μm

[0285] C: The minimum opening pattern size is 15 μm or more and less than 20 μm

[0286] D: The minimum opening pattern size is 20 μm or more

[0287] In the present invention, it is considered that the result of C or more is preferable.

[0288] (4) Measurement of dielectric properties (relative dielectric constant: Dk, dielectric loss tangent: Df)

[0289] A 6-inch silicon wafer (manufactured by Fujimi Electronics Industry Co., Ltd., with a thickness of 625±25μm) was sputtered with aluminum (Al) with a thickness of 100nm using a sputtering device (L-440S-FHL, manufactured by CANON ANELVA) to prepare a sputtered Al wafer substrate. A photosensitive resin composition prepared by the following method was spin-coated on the above-mentioned sputtered Al wafer substrate using a spin coating device (D-spin60A, manufactured by SOKUDO), and heated and dried at 110°C for 180 seconds to form a photosensitive resin layer with a thickness of about 13.5μm. Thereafter, an aligner (PLA-501F, manufactured by Canon) was used with an exposure amount of 600mJ / cm 2 The whole surface was exposed to GHI rays, and a vertical curing furnace (manufactured by Koyo Lindberg, model name VF-2000B) was used to perform heat curing treatment at 230°C for 2 hours in a nitrogen environment to produce a cured film containing resin with a thickness of about 10 μm on the Al wafer. A dicing saw (manufactured by DISCO, model name DAD-2H / 6T) was used to cut the cured film into 80 mm in length and 62 mm in width (for 10 GHz measurement) and 40 mm in length and 30 mm in width (for 40 GHz measurement), and the film was impregnated in a 10% hydrochloric acid aqueous solution and peeled off from the silicon wafer to prepare a thin film sample. For the thin film samples, the relative dielectric constant (Dk) and dielectric loss tangent (Df) at 10 GHz and 40 GHz were measured respectively by the cavity resonator perturbation method. The details of the measurement method are described below.

[0290] (Measurement method)

[0291] Disturbance Split Cylindrical Resonant Cavity Method

[0292] (Measurement sample humidity adjustment)

[0293] Leave at 23℃ / 50%RH for 24 hours

[0294] (Measurement conditions)

[0295] 23℃ / 50%RH

[0296] (Device Configuration)

[0297] Network Analyzer:

[0298] PNANetwork analyzer N5224B

[0299] (Manufactured by KEYSIGHT)

[0300] Split Cylindrical Resonator:

[0301] CR-710 (manufactured by Kanto Electronics Application Development Co., Ltd., measuring frequency: about 10 GHz)

[0302] CR-740 (manufactured by Kanto Electronics Application Development Co., Ltd., measuring frequency: about 40 GHz)

[0303] (5) Determination of residual film rate after curing

[0304] On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industry Co., Ltd., thickness 625±25μm), a sputtering device (L-440S-FHL, manufactured by CANON ANELVA) was used to sputter Ti with a thickness of 200nm and Cu with a thickness of 400nm in sequence. Next, on the wafer, a coating and developing device (D-Spin60A, manufactured by SOKUDO) was used to spin-coat the photosensitive resin composition prepared by the following method, and heated and dried on a hot plate at 110°C for 3 minutes, thereby forming a photosensitive resin layer with a thickness of about 13.5μm. Thereafter, an aligner (PLA-501F, manufactured by Canon) was used with an exposure amount of 800mJ / cm 2 The entire surface is exposed to GHI rays. After that, the coating formed on the wafer is spray developed using cyclopentanone using a coating development device (D-SPIN636, manufactured by Dainippon Screen Mfg, Japan). And, after rinsing with propylene glycol methyl ether acetate, it is dried by spin drying. The thickness of the film after development is measured as film thickness 1. Furthermore, a vertical curing furnace (manufactured by Koyo Lindberg, model name VF-2000B) is used to heat and cure the developed film at 230°C for 2 hours in a nitrogen environment. The thickness of the film after the heat treatment is measured as film thickness 2. Using these film thicknesses, the residual film rate after curing (ratio and %) is calculated by the following formula.

[0305] Residual film rate after curing (ratio) = film thickness 2 / film thickness 1

[0306] Residual film rate after curing (%) = film thickness 2 / film thickness 1×100

[0307] In addition, the residual film rate (ratio) after curing and the dielectric loss tangent (tanδ 40 ) quotient (RFA (ratio) / tanδ 40 ).

[0308] (6) Copper adhesion evaluation

[0309] On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industry Co., Ltd., thickness 625±25μm), a sputtering device (L-440S-FHL, manufactured by CANON ANELVA) was used to sputter Ti with a thickness of 200nm and Cu with a thickness of 400nm in sequence. Next, on the wafer, a coating and developing device (D-Spin60A, manufactured by SOKUDO) was used to spin-coat the photosensitive resin composition prepared by the following method, and heated and dried on a hot plate at 110°C for 3 minutes, thereby forming a photosensitive resin layer with a thickness of about 13.5μm. Thereafter, an aligner (PLA-501F, manufactured by Canon) was used with an exposure amount of 800mJ / cm 2 The whole surface was exposed to GHI rays, and a vertical curing furnace (manufactured by Koyo Lindberg, model name VF-2000B) was used to perform heat curing treatment at 230°C for 2 hours in a nitrogen environment to produce a cured film containing resin with a thickness of about 10 μm on the Cu wafer. For the film after heat treatment, the adhesion properties between the copper substrate and the cured resin coating film were evaluated based on the following criteria according to the crosscut method of JIS K5600-5-6 standard.

[0310] (Evaluation Criteria)

[0311] A: The number of grids of the cured resin coating film bonded to the substrate is 80 or more to 100

[0312] B: The number of cells of the cured resin coating film bonded to the substrate is 60 or more and less than 80

[0313] C: The number of cells of the cured resin coating film bonded to the substrate is 40 or more and less than 60

[0314] D: The number of grids of the cured resin coating film bonded to the substrate is less than 40

[0315] In the present invention, it is considered that the result of B or more is preferable.

[0316] (7) Storage stability

[0317] The following photosensitive resin composition was prepared, and after standing at room temperature for 24 hours, the viscosity was measured at 23°C using an E-type viscometer (VISCOMATE VM-150III manufactured by Toki Sangyo). The initial viscosity was taken as viscosity 1. The measured photosensitive resin composition was stored at 40°C for 3 days, and the viscosity was measured again under the same conditions. The viscosity after the heat treatment was taken as viscosity 2. Using these viscosities, the storage stability was calculated by the following formula.

[0318] Viscosity change rate (%) = (|viscosity 2 - viscosity 1| / viscosity 1) × 100

[0319] (Evaluation Criteria)

[0320] A: Viscosity change rate is less than 3%

[0321] B: Viscosity change rate is 3% or more and less than 5%

[0322] C: Viscosity change rate is 5% or more and less than 10%

[0323] D: Viscosity change rate is more than 10%

[0324] In the present invention, it is considered that the result of C or more is preferable.

[0325] <Production of diamine X-1>

[0326] A 5L four-necked flask was replaced with Ar, and 172.02g of 4,4'-butylindenebis(6-tert-butyl-m-methylphenol), 155.84g of 4-chloronitrobenzene, and 1.5L of DMF were added and stirred. K2CO3186.42g was added thereto, heated at 150°C for 5 hours, and the disappearance of the raw materials and intermediates was confirmed by TLC. After cooling to room temperature, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure at 80°C. The concentrated residue was injected into 1.6L of ion exchange water, and 2.5L of ethyl acetate was added, and liquid separation and purification were performed three times. The organic layer was recovered, and MgSO4 was added to dry it. After drying, it was filtered to remove impurities, 800mL of toluene was added to dissolve it, and the dissolved substance was added to 4.0L of methanol and stirred for 30 minutes. After stirring, the filtrate was recovered by filtration and dried at 80°C for 12 hours. The reaction product obtained by drying was placed in a 5L four-necked flask replaced with Ar, and 19.04g of 5% Pd / C(EA) and 1.9L of THF were added and stirred. The flask was heated to 40°C, H2 was bubbled (10mL / min), and the reduction reaction was carried out for 24 hours. The reaction solution was filtered through diatomaceous earth, and the fraction of the target product was recovered by silica gel chromatography, and the diamine X-1 was obtained by vacuum concentration.

[0327] <(A) Production of diamine compound having repeating units of polyimide structure>

[0328] Synthesis of polyimide (diamine oligomer W-1):

[0329] In a 0.5-liter separable flask equipped with a Dean-Stark tube and a condenser, 41.6 g of 4,4'-(4,4'-isopropyldiphenyloxy)diphthalic anhydride (BPADA) as an acid component, 34.0 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) as a diamine component, and 176.4 g of N-methylpyrrolidone (NMP) as a solvent were added and dissolved while stirring. Furthermore, 42.3 g of toluene was added and stirred, and then the temperature was raised to 185° C. under a nitrogen gas stream. After stirring at 185° C. for 2.5 hours, the toluene in the system and the water generated by imidization were removed over 1.5 hours. Thereafter, the solution was cooled to room temperature to obtain a solution of a diamine oligomer W-1 having a repeating unit of a polyimide structure. The weight average molecular weight (Mw) of the diamine oligomer W-1 was measured and found to be 3,000. Diamine oligomer W-1 1 The imide ring closure rate was confirmed by comparing the peak derived from the amide bond of the polyimide with the peak derived from the aromatic ring in H-NMR measurement. The imide ring closure rate was 99% or more.

[0330] Synthesis of polyimide (diamine oligomer W-2):

[0331] The diamine oligomer W-2 solution was obtained by the above-mentioned synthesis method of the diamine oligomer W-1, except that 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 synthesis method of the diamine oligomer W-1. The weight average molecular weight (Mw) of the diamine oligomer W-2 was measured and found to be 5,000. 1 The imide ring closure rate obtained by H-NMR measurement was 99% or more.

[0332] Synthesis of polyimide (diamine oligomer W-3):

[0333] The above-mentioned synthesis method of diamine oligomer W-1 was used, except that 24.8 g of 4,4'-oxydiphthalic anhydride (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 synthesis method of 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 measured and the result was 2,700. In the same manner as diamine oligomer W-1, 1 The imide ring closure rate obtained by H-NMR measurement was 99% or more.

[0334] Synthesis of polyimide (diamine oligomer W-4):

[0335] The diamine oligomer W-4 solution was obtained by the same method as described in the synthesis method of the diamine oligomer W-1 except that 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 weight average molecular weight (Mw) of the diamine oligomer W-4 was measured to be 3,000. 1 The imide ring closure rate obtained by H-NMR measurement was 99% or more.

[0336] Synthesis of polyimide (diamine oligomer W-5):

[0337] The diamine oligomer W-5 solution was obtained by the same method as described in the synthesis method of the diamine oligomer W-1 except that 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 weight average molecular weight (Mw) of the diamine oligomer W-5 was measured to be 3,500. 1 The imide ring closure rate obtained by H-NMR measurement was 99% or more.

[0338] Synthesis of polyimide (diamine oligomer W-6):

[0339] The diamine oligomer W-6 solution was obtained by the above-mentioned synthesis method of diamine oligomer W-1, except that 55.8 g of 9,9-bis(4-aminophenyl)fluorene (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 synthesis method of diamine oligomer W-1. The weight average molecular weight (Mw) of diamine oligomer W-6 was measured and the result was 2,900. 1 The imide ring closure rate obtained by H-NMR measurement was 99% or more.

[0340] Synthesis of polyimide (diamine oligomer W-7):

[0341] The diamine oligomer W-7 solution was obtained by the same method as described in the synthesis method of the diamine oligomer W-1 except that 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 weight average molecular weight (Mw) of the diamine oligomer W-7 was measured to be 8,200. 1 The imide ring closure rate obtained by H-NMR measurement was 99% or more.

[0342] Synthesis of polyimide (diamine oligomer W-8):

[0343] The diamine oligomer W-8 solution was obtained by the same method as described in the synthesis method of the diamine oligomer W-1 except that 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 weight average molecular weight (Mw) of the diamine oligomer W-8 was measured to be 2,500. 1 The imide ring closure rate obtained by H-NMR measurement was 99% or more.

[0344] Synthesis of polyimide (diamine oligomer W-9):

[0345] The above-mentioned synthesis method of diamine oligomer W-1 was used, and 35.5.8 g of 4,4'-(hexafluoroisopropylidene)diphthalic 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 synthesis method of 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 measured and the result was 3,200. In the same manner as diamine oligomer W-1, 1 The imide ring closure rate obtained by H-NMR measurement was 99% or more.

[0346] Synthesis of polyimide (diamine oligomer W-10):

[0347] The diamine oligomer W-1 solution was obtained by the same method as described in the synthesis method of the diamine oligomer W-1 except that 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 weight average molecular weight (Mw) of the diamine oligomer W-10 was measured to be 3,700. 1 The imide ring closure rate obtained by H-NMR measurement was 99% or more.

[0348] <(A) Production of copolymer resin containing polyimide and polyimide precursor>

[0349] Synthesis of polymer A-1:

[0350] 20.9 g of BPADA as an acid component was added to a 1-liter separable flask, and 10.9 g of 2-hydroxyethyl methacrylate (HEMA) and 42 g of γ-butyrolactone (GBL) were added. 6.4 g of pyridine was added while stirring at room temperature, and heated at 50°C for 4 hours. After the heat generated by the reaction ended, the mixture was allowed to cool to room temperature. The mixture was then allowed to stand for 16 hours to obtain a reaction mixture.

[0351] Next, under ice-cooling, 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 while stirring, and then 91.0 g of GBL was added. Next, a solution obtained by mixing 101.7 g of an NMP solution of the diamine oligomer W-2 prepared in the above manner as a diamine component with 66.5 g of GBL was added over 20 minutes while stirring. Furthermore, a solution obtained by dissolving 2.4 g of m-TB in 7 g of GBL was added over 5 minutes while stirring. Furthermore, after stirring at room temperature for 4 hours, 6.4 g of ethanol was added and stirred for 30 minutes, and then 49.0 g of GBL was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.

[0352] The obtained reaction solution was added to 1000 g of ethanol to generate a precipitate containing a crude polymer. The generated crude polymer was filtered out and dissolved in 270 g of γ-butyrolactone to obtain a crude polymer solution. An anion exchange resin ("Amberlyst" manufactured by Organo Co., Ltd.) was used to obtain a crude polymer solution. TM 15JWET”), the obtained crude polymer solution is purified to obtain a polymer solution. The obtained polymer solution is added dropwise to 3800g of water to precipitate the polymer, and the obtained precipitate is filtered out and then vacuum dried to obtain a powdered polymer A-1. The weight average molecular weight (Mw) of the polymer A-1 is 30,000, and the imide group introduction rate is 0.43. In addition, the imide group concentration U of each repeating unit of the polyimide obtained from the polymer A-1 is 16.0wt%. It should be noted that the "imide group concentration U" is calculated by converting the polyimide into a polyimide cured film obtained by heating and curing at 350°C (the same applies below).

[0353] Synthesis of polymer A-2:

[0354] 15.2 g of BPADA as an acid component was added to a 1-liter separable flask, and 7.9 g of HEMA and 30.8 g of γ-butyrolactone (GBL) were added. 4.6 g of pyridine was added while stirring at room temperature, and the mixture was heated at 50°C for 4 hours. After the heat generated by the reaction was stopped, the mixture was allowed to cool to room temperature. The mixture was then allowed to stand for 16 hours to obtain a reaction mixture.

[0355] Next, under ice cooling, 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 while stirring, and then 91.0 g of GBL was added. Next, a solution obtained by mixing 111.5 g of an NMP solution of the diamine oligomer W-1 prepared in the above manner as a diamine component and 72.9 g of GBL was added over 20 minutes while stirring. Furthermore, after stirring at room temperature for 4 hours, 49.0 g of GBL was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.

[0356] The subsequent purification step is to react in the same manner as described in the synthesis method of polymer A-1, thereby obtaining polymer A-2. The weight average molecular weight (Mw) of polymer A-2 is 24,000, and the imide group introduction rate is 0.58. In addition, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-2 is 20.1wt%.

[0357] Synthesis of polymer A-3:

[0358] 15.2 g of BPADA as an acid component was added to a 1-liter separable flask, and 7.9 g of HEMA (first substituent-introducing compound) and 30.8 g of GBL were added. 4.6 g of pyridine was added while stirring at room temperature, and the mixture was heated at 50°C for 4 hours. After the heat generated by the reaction was stopped, the mixture was allowed to cool to room temperature. The mixture was then allowed to stand for 16 hours to obtain a reaction mixture (first reaction).

[0359] In a separately prepared 0.5-liter three-necked flask, 111.5 g of an NMP solution of a diamine oligomer W-1 as a diamine component and 72.9 g of GBL were mixed, and while stirring under ice-cooling, 3.1 g of 2-isocyanatoethyl methacrylate (a second substituent-introducing compound) was dissolved in 15.5 g of GBL, and the mixture was stirred for 1 hour under ice-cooling to obtain a reaction mixture solution with the diamine oligomer W-1 (second reaction).

[0360] Simultaneously with the second reaction, 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 over 40 minutes while stirring under ice cooling. Next, a reaction mixture solution of the diamine oligomer W-1 obtained by the second reaction as a diamine component was added over 60 minutes while stirring. Furthermore, after stirring at room temperature for 4 hours, 49.0 g of GBL was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.

[0361] The subsequent purification step is to react 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 18,000, and the imide group introduction rate is 0.58. In addition, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-3 is 20.1wt%.

[0362] Synthesis of polymer A-4:

[0363] In the synthesis method of the polymer A-1, BPADA 17.0 g was used instead of BPADA 20.9 g, HEMA 8.8 g was used instead of 10.9 g, DCC 13.3 g was used instead of 16.3 g, and NMP solution 127.2 g of diamine oligomer W-2 was used instead of NMP solution 101.7 g of diamine oligomer W-2 and mTB 2.4 g. 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 the polymer A-3 was 35,000, and the imide group introduction rate was 0.53. In addition, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-4 was 15.2 wt%.

[0364] Synthesis of polymer A-5:

[0365] In the synthesis method of the above polymer A-2, 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 of HEMA, 10.7 g of DCC was used instead of 11.9 g of HEMA, 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. In addition, 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 the polymer A-5 was 22,000, and the imide group introduction rate was 0.63. In addition, the imide group concentration U of each repeating unit of the polyimide obtained from polymer A-4 was 20.5 wt%.

[0366] Synthesis of polymer A-6:

[0367] In the synthesis method of the above polymer A-2, 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 of HEMA, 10.7 g of DCC was used instead of 11.9 g of HEMA, 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. In addition, 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 the polymer A-6 was 23,000, and the imide group introduction rate was 0.63. In addition, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-6 was 19.6 wt%.

[0368] Synthesis of polymer A-7:

[0369] In the synthesis method of the above polymer A-1, 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. In addition, the reaction was carried out in the same manner as the method described in the synthesis method of polymer A-1, thereby obtaining polymer A-7. The weight average molecular weight (Mw) of the polymer A-7 is 21,000, and the imide group introduction rate is 0.43. In addition, the imide group concentration U of each repeating unit of the polyimide obtained by polymer A-7 is 16.7 wt%.

[0370] Synthesis of polymer A-8:

[0371] 12.4 g of ODPA as an acid component was added to a 1-liter separable flask, and 10.8 g of HEMA (first substituent-introducing compound) and 26.0 g of GBL were added. 6.3 g of pyridine was added while stirring at room temperature to obtain a reaction mixture (first reaction). After the heat generated by the reaction was terminated, the mixture was allowed to cool to room temperature and then allowed to stand for 16 hours.

[0372] Next, 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 while stirring under ice cooling. Next, 1.1 g of allylamine (second substituent introduction compound) was dissolved in 5.5 g of GBL, and the GBL solution was added over 5 minutes while stirring (second reaction). A solution obtained by dissolving 143.1 g of an NMP solution of a diamine oligomer W-5 as a diamine component in 93.6 g of GBL was added to the reaction mixture of the second reaction over 60 minutes while stirring. Furthermore, after stirring at room temperature for 4 hours, 6.4 g of ethanol was added and stirred for 30 minutes, and then 49.0 g of GBL was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.

[0373] The subsequent purification step was carried out in the same manner as described in the synthesis method of polymer A-1, thereby obtaining polymer A-8. The weight average molecular weight (Mw) of polymer A-8 was 19,000, and the imide group introduction rate was 0.43. In addition, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-8 was 16.7wt%.

[0374] Synthesis of polymer A-9:

[0375] In the synthesis method of the above polymer A-1, 105.6 g of the NMP solution of the diamine oligomer W-6 was used instead of 101.7 g of the NMP solution of the diamine oligomer W-2 and 2.4 g of m-TB. The reaction was carried out in the same manner as described in the synthesis method of the polymer A-1, thereby obtaining a polymer A-9. The weight average molecular weight (Mw) of the polymer A-9 was 29,000, and the imide group introduction rate was 0.43. In addition, the imide group concentration U per repeating unit of the polyimide obtained from the polymer A-9 was 16.8 wt%.

[0376] Synthesis of polymer A-10:

[0377] In the synthesis method of the polymer A-2, BPADA 4.6 g was used instead of BPADA 15.2 g, HEMA 2.4 g was used instead of 7.9 g, DCC 3.6 g was used instead of 11.9 g, and NMP solution 174.4 g of diamine oligomer W-7 was used instead of NMP solution 111.5 g of diamine oligomer W-1. 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 the polymer A-10 was 40,000, and the imide group introduction rate was 0.88. In addition, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-10 was 16.8 wt%.

[0378] Synthesis of polymer A-11:

[0379] In the synthesis method of the polymer A-3, BPADA 4.6 g was used instead of BPADA 15.2 g, HEMA 2.4 g was used instead of 7.9 g, DCC 3.6 g was used instead of 11.9 g, NMP solution 174.4 g of diamine oligomer W-7 was used instead of NMP solution 111.5 g of diamine oligomer W-1, and methacryloyl chloride 2.1 g and pyridine 1.4 g were used instead of 2-isocyanatoethyl methacrylate 3.1 g. 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 the polymer A-11 was 36,000, and the imide group introduction rate was 0.88. In addition, the imide group concentration U per repeating unit of the polyimide obtained from the polymer A-11 was 16.8 wt%.

[0380] Synthesis of polymer A-12:

[0381] In the synthesis method of the above polymer A-1, 12.1 g of ODPA was used instead of 20.9 g of BPADA, and 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. In addition, the reaction was carried out in the same manner as the method described in the synthesis method of polymer A-1, thereby obtaining polymer A-12. The weight average molecular weight (Mw) of the polymer A-12 was 26,000, and the imide group introduction rate was 0.58. In addition, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-12 was 23.6 wt%.

[0382] Synthesis of polymer A-13:

[0383] In the synthesis method of the polymer A-1, 17.3 g of 6FDA was used instead of 20.9 g of BPADA, and 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. 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 the polymer A-13 was 28,000, and the imide group introduction rate was 0.44. In addition, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-13 was 17.1 wt%.

[0384] Synthesis of polymer A-14:

[0385] In the synthesis method of the polymer A-2, 7.7 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 15.2 g of BPADA, 7.1 g of HEMA was used instead of 7.9 g of HEMA, 10.7 g of DCC was used instead of 11.9 g of HEMA, 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. In addition, 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 the polymer A-14 was 21,000, and the imide group introduction rate was 0.63. In addition, the imide group concentration U per repeating unit of the polyimide obtained from the polymer A-14 was 19.8 wt%.

[0386] Synthesis of polymer A-15:

[0387] In the synthesis method of the polymer A-1, 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. 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 the polymer A-15 was 28,000, and the imide group introduction rate was 0.16. In addition, the imide group concentration U per repeating unit of the polyimide obtained from the polymer A-15 was 15.8 wt%.

[0388] Synthesis of polymer A-16:

[0389] In the synthesis method of the polymer A-1, 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. 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 was 26,000, and the imide group introduction rate was 0.44. In addition, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-16 was 21.1 wt%.

[0390] Synthesis of polymer A-17:

[0391] In the synthesis method of the polymer A-2, 13.9 g of glycerol dimethacrylate was used instead of 7.9 g of HEMA. The reaction was carried out in the same manner as described in the synthesis method of the polymer A-2, thereby obtaining a polymer A-17. The weight average molecular weight (Mw) of the polymer A-17 was 24,000, and the imide group introduction rate was 0.58. In addition, the imide group concentration U per repeating unit of the polyimide obtained from the polymer A-17 was 20.1 wt%.

[0392] Synthesis of polymer A-18:

[0393] In the synthesis method of the polymer A-2, 7.8 g of 2-aminoethyl methacrylate was used instead of 7.9 g of HEMA, and the reaction was carried out in the same manner as described in the synthesis method of the polymer A-2, thereby obtaining a polymer A-18. The weight average molecular weight (Mw) of the polymer A-18 was 24,000, and the imide group introduction rate was 0.58. In addition, the imide group concentration U per repeating unit of the polyimide obtained from the polymer A-18 was 20.1 wt%.

[0394] Synthesis of polymer A-19:

[0395] In the synthesis method of the polymer A-2, 7.7 g of 2-hydroxybutyl methacrylate (HBMA) and 0.7 g of allyl alcohol were used instead of 7.9 g of HEMA. The reaction was carried out in the same manner as described in the synthesis method of the polymer A-2, thereby obtaining a polymer A-19. The weight average molecular weight (Mw) of the polymer A-19 was 24,000, and the imide group introduction rate was 0.58. In addition, the imide group concentration U per repeating unit of the polyimide obtained from the polymer A-19 was 20.1 wt%.

[0396] Synthesis of polyimide precursor (polymer A-20):

[0397] 60.2 g of ODPA as an acid component was added to a 1-liter separable flask, and 54.2 g of HEMA and 137.5 g of GBL were added. 31.6 g of pyridine was added while stirring at room temperature to obtain a reaction mixture. After the heat generated by the reaction was stopped, the mixture was allowed to cool to room temperature and then allowed to stand for 16 hours.

[0398] Next, 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 while stirring under ice cooling. Furthermore, a solution obtained by dissolving 36.4 g of m-TB as a diamine component in 109.2 g of GBL was added over 60 minutes while stirring. Furthermore, after stirring at room temperature for 2.5 hours, 15 g of ethanol was added and stirred for 30 minutes, and then 150 g of γ-butyrolactone was added and stirred at 50° C. for 0.5 hour. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.

[0399] The obtained reaction solution was added to 2700 g of ethanol to generate a precipitate containing a crude polymer. The generated crude polymer was filtered out and dissolved in 1000 g of γ-butyrolactone to obtain a crude polymer solution. An anion exchange resin ("Amberlyst" manufactured by Organo Co., Ltd.) was used to obtain a crude polymer solution. TM 15”) to purify the obtained crude polymer solution to obtain a polymer solution. The obtained polymer solution was dropped into 8000g of water to precipitate the polymer, and the obtained precipitate was filtered out and then vacuum dried to obtain a powdered polymer A-20. The weight average molecular weight (Mw) of the polymer A-20 was 19,000, and the imide group introduction rate was 0. In addition, the imide group concentration U of each repeating unit of the polyimide obtained from the polymer A-20 was 28.8wt%.

[0400] Synthesis of polyimide precursor (polymer A-21):

[0401] In the synthesis method of the polymer A-20, except that 63.3 g of BAPP was used instead of 36.4 g of m-TB, the reaction was carried out in the same manner as described in the synthesis method of the polymer A-20, thereby obtaining a polymer A-21. The weight average molecular weight (Mw) of the polymer A-21 was 21,000, and the imide group introduction rate was 0. In addition, the imide group concentration U per repeating unit of the polyimide obtained from the polymer A-21 was 20.5 wt%.

[0402] Synthesis of polyimide precursor (polymer A-22):

[0403] In the synthesis method of the polymer A-20, BPDA 58.8 g was used instead of ODPA 62.0 g, and 4,4'-diaminodiphenyl ether (DADPE) 34.3 g was used instead of m-TB 36.4 g. In addition, the reaction was carried out in the same manner as the method described in the synthesis method of the polymer A-20, thereby obtaining a polymer A-22. The weight average molecular weight (Mw) of the polymer A-22 was 22,000, and the imide group introduction rate was 0. In addition, the imide group concentration U per repeating unit of the polyimide obtained from the polymer A-22 was 30.5wt%.

[0404] Synthesis of polyimide precursor (polymer A-23):

[0405] In the synthesis method of the polymer A-20, except that 81.3 g of BAPP was used instead of 36.4 g of m-TB, the same reaction was carried out as in the synthesis method of the polymer A-20, thereby obtaining a polymer A-23. The weight average molecular weight (Mw) of the polymer A-23 was 16,000, and the imide group introduction rate was 0. In addition, the imide group concentration U per repeating unit of the polyimide obtained from the polymer A-23 was 20.5 wt%.

[0406] Synthesis of polyimide (polymer A-24):

[0407] In a 1-liter separable flask equipped with a Dean-Stark tube and a condenser, 97.7 g of 6FDA as an acid component, 64.1 g of TFMB as a diamine component, and 529.2 g of N-methylpyrrolidone (NMP) as a solvent were added and dissolved while stirring. Furthermore, 126.9 g of toluene was added and stirred, and then the temperature was raised to 185°C under a nitrogen gas flow. After stirring at 185°C for 2.5 hours, the toluene in the system and the water generated by imidization were removed over 1.5 hours. Thereafter, the mixture was cooled to room temperature to obtain a polyimide solution.

[0408] The obtained polyimide solution was added to 1000 g of methanol to generate a precipitate containing a crude polymer. The generated crude polymer was filtered out and the polymer was washed again with methanol. The washed polymer was vacuum dried at 50°C to obtain a powdered polymer A-24. The weight average molecular weight (Mw) of the polymer A-24 was 25,000. 1H-NMR measurement was performed to compare the peak derived from the amide bond of the polyimide with the peak derived from the aromatic ring, thereby confirming the imide ring closure rate. The imide ring closure rate was 99% or more. In addition, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-24 was 19.2wt%.

[0409] <Ingredients (B) to (G)>

[0410] Photopolymerization initiator B1: 3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]acetone-1-(O-acetyl oxime) (trade name: PBG-304, manufactured by Changzhou Qiangli Electronics Co., Ltd.)

[0411] 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.)

[0412] Photopolymerization initiator B3: 1-[4-(phenylthio)phenyl]-3-propane-1,2-dione-2-(O-acetyl oxime) (trade name: PBG-3057, manufactured by Changzhou Qiangli Electronics Co., Ltd.)

[0413] Solvent C1: γ-butyrolactone

[0414] Solvent C2: dimethyl sulfoxide (DMSO)

[0415] Solvent C3: 3-methoxy-N,N-dimethylpropionamide

[0416] Silane coupling agent D-1: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0417] Silane coupling agent D-2: N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0418] Silane coupling agent D-3: tert-butyl carbamate (3-triethoxysilylpropyl)

[0419] Silane coupling agent D-4: ureidopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0420] Silane coupling agent D-5: X-12-1214A (manufactured by Shin-Etsu Chemical Co., Ltd., trade name)

[0421] Silane coupling agent D-6: tris(trimethoxysilylpropyl)isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0422] Radically polymerizable compound E-1: 1,6-hexanediol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0423] Radical polymerizable compound E-2: Pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0424] Radically polymerizable compound E-3: (PO (Propylene Oxide, propylene oxide) modified) trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0425] Radically polymerizable compound E-4: dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0426] Thermal crosslinking agent F-1: bismaleimide compound (manufactured by Yamato Chemical Industry Co., Ltd., BMI-5100)

[0427] Thermal crosslinking agent F-2: blocked isocyanate (manufactured by Asahi Kasei Corporation, SBB70P)

[0428] Thermal crosslinking agent F-3: an alkoxymethyl compound having the following structure (manufactured by Daito Chemix, CROLIN-318)

[0429]

[0430] Filler G-1: spherical silica (manufactured by Admatechs, K180SP-CY1)

[0431] <Example 1>

[0432] As shown in Table 3, 100 g of polymer A-1 as component (A) and 7 g of photopolymerization initiator B-1 as component (B) were dissolved in a mixed solvent (weight ratio 90:10) containing γ-butyrolactone and DMSO as solvent (C) to prepare a photosensitive resin composition solution. The composition was evaluated by the above method.

[0433] <Examples 2 to 37, Comparative Examples 1 to 9>

[0434] A photosensitive resin composition solution was prepared and evaluated by the same method as in Example 1 except that the types and amounts of the components were adjusted to the ratios described in Tables 3 to 6. Only in Comparative Example 8, the prepared photosensitive resin composition solution was left to stand at 40° C. for 240 hours. Using the photosensitive resin composition after standing, the imidization rate as the photosensitive resin composition layer was measured by the above-mentioned method for measuring the imide structure introduction rate, and the result was 0.45. The characteristics and evaluation results are shown in Tables 7 to 10.

[0435] [Table 1]

[0436] Table 1.

[0437]

[0438] [Table 2]

[0439]

[0440] [Table 3]

[0441]

[0442] [Table 4]

[0443]

[0444] [Table 5]

[0445]

[0446] [Table 6]

[0447]

[0448] As can be seen from Tables 1 to 10, in the embodiments, by introducing a polyimide block structure at a specific ratio, a photosensitive resin composition having low dielectric properties, low curing shrinkage, and good storage stability can be provided, and phase separation during coating is reduced, and a cured relief pattern having high resolution and high copper adhesion can be formed. On the other hand, in Comparative Examples 1 to 6 that do not have a polyimide structure, the results are high dielectric loss tangent and low residual film rate after curing. In Comparative Example 7 in which polyimide is blended into a polyimide precursor having an imide group introduction rate of 0, the compatibility is poor and it cannot be evenly coated, so it is difficult to evaluate the resolution. In addition, it is believed that phase separation leads to the result of high dielectric loss tangent and low copper adhesion. It is believed that in Comparative Example 8 using a partially imidized polyimide precursor, although the dielectric loss tangent shows a low result, it is difficult to control imidization, so the result is that the film after coating is turbid and the resolution is poor. In Comparative Example 9 using 100% imide polymer, a radical polymerizable monomer is required for patterning, and although the residual film rate after curing shows a high value, the dielectric loss tangent is high and the resolution is low. As can be seen from the above results, no satisfactory results were obtained in the comparative examples.

[0449] Industrial Applicability

[0450] The photosensitive resin composition of the present invention can be preferably used in the field of photosensitive materials useful for production of electric and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

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

90.

2. The photosensitive resin composition according to claim 1, wherein The photopolymerizable functional group includes a structure represented by the following general formula (2): 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.

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

90.

4. The photosensitive resin composition according to claim 1 or 2, wherein The copolymer resin (A) containing polyimide and a polyimide precursor does not contain a halogen atom.

5. The photosensitive resin composition according to claim 1 or 2, wherein In the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350° C., the ratio of the molecular weight of the imide group to the molecular weight of the repeating unit containing the structure derived from tetracarboxylic dianhydride and diamine, i.e., the imide group concentration U, is 12 wt % to 26 wt %.

6. The photosensitive resin composition according to claim 1 or 2, wherein X1, X2 and X3 of the copolymer resin (A) comprising polyimide and a polyimide precursor include a structure represented by the following general formula (4), In formula (4), R8 and R9 are each independently an organic group having 1 to 10 carbon atoms, m2 and m3 are integers selected from 0 to 4, satisfying m2+m3≥1, Z1 is selected from any one of the group consisting of a single bond, an organic group having 1 to 30 carbon atoms, and an organic group containing a heteroatom, two of the * represent bonds bonded to the main chain of the resin, and the other two represent bonds bonded to the side chain in the general formula (1); and / or, Y1 and / or Y2 include a structure represented by the following general formula (7), In formula (7), 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 the group consisting of a single bond, an organic group with 1 to 30 carbon atoms and an organic group containing a heteroatom, and * indicates bonding to the main chain of the resin.

7. The photosensitive resin composition according to claim 1 or 2, wherein The copolymer resin (A) comprising a polyimide and a polyimide precursor has a reactive substituent which is polymerized by heat or light, different from the photopolymerizable functional group contained in the repeating unit, at a resin terminal. 8 . The photosensitive resin composition according to claim 1 , further comprising (D) a silane coupling agent. 9 . The photosensitive resin composition according to claim 1 , further comprising (E) a radical polymerizable compound. 10 . The photosensitive resin composition according to claim 1 , further comprising (F) a thermal crosslinking agent. 11 . The photosensitive resin composition according to claim 1 , further comprising (G) a filler.

12. A method for producing a polyimide cured film, comprising the following steps (1) to (5): (1) a step of coating the photosensitive resin composition according to claim 1 or 2 on a substrate to form a photosensitive resin layer on the substrate; (2) a step of heating and drying the obtained photosensitive resin layer; (3) exposing the heated and dried photosensitive resin layer to light; (4) a step of developing the exposed photosensitive resin layer; and (5) A step of heat-treating the developed photosensitive resin layer to form a polyimide cured film.

13. A method for producing a cured film, comprising applying the resin composition according to claim 1 or 2 onto a substrate, performing an exposure treatment, a development treatment, and then performing a heat treatment to obtain a cured film, wherein the dielectric loss tangent of the cured film measured by a perturbation split cylindrical resonant cavity method at 40 GHz is 0.003 to 0.

011.

14. A polyimide cured film, wherein the dielectric loss tangent at a frequency of 40 GHz measured by a perturbation split cylindrical resonant cavity method is 0.003 to 0.011, the RFA is 0.81 to 0.93, and the film satisfies the following formula: 85<RFA / tanδ 40 <175 Where, RFA represents the residual film rate (ratio) after thermal curing, tanδ 40 It represents the dielectric loss tangent at a frequency of 40 GHz measured by the perturbation split cylindrical resonator method.

15. A method for producing a copolymer, which is a method for producing a copolymer comprising polyimide and a polyimide precursor, the method comprising the following steps: (i) subjecting a first tetracarboxylic dianhydride or its acid / substituent adduct to a condensation reaction with a first diamine compound to perform imidization, thereby obtaining a diamine oligomer having a repeating unit of a polyimide structure; (ii) subjecting the diamine oligomer to a condensation reaction with a second tetracarboxylic dianhydride or an acid / substituent adduct thereof to synthesize a polyimide-imide precursor portion having a polyimide block portion; and (iii) synthesizing a polyimide precursor by condensing the polyimide-imide precursor with a third tetracarboxylic dianhydride or an acid / substituent adduct thereof 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 having a photopolymerizable functional group, and the first diamine compound and the second diamine compound may be the same or different from each other.

16. A method for producing a photosensitive resin composition, comprising: Manufacturing a copolymer resin comprising polyimide and a polyimide precursor by the method according to claim 15; as well as, A step of mixing (A) 100 parts by mass of the copolymer resin containing the polyimide and the polyimide precursor, (B) 0.5 to 30 parts by mass of a photopolymerization initiator, and (C) 100 to 1000 parts by mass of a solvent to obtain a photosensitive resin composition.

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