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

Abstract

The present disclosure provides a method for producing a copolymer resin that can provide a photosensitive resin composition having low dielectric properties, low curing shrinkage, and good storage stability, reduced phase separation during coating, and capable of forming a cured relief pattern with high resolution and high copper adhesion. [Solution] The method for producing a copolymer resin comprising a polyimide and a polyimide precursor according to the present disclosure includes: (i) obtaining a diamine oligomer by condensing a first tetracarboxylic dianhydride or its acid / substituent adduct with a first diamine compound to imidize it; (ii) synthesizing a polyimide-imide precursor portion (unit n2) by condensing the diamine oligomer with a second tetracarboxylic dianhydride or its acid / substituent adduct; and (iii) synthesizing a polyimide precursor portion (unit n3) by condensing the polyimide-imide precursor portion with a third tetracarboxylic dianhydride or its acid / substituent adduct and a second diamine compound. 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.

Description

[Technical Field]

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

[0002] Conventionally, polyimide resins, polybenzoxazole resins, phenolic resins, and the like have been used as insulating materials for electronic components, and as passivation films, surface protective films, and interlayer insulating films for semiconductor devices, possessing excellent heat resistance, electrical properties, and mechanical properties. Among these resins, those provided in the form of photosensitive resin compositions allow for the easy formation of heat-resistant relief pattern films through ring-closing treatment (imidization, benzoxazoleization) or thermal crosslinking by coating, exposure, development, and curing of the composition. Such photosensitive resin compositions have the advantage of significantly shortening the process compared to conventional non-photosensitive materials and are used in the fabrication of semiconductor devices.

[0003] Incidentally, semiconductor devices (hereinafter also referred to as "devices") are mounted on printed circuit boards in various ways depending on the purpose. Conventionally, devices were generally manufactured using the wire bonding method, in which thin wires are connected from the external terminals (pads) of the device to the lead frame. However, with the increasing speed of devices and the fact that operating frequencies have reached GHz, differences in the wiring length of each terminal during mounting now affect the operation of the device. Therefore, in mounting devices for high-end applications, it has become necessary to precisely control the length of the mounting wiring, and wire bonding has become difficult to meet this requirement.

[0004] Therefore, flip-chip mounting has been proposed, in which a redistribution layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed on top of it, and then the chip is flipped over and directly mounted on a printed circuit board. Because the wiring distance can be precisely controlled with this flip-chip mounting, it has been adopted for high-end devices that handle high-speed signals, and also for mobile phones and other devices due to its small mounting size, and demand is rapidly expanding. More recently, a semiconductor chip mounting technology called fan-out wafer-level packaging (FOWLP) has been proposed, in which individual chips are manufactured by dicing a wafer that has undergone pre-processing, the individual chips are reconstructed on a support and sealed with molding resin, and then the redistribution layer is formed after peeling off the support (for example, Patent Document 1). With fan-out wafer-level packaging, the redistribution layer is formed with a thin film thickness, so the height of the package can be reduced, and there are advantages such as high-speed transmission and cost reduction.

[0005] In recent years, with the remarkable increase in the volume of information and communication traffic, it has become necessary to achieve communication speeds beyond conventional levels. This has necessitated a shift to fifth-generation communication (5G) using frequencies of 3 GHz or higher, or to ultra-high frequency bands such as the quasi-millimeter wave band (20 GHz to 30 GHz) to the millimeter wave band (30 GHz or higher), where wider frequency bandwidths can be easily secured. As a result, high-frequency compatibility is required not only for printed circuit boards but also for the semiconductor chips on which the boards are mounted. Therefore, in order to reduce transmission loss, antenna-in-package (AiP) designs have been developed in which the front-end module (FEM) that transmits and receives radio waves and the antenna are integrated (see, for example, Patent Document 2 below). In AiP, the wiring length is short, making it possible to suppress transmission loss, which increases in proportion to the wiring length. However, as the communication frequency bandwidth increases, there is a requirement for low dielectric properties in the redistribution material. In addition, since AiP requires multiple redistribution layers, similar to conventional FOWLP, planarization of the redistribution layers is also required.

[0006] As means for solving the above problems, in order to reduce transmission loss in the high-frequency band, there are roughly two methods: a method for reducing dielectric loss and a method for reducing conductor loss. For the former, low dielectric characteristics (low dielectric tangent, low dielectric constant) are required for the photosensitive resin composition, and Patent Document 3, Patent Document 4, and Patent Document 5 can be cited as examples. However, in Patent Document 3, since the measurement frequency is as low as 1 GHz, it is insufficient as a rewiring layer for AiP which is for high-frequency applications. In Patent Document 4, since a polyimide precursor resin and a polyimide resin are blended, there are concerns about the storage stability of the photosensitive resin composition and phase separation during coating. In Patent Document 5, a varnish containing a polyimide precursor resin is subjected to heat aging to produce a partially imidized polyimide precursor in the varnish. 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 means for planarizing the rewiring layer, a method for suppressing the curing shrinkage of the rewiring layer can be considered, and Patent Document 6 can be cited as an example. In Patent Document 6, high planarization is achieved by using a polyfunctional (meth)acrylate in a polyimide resin. However, there is no description about dielectric characteristics, and there are concerns about deterioration of dielectric characteristics at high frequencies due to the influence of a large amount of polyfunctional (meth)acrylate.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

[0009] In recent years, the diversification of package mounting technologies has led to a greater variety of support materials and multi-layered redistribution layers, resulting in a greater influence of the dielectric constant and dielectric loss tangent (tanδ) of the insulating material used for wiring formation. High dielectric constant and dielectric loss tangent increase dielectric loss, leading to increased transmission loss. While polyimide resins offer excellent insulation performance and thermomechanical properties, resulting in high material reliability, their high dielectric constant and dielectric loss tangent due to the influence of polar functional groups derived from imide groups, polar functional groups added for photosensitivity, and additives is considered problematic. Furthermore, the multi-layering of redistribution layers can sometimes lead to problems with the flatness of the redistribution layer due to low curing shrinkage.

[0010] The present disclosure aims to provide a photosensitive resin composition that has low dielectric properties, low curing shrinkage, and good storage stability, reduces phase separation during coating, and can form 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 a polyimide cured film. [Means for solving the problem]

[0011] Examples of embodiments of this disclosure are listed in the following sections [1] to

[16] . [1] (A) 100 parts by mass of a copolymer resin containing polyimide and a polyimide precursor; (B) 0.5 to 30 parts by mass of photopolymerization initiator; (C) 100 to 1000 parts by mass of solvent; A photosensitive resin composition comprising, The copolymer resin comprising the polyimide and the polyimide precursor has a structure represented by the following general formula (1): [ka] 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 photosensitive resin composition containing the polyimide and the polyimide precursor is a photosensitive resin composition satisfying 0.10 < n2 / (n2 + n3) < 0.90. [2] The photopolymerizable functional group is The photosensitive resin composition according to item 1, which contains a structure represented by the following general formula (2). [Chemical formula] (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 item 1 or 2, wherein 0.40 < n2 / (n2 + n3) < 0.90. [4] The photosensitive resin composition according to any one of items 1 to 3, wherein the copolymer resin containing the polyimide and the polyimide precursor does not contain a halogen atom. [5] In the polyimide of the polyimide cured film obtained by heating and curing the photosensitive resin composition at 350°C, the imide group concentration U, which is 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, is 12 wt% to 26 wt%. The photosensitive resin composition according to any one of items 1 to 4. [6] X1, X2, and X3 of the copolymer resin containing the polyimide and the polyimide precursor contain a structure represented by the following general formula (4), [Chemical formula] In formula (4), R8 and R9 are each independently organic groups 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 single bonds, organic groups having 1 to 30 carbon atoms, and organic groups containing heteroatoms, two of the *s represent bonds to the main chain of the resin, and the other two represent bonds to the side chain in the general formula (1) above; and / or, Y1 and / or Y2 include the structure shown in the following general formula (7): [ka] The photosensitive resin composition according to any one of items 1 to 5, wherein R8 and R9 are each independently organic groups 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 single bonds, organic groups having 1 to 30 carbon atoms, and organic groups containing heteroatoms, and * means bonding to the main chain of the resin. [7] The photosensitive resin composition according to any one of items 1 to 6, wherein the copolymer resin comprising the (A) polyimide and the polyimide precursor has other reactive substituents at the resin ends that polymerize by heat or light, different from the photopolymerizable functional groups contained in the repeating units. [8] (D) A photosensitive resin composition according to any one of items 1 to 7, further comprising a silane coupling agent. [9] (E) A photosensitive resin composition according to any one of items 1 to 8, further comprising a radical polymerizable compound.

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

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

[12] The following steps (1) to (5): (1) A step of applying a photosensitive resin composition described in any one of items 1 to 11 onto a substrate to form a photosensitive resin layer on the substrate; (2) A step of heating and drying the obtained photosensitive resin layer; (3) A step of exposing the photosensitive resin layer after heating and drying; (4) A step of developing the photosensitive resin layer after exposure; and (5) A step of heat-treating the photosensitive resin layer after development to form a polyimide cured film; A method for producing a polyimide cured film, including the following:

[13] A method for producing a cured film, comprising applying a resin composition described in any one of items 1 to 11 onto a substrate, performing an exposure treatment, a developing treatment, and then a heat treatment, wherein the cured film has a dielectric loss tangent of 0.003 to 0.011 as measured by a perturbation-type split-cylinder resonator at 40 GHz.

[14] A polyimide cured film having a dielectric loss tangent of 0.003 to 0.011 at a frequency of 40 GHz as measured by a perturbation-type split-cylinder resonator method, and an RFA of 0.81 to 0.93, and the following formula: 85 <RFA / tanδ 40 <175 {In the formula, RFA represents the residual film percentage (ratio) after thermosetting, and tanδ 40 This shows the dielectric loss tangent at a frequency of 40 GHz using a perturbed split-cylinder resonator method. A polyimide cured film satisfying}.

[15] A method for producing a copolymer containing a polyimide and a polyimide precursor, the method comprising the following steps: (i) A diamine oligomer having repeating units of a polyimide structure is obtained by condensing a first diamine compound with a first tetracarboxylic dianhydride or its acid / substituted adduct and imidizing it; (ii) Synthesizing a polyimide-imide precursor moiety having a polyimide block moiety by condensing the diamine oligomer with a second tetracarboxylic dianhydride or its acid / substituted adduct; (iii) Synthesizing the polyimide precursor by condensing the polyimide-imide precursor with a third tetracarboxylic dianhydride or its acid / substituted adduct and a second diamine compound. Includes, A method for producing a copolymer, wherein 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 / substituted 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, wherein the method is: A copolymer resin containing polyimide and a polyimide precursor is produced by the method described in item 15; (A) A copolymer resin containing 100 parts by mass of the 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 are mixed to obtain a photosensitive resin composition. A method for producing a photosensitive resin composition containing [the specified substance]. [Effects of the Invention]

[0012] According to this disclosure, a photosensitive resin composition having low dielectric properties, low curing shrinkage, and good storage stability, reduced phase separation during coating, and capable of forming a cured relief pattern with high resolution and high copper adhesion can be provided, as well as a method for producing a polyimide cured film using the same and a polyimide cured film. [Modes for carrying out the invention]

[0013] Embodiments of this disclosure will be described in detail below. Throughout this specification, structures represented by the same symbols in a general formula, if present in multiple locations within a molecule, are selected independently unless otherwise specified and may be identical or different from one another. Similarly, structures represented by common symbols in different general formulas are also selected independently unless otherwise specified and may be identical or different from one another.

[0014] <Photosensitive resin composition> The photosensitive resin composition of this disclosure contains (A) 100 parts by mass of a copolymer resin comprising a specific 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. The photosensitive resin composition of this disclosure may optionally further contain, in addition to the above components, (D) a silane coupling agent, (E) a radical polymerizable compound, (F) a thermal crosslinking agent, (G) a filler, and other components.

[0015] (A) Copolymer resin containing polyimide and polyimide precursor A copolymer resin containing polyimide and a polyimide precursor (hereinafter also simply referred to as "copolymer resin") preferably contains a structure represented by the following general formula (1). General formula (1): [ka] In formula (1), X1, X2, and X3 are each independently tetravalent organic groups having 6 to 40 carbon atoms, and Y1 and Y2 are each independently divalent organic groups 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 from 2 to 30. n2 and n3 are each independently integers from 2 to 150. In this disclosure, the n1 unit of formula (1) is referred to as the "polyimide block portion," the n2 unit as the "polyimide-imide precursor portion," and the n3 unit as the "polyimide precursor portion." Although formula (1) only describes one polyimide-imide precursor portion and one polyimide precursor portion for simplicity, the copolymer resin may have multiple polyimide-imide precursor portions and multiple polyimide precursor portions randomly arranged with respect to each other.

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

[0017] In formula (1), R1, R2, R3, and R4 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms. However, at least one of R1, R2, R3, and R4 is a photopolymerizable functional group, and examples include at least one group selected from (meth)acryloyloxyalkyl groups, allyl groups, ethynyl groups, and styryl groups, with (meth)acryloyloxyalkyl groups being more preferred. Z3, Z4, Z5, and Z6 are even more preferably photopolymerizable functional groups represented by the following general formula (2). General formula (2): [ka] 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 a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and a methyl group is preferred. R5 is preferably a hydrogen atom or a methyl group, R6 and R7 are preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. 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 each independently more preferably a photopolymerizable functional group represented by the above general formula (2).

[0018] The copolymer resin containing a polyimide and a polyimide precursor has a ratio of the number of moles of the polyimide-imide precursor portion (unit of n2) to the total number of moles of the polyimide-imide precursor portion (unit of n2) and the polyimide precursor portion (unit of n3) (hereinafter, also referred to as "imide structure introduction rate") satisfying 0.10 < n2 / (n2 + n3) < 0.90. As a result, the cured polyimide has low dielectric characteristics and low curing shrinkage, and a photosensitive resin composition capable of forming a cured relief pattern with good storage stability and high resolution can be obtained.

[0019] The inclusion of the structure represented by the above general formula (1) results in a relief pattern with good resolution, low dielectric properties, and a cured film with low curing shrinkage. Although not constrained by theory, it is believed that the resolution of the relief pattern is improved because the polyimide block portion (unit n1) and the polyimide precursor structure (i.e., the imide precursor structure in units n2 and n3) are contained within the same molecule, and the polyimide-imide precursor portion is present in a specific ratio, thereby suppressing swelling in the exposed area and making it easier to ensure contrast with the unexposed area. Furthermore, since a portion of the copolymer resin contains the polyimide block portion, it is believed that curing shrinkage is suppressed and low dielectric properties can be achieved by reducing the amount of side chain structure removed during ring closure. In addition, by containing the polyimide block portion and the polyimide precursor structure within the same molecule, the less soluble polyimide structure can exist stably in the photosensitive resin composition solution (hereinafter also referred to as "varnish"). This is believed to prevent the storage stability of the varnish from being impaired. On the other hand, when a varnish containing a polyimide precursor resin is heated to form an imide structure, photosensitive groups that have detached from the side chain structure remain in the varnish, resulting in increased curing shrinkage.

[0020] From the viewpoint of resolution, low dielectric properties, and low curing shrinkage, the imide structure introduction rate is preferably 0.10 to 0.90. From the viewpoint of resolution, a lower imide structure introduction rate is preferable, and from the viewpoint of low dielectric properties and low curing shrinkage, a higher n2 / (n2+n3) is preferable. Therefore, the imide structure introduction rate is more preferably 0.20 to 0.90, even more preferably 0.30 to 0.90, even more preferably 0.40 to 0.90, particularly preferably 0.43 to 0.80, and particularly preferably 0.45 to 0.75.

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

[0022] In the above general formula (1), n2 is preferably an integer between 3 and 100, more preferably an integer between 5 and 70, from the viewpoint of photosensitive properties and mechanical properties of the photosensitive resin composition. n3 is preferably an integer between 3 and 100, more preferably an integer between 5 and 70, from the viewpoint of photosensitive properties and mechanical properties. n1 is preferably an integer between 2 and 30, more preferably an integer between 5 and 20, from the viewpoint of coatability and dielectric loss tangent. The larger n1 is, the higher the imide structure introduction rate and the better the dielectric loss tangent. On the other hand, if n1 is too large, the coatability is impaired, so finding the right balance is important.

[0023] In the above general formula (1), the tetravalent organic groups represented by X1, X2, and X3 are preferably organic groups having 6 to 40 carbon atoms, in terms of achieving both heat resistance and photosensitive properties, and more preferably aromatic groups or alicyclic aliphatic groups in which the -COOR1 and -COOR2 groups and the -CONH- group are in the ortho position relative to each other. Specifically, the tetravalent organic groups represented by X1, X2, and X3 are organic groups having 6 to 40 carbon atoms containing an aromatic ring, for example, the following general formula (3): [ka] {In formula (3), R 11X1, X2, and X3 are monovalent groups 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, where m5 is an integer from 1 to 2, m6 is an integer from 1 to 3, and m7 is an integer from 1 to 4. Examples of groups having the structure represented by} include, but are not limited to, these. The tetravalent organic groups represented by X1, X2, and X3 may be one type or a combination of two or more types. The X1, X2, and X3 groups having the structure represented by the above formula (3) are particularly preferred in that they achieve both heat resistance and photosensitive properties.

[0024] In the above general formula (1), X1, X2, and X3 preferably include the structure shown in the following general formula (4) from the viewpoint of resolution and low dielectric properties. General formula (4): [ka] {In the formula, R8 and R9 are each independently organic groups 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 the group consisting of single bonds, organic groups having 1 to 30 carbon atoms, and organic groups containing heteroatoms. Two of the asterisks indicate bonding to the main chain of the resin, and the other two indicate bonding to the side chains in the general formula (1) above (i.e., Z3-(C=O)- and Z4-(C=O)-, or Z5-(C=O)- and Z6-(C=O)-).} [ka] {In the formula, Z2 is selected from the group consisting of single bonds, organic groups having 1 to 30 carbon atoms, and organic groups containing heteroatoms. Two of the asterisks represent bonds to the main chain of the resin, and the other two represent bonds to the side chains in the general formula (1) above.}

[0025] The organic groups having 1 to 10 carbon atoms represented by R8 and R9 in the above general formula (4) are preferably linear or branched alkyl groups. Introducing alkyl groups to the aromatic ring improves the solubility of the (A) copolymer resin in the developer, making it easier to ensure contrast with the exposed area and improving the resolution of the relief pattern. In addition, introducing alkyl groups to the aromatic ring reduces the polarizability, resulting in low dielectric properties.

[0026] In the above general formula (4), R8 and R9 are preferably organic groups having 1 to 4 carbon atoms, more preferably alkyl groups having 1 to 4 carbon atoms, from the viewpoint of chemical resistance. Examples include methyl groups, ethyl groups, propyl groups, and butyl groups, with methyl groups being particularly preferred.

[0027] In the above general formula (1), it is more preferable that the structures represented by X1, X2, and X3 include at least one structure selected from the group consisting of the following general formula (5). General formula (5): [ka] *Two of the elements represent bonding to the resin main chain, and the other two represent bonding to the side chains in the general formula (1) above. The structures of X1, X2, and X3 in the general formula (1) above are not limited to the structures listed in (3), (4), and (5) above. The above structures may be one type or a combination of two or more types.

[0028] In the above general formula (1), the divalent organic groups represented by Y1 and Y2 are aliphatic chains (alkylene groups) having 6 to 40 carbon atoms, preferably 6 to 20 carbon atoms, such as heptylene, octylene, nonylene, decylene, and undecylene groups; and aromatic groups having 6 to 40 carbon atoms. In terms of achieving both heat resistance and photosensitivity, aromatic groups are preferred, more preferably aromatic groups having 6 to 40 carbon atoms, for example, the following general formula (6): [ka] {In formula (6), R 11m6 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, m7 is an integer from 1 to 3, and m6 is an integer from 1 to 4. Examples of groups having the structure represented by} include, but are not limited to, these. The divalent organic groups represented by Y1 and Y2 may be one type or a combination of two or more types. The Y1 and Y2 groups having the structure represented by the above formula (6) are particularly preferred in that they achieve both heat resistance and photosensitive properties.

[0029] In the above general formula (1), Y1 and / or Y2 preferably include the structure shown in the following general formula (7) from the viewpoint of resolution and low dielectric properties. General formula (7): [ka] {In the formula, R8 and R9 are each independently organic groups 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 the group consisting of single bonds, organic groups having 1 to 30 carbon atoms, and organic groups containing heteroatoms. * indicates bonding to the main chain of the resin.}

[0030] The organic groups having 1 to 10 carbon atoms represented by R8 and R9 in the above general formula (7) are preferably linear or branched alkyl groups. Introducing alkyl groups to the aromatic ring improves the solubility of the (A) copolymer resin in the developer, making it easier to ensure contrast with the exposed area and improving the resolution of the relief pattern. In addition, introducing alkyl groups to the aromatic ring reduces the polarizability, resulting in low dielectric properties.

[0031] In the above general formula (7), R8 and R9 are preferably organic groups having 1 to 4 carbon atoms, more preferably alkyl groups having 1 to 4 carbon atoms, from the viewpoint of chemical resistance, such as methyl groups, ethyl groups, propyl groups, and butyl groups, and particularly preferably methyl groups. Examples of the above general formula (7) preferably include at least one structure selected from the group consisting of the following general formula (8). General formula (8): [ka] * indicates bonding to the main chain of the resin.

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

[0033] In the above general formula (1), it is preferable that at least one or all of X1, X2, X3, Y1, and Y2 do not contain halogen atoms from the viewpoint of suppressing copper corrosion in the thermosetting process. That is, it is more preferable that the copolymer resin (A) does not contain halogen atoms.

[0034] (A) In the copolymer resin, it is preferable that at least one of the skeletal components X1, X2, and X3 derived from the tetracarboxylic acid compound, and the skeletal components Y1 and Y2 derived from the diamine compound, has two or more benzene rings. The two or more benzene rings may be bonded to each other directly or via divalent or higher organic groups. The number of benzene rings may be three or more, four or more, six or less, five or less, or four or less, and more preferably four. It is even more preferable that the sum of the number of carbon atoms constituting X1, X2, and X3, which exhibit structures derived from the tetracarboxylic acid compound, and Y1 and Y2, which exhibit structures derived from the diamine compound, is greater than 39. (A) The copolymer resin having such a structure maintains the resolution of the negative-type photosensitive resin composition and tends to have low dielectric properties in the resulting cured relief pattern.

[0035] The photosensitive resin composition of this disclosure has an imide group concentration U in the polyimide of the polyimide of the polyimide-cured film obtained by heating and curing the photosensitive resin composition, which is 12 wt% to 26 wt%. In this specification, "imide group concentration U" refers to the ratio of the molecular weight of the imide group to the molecular weight of the repeating units containing structures derived from tetracarboxylic dianhydride and diamine compounds in the polyimide of the polyimide-cured film obtained by heating and curing the photosensitive resin composition at 350°C. The condition of heating and curing at 350°C is to clarify the standard for the aliphatic hydrocarbon group concentration T by using a state in which the copolymer resin is almost 100% imidized as the standard, and it is not intended that the photosensitive resin composition will be heated and cured at 350°C in actual use.

[0036] When the imide group concentration U is 12.0 wt% or higher, the resolution of the relief pattern tends to be good. The imide group concentration U is preferably 15 wt% or higher, and more preferably 17.5 wt% or higher. On the other hand, when the imide group concentration U is 26 wt% or lower, the dielectric loss tangent of the resulting polyimide cured film tends to be good. The imide group concentration U is more preferably 23.0 wt% or lower, and even more preferably 20.5 wt% or lower.

[0037] The imide group concentration U in the repeating units of the polyimide cured film is given by the following formula (I), using the molecular weight of the tetracarboxylic dianhydride and the molecular weight of the diamine compound used in the preparation of the copolymer resin (A): 70.02×2 / [Mw(A)+Mw(B)-36]×100 (I) {In formula (I), Mw(A) represents the molecular weight of the tetracarboxylic dianhydride, and Mw(B) represents the molecular weight of the diamine.} Furthermore, when using two or more types of tetracarboxylic dianhydrides and / or diamine compounds, for example, when preparing using two types of tetracarboxylic dianhydrides and / or diamines, the following formula (II) is used: 70.02×2 / [Mw(A1)×a1+Mw(A2)×a2+Mw(B1)×b1+Mw(B2)×b2-36]×100 (II) {In formula (II), Mw(A1) represents the molecular weight of the first tetracarboxylic dianhydride, Mw(A2) represents the molecular weight of the second tetracarboxylic dianhydride, a1 represents the content of the first tetracarboxylic dianhydride, a2 represents the content of the second tetracarboxylic dianhydride, Mw(B1) represents the molecular weight of the first diamine compound, Mw(B2) represents the molecular weight of the second diamine compound, b1 represents the content of the first diamine compound, and b2 represents the content of the second diamine compound. However, a1, a2, b1, and b2 satisfy a1+a2=1 and b1+b2=1, respectively.} This can be expressed similarly when three or more types of tetracarboxylic dianhydrides and / or diamines are used. When tetracarboxylic acids and / or tetracarboxylic dichlorides are used as raw materials, the calculation is performed using the mass of the corresponding tetracarboxylic dianhydride.

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

[0039] General formula (E1): [ka] In formula (E1), a1 comprises at least one bond of an amide bond, imide bond, urea bond, or urethane bond, b1 is a reactive substituent that crosslinks with heat or light, and e1 is a monovalent organic group having 1 to 30 carbon atoms. 12 , R 15 Each is independently a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and R 13 , R 14They are each independently a hydrogen atom, a monovalent or divalent organic group having 1 to 30 carbon atoms, or both are part of an aromatic ring or an aliphatic ring. However, R 13 and R 14 are not both hydrogen atoms, and R 13 and / or R 14 is linked to the main chain structure.

[0040] General formula (E2):

Chemical formula

[0041] The reactive substituent b1 that is crosslinked by heat or light is preferably at least one selected from, for example, an acrylic group, a methacrylic group, a vinyl group, an alkenyl group, a cycloalkenyl group, an alkadienyl group, a cycloalkadienyl group, a styryl group, an ethynyl group, an imino group, an isocyanate group, a cyanate group, a cycloalkyl group, an epoxy group, an oxetanyl group, a carbonate group, a hydroxyl group, a mercapto group, a methylol group, and an alkoxyalkyl group. From the viewpoint of film thickness uniformity, b1 is preferably at least one selected from an acrylic group, a methacrylic group, a vinyl group, an alkenyl group, a cycloalkenyl group, an alkadienyl group, a cycloalkadienyl group, a styryl group, and an ethynyl group. The methacrylic group is particularly preferred.

[0042] The reactive substituent g1 that crosslinks with heat or light is, for example, at least one selected from acrylic group, methacrylic group, vinyl group, alkenyl group, cycloalkenyl group, alkadienyl group, cycloalkadienyl group, styryl group, ethynyl group, imino group, isocyanate group, cyanate group, cycloalkyl group, epoxy group, oxetanyl group, carbonate group, hydroxyl group, mercapto group, methylol group, and alkoxyalkyl group. From the viewpoint of film thickness uniformity, it is preferable that g1 is at least one selected from acrylic group, methacrylic group, vinyl group, alkenyl group, cycloalkenyl group, alkadienyl group, cycloalkadienyl group, styryl group, and ethynyl group. Methacrylic group is particularly preferred for g1.

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

[0044] [ka]

[0045] (A) Method for producing a copolymer containing polyimide and a polyimide precursor A method for producing a copolymer comprising the polyimide and polyimide precursor of this disclosure comprises the following steps: (i) A diamine oligomer having repeating units of a polyimide structure is obtained by condensing a first diamine compound with a first tetracarboxylic dianhydride or its acid / substituted adduct and imidizing it; (ii) Synthesizing a polyimide-imide precursor moiety having a polyimide block moiety by condensing the above-mentioned diamine oligomer with a second tetracarboxylic dianhydride or its acid / substituted adduct; (iii) The polyimide precursor portion is synthesized by condensing the polyimide-imide precursor portion with a third tetracarboxylic dianhydride or its acid / substituted adduct and a second diamine compound. The first tetracarboxylic dianhydride, the second tetracarboxylic dianhydride and the third tetracarboxylic dianhydride may be the same or different from each other, at least one of the second tetracarboxylic dianhydride and the third tetracarboxylic dianhydride may be in the form of an acid / substituted 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.

[0046] (Preparation of acid / substituent adducts) The first, second, and third tetracarboxylic dianhydrides used in steps (i), (ii), and (iii) may be in the form of acidic dianhydrides, or in the form having an acidic moiety (HO-C(=O)-) and a substituent-added moiety (ZC(=O)-, where Z corresponds to Z3 to Z6 of general formula (1)) by pre-adding substituents to the side chains of the acidic dianhydrides (also referred to in this disclosure as "acid / substituted adduct"). However, at least one of the second and third tetracarboxylic dianhydrides is in the form of an acid / substituted adduct having a photopolymerizable functional group. Z3, Z4, Z5, and Z6 can be ester-linked (hereinafter also referred to as "acid / ester") or amide-linked (hereinafter also referred to as "acid / amide") as described above, and by using such acid / ester or acid / amide, ester-linked or amide-linked polyimide precursors can be prepared. Tetracarboxylic dianhydrides having a tetravalent organic group X1 with 6 to 40 carbon atoms, which are suitably used to prepare ester-linked or amide-linked polyimide precursors, are not limited to the tetracarboxylic dianhydrides derived from the structures listed above, but include, for example, pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, and biphenyl-3,3',4,4'-tetracarboxylic dianhydride. Examples include dianhydrides of tetracarboxylic acids, diphenylsulfone-3,3',4,4'-tetracarboxylic acid dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic acid dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, 4,4'-(4,4'-isopropylidene diphenoxy)phthalic anhydride, and 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride. Tetracarboxylic acid dianhydrides may be used individually or in combination of two or more.

[0047] These tetracarboxylic dianhydrides containing a tetravalent organic group X1 with 6 to 40 carbon atoms can be reacted with a compound having a photoreactive substituent (photopolymerizable functional group) (hereinafter also referred to as a "substituted compound") to obtain esterified or amidated tetracarboxylic acids (acid / ester or acid / amide). Furthermore, the above-mentioned substituted compound can be used to introduce reactive substituents to the ends of the main chain of copolymer (A). The order of the reaction varies depending on the introduction method.

[0048] Examples of substituent compounds (hereinafter referred to as "first substituent compound") suitably used in the synthesis of esterified tetracarboxylic acids (acids / esters) include alcohols having photopolymerizable functional groups. Preferred examples of alcohols having photopolymerizable functional groups include alcohols containing the structure of general formula (2), such as 2-hydroxyethyl methacrylate (HEMA), 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, and 2-hydroxy-3-t-butoxypropyl Examples include propyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

[0049] In addition to the alcohols having the above-mentioned photopolymerizable functional groups, saturated aliphatic alcohols having 1 to 4 carbon atoms are preferably used as optional saturated aliphatic alcohols. Specific examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, and the like.

[0050] Examples of substituent compounds (hereinafter referred to as "first substituent compound") that are suitably used in the synthesis of amidated tetracarboxylic acids (acid / amide compounds) include amines having photopolymerizable functional groups. Preferred examples of amines having photopolymerizable functional groups include amines containing the structure of general formula (2), such as 2-aminoethyl methacrylate, 2-aminoethyl acrylate, and 2-(tert-butylamino)ethyl methacrylate.

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

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

[0053] (Preparation of diamine oligomers) Process (i): A diamine oligomer having repeating units of a polyimide structure can be obtained by condensing a first tetracarboxylic dianhydride or its acid / substituted adduct with a first diamine compound and imidizing the resulting product. The first tetracarboxylic dianhydride used in the condensation reaction is preferably in the form of an acid dianhydride rather than an acid / substituted adduct, from the viewpoint of increasing the imide cyclization rate. For example, a first tetracarboxylic dianhydride containing a tetravalent organic group X1 with 6 to 40 carbon atoms can be condensed with an excess amount of a first diamine compound containing a divalent organic group Y1 with 6 to 40 carbon atoms, followed by heating and cyclization. The imidization conditions are not limited, but for example, heating at 160°C to 300°C for 1 to 10 hours is sufficient. A higher imide cyclization rate is preferable, and is not limited, but for example, 90% or more, 95% or more is preferred, and 99% or more or 100% is more preferred.

[0054] Examples of first diamine compounds having a divalent organic group Y1 with 6 to 40 carbon atoms, which are raw materials for diamine oligomers having a polyimide structure, include diamines having an aliphatic chain (alkylene group) with 6 to 40 carbon atoms, preferably 6 to 20 carbon atoms, such as 1,7-diaminoheptane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane; and diamines having an aromatic group with 6 to 40 carbon atoms. In addition to the diamines derived from the structures listed above, other diamines having aromatic groups include, for example, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl Nylmethane, 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,Examples include 2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, and bis{4-(4-aminophenoxy)phenyl}ketone, as well as those in which some of the hydrogen atoms on the benzene ring are substituted with alkyl chains such as methyl or ethyl groups, such as 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethitoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof. However, diamine compounds are not limited to these. These diamine compounds may be used individually or in combination of two or more. These diamine compounds can also be used as a second diamine compound.

[0055] (Preparation of copolymers containing polyimide and polyimide precursors) Step (ii): A polyimide-imide precursor portion (unit n2) having a polyimide block portion (unit n1) can be synthesized by condensing the diamine oligomer obtained above as a diamine with the second tetracarboxylic dianhydride or its acid / substituted adduct. The second tetracarboxylic dianhydride is preferably in the form of an acid / substituted adduct having a photopolymerizable functional group. The acid / substituted adduct is typically in a solution state dissolved in the reaction solvent after preparing the acid / substituted adduct by the above method. Preferably, under ice cooling, a suitable dehydrating condensation agent is added and mixed to make the acid / substituted adduct a polyacid anhydride. Then, a solvent in which the diamine oligomer obtained above is dissolved or dispersed is added dropwise, and the two are subjected to amide polycondensation to obtain a polyimide-imide precursor portion (unit n2). Diaminosiloxanes may be used in combination with the diamines having the divalent organic group Y1, which are used as raw materials for the diamine oligomer having a polyimide structure. Examples of the above-mentioned dehydration condensing agents include dicyclohexylcarbodiimide (DCC), 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate. In this manner, the intermediate polyacid anhydride is obtained.

[0056] Step (iii): The obtained polyimide-imide precursor portion can be further condensed with a third tetracarboxylic dianhydride or its acid / substituent adduct and a second diamine compound to synthesize a polyimide precursor portion (n3 unit). If the second tetracarboxylic dianhydride (or its acid / substituent adduct) and the third tetracarboxylic dianhydride (or its acid / substituent adduct) are identical, the excess amount of the second tetracarboxylic dianhydride (or its acid / substituent adduct) present in the reaction solvent after the synthesis of the polyimide-imide precursor portion may be used directly as the third tetracarboxylic dianhydride (or its acid / substituent adduct). A desired tetracarboxylic dianhydride (or its acid / substituent adduct) may be added to the system. If the first diamine compound and the second diamine compound are identical, the excess amount of the first diamine compound present in the reaction solvent after the synthesis of the diamine oligomer may be used directly as the second diamine compound. A desired diamine compound may be added to the system.

[0057] (Reactive resin end formation) By the following method, other reactive substituents that polymerize by heat or light, different from the photopolymerizable functional groups contained in the repeating units of copolymer (A), can be introduced to the ends of the main chain. (1) Prepare an acid / substituted adduct having a photopolymerizable functional group and a reactive substituent by reacting a second and / or third tetracarboxylic dianhydride with a first substituent-introduced compound having a photopolymerizable functional group, and then reacting it with a second substituent-introduced compound having a reactive substituent that reacts with heat or light different from that of the first substituent-introduced compound; or obtain an acid / substituted adduct having a photopolymerizable functional group and a reactive substituent by reacting a second and / or third tetracarboxylic dianhydride with a second substituent-introduced compound, and then reacting it with the first substituent-introduced compound; and / or (2) To prepare a diamine oligomer having a second reactive substituent by reacting a diamine oligomer with a compound to which a second substituent has been introduced; (3) Using the acid / substituted adduct having a photopolymerizable functional group and a reactive substituent obtained in (1) above, and / or the diamine oligomer having a reactive substituent obtained in (2) above, steps (ii) and (iii) of the method for producing copolymer (A) can be used to introduce a reactive substituent derived from the second substituent-introducing compound to the acid terminus and / or amine terminus of the main chain of copolymer (A).

[0058] The second substituent-introduced compound is preferably a compound that introduces the structures represented by the general formulas (E1) and (E2) above. Examples, though not limited to them, include 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 2-(2-methacryloyloxyethyloxy)ethyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, allylamine, and methacrylate chloride.

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

[0060] After the amide polycondensation reaction is complete, any water-absorbing by-products of the dehydrating condensation agent present in the reaction solution are filtered off as needed. Then, a suitable poor solvent, such as water, aliphatic lower alcohol, or a mixture thereof, is added to the solution containing the polymer components to precipitate the polymer components. Further purification of the polymer is carried out by repeating operations such as redissolution and reprecipitation as needed, and then vacuum drying is performed to isolate the copolymer containing the target polyimide and polyimide precursor. To improve the degree of purification, the polymer solution may be passed through a column packed with anion and / or cation exchange resin swollen with a suitable organic solvent to remove ionic impurities.

[0061] (A) The weight-average molecular weight of the copolymer 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 as polystyrene-equivalent weight-average molecular weight by gel permeation chromatography (GPC), from the viewpoint of the heat resistance and mechanical properties of the film obtained after heat treatment. A weight-average molecular weight of 8,000 or more is preferred because it has good mechanical properties, while a weight-average molecular weight of 150,000 or less is preferred because it has good dispersibility in the developer and good resolution of the relief pattern. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended to select the standard monodisperse polystyrene from STANDARD SM-105, an organic solvent standard sample manufactured by Showa Denko Corporation.

[0062] (B) Photopolymerization initiator (B) Photopolymerization initiators are compounds that generate radicals upon exposure to active light, enabling polymerization of compounds containing ethylenically unsaturated groups, etc. Examples of initiators that generate radicals upon exposure to active light include compounds containing structures such as benzophenone, N-alkylaminoacetophenone, oxime esters, acridine, and phosphine oxide.Examples include benzophenone, N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone), N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, acrylic benzophenone, 4-benzoyl-4'-methyldiphenyl Aromatic ketones such as rusulfides; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime) (manufactured by BASF Japan Ltd., Irgacure) Examples of oxime ester compounds include, but are not limited to, oxime ester compounds such as Oxe02, 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(o-benzoyl oxime) (manufactured by Joshu Kyoryoku Denshi Materials Co., Ltd., PBG305), and 1,2-propanedione,3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazole-3-yl]-,2-(o-acetyl oxime) (manufactured by Nikko Chemtec Co., Ltd., TR-PBG-326, product name); benzyl derivatives such as benzyldimethylketal; acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; N-phenylglycine derivatives such as N-phenylglycine; coumarin compounds; oxazole compounds; and phosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. The polymerization initiators described above (C) can be used individually or in combination of two or more. Among the above photopolymerization initiators, oxime ester compounds are particularly preferred from the viewpoint of resolution. Among these,

[0063] The amount of photopolymerization initiator added is 0.5 parts by mass or more and 30 parts by mass or less, preferably 3 parts by mass or more and 15 parts by mass or less, per 100 parts by mass of copolymer containing (A) polyimide and polyimide precursor. The above amount is preferably 0.5 parts by mass or more from the viewpoint of photosensitivity or patternability, and preferably 30 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the photosensitive resin composition.

[0064] (C) Solvent (C) The solvent is not limited to any solvent that can uniformly dissolve or suspend (A) a copolymer containing a polyimide and a polyimide precursor, and (B) a photopolymerization initiator. Examples of such solvents include γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoethyl, N,N-dimethylacetacetamide, ε-caprolactone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N,N-dimethylacetamide. These solvents may be used individually or in combination of two or more.

[0065] The above solvent can be used in an amount of, for example, 30 to 1,500 parts by mass, preferably 100 to 1,000 parts by mass, per 100 parts by mass of the copolymer containing (A) polyimide and polyimide precursor, depending on the desired coating film thickness and viscosity of the photosensitive resin composition. If 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 content of the alcohol without an olefinic double bond is 5% by mass or more, the storage stability of the photosensitive resin composition is improved, and when it is 50% by mass or less, the solubility of the copolymer containing (A) polyimide and polyimide precursor is improved.

[0066] (D) Silane coupling agent To improve the adhesion of the relief pattern, the photosensitive resin composition may optionally contain (D) a silane coupling agent. The (D) silane coupling agent preferably has a structure represented by the following general formula (9). General formula (9): [ka] In formula (9), R 21 R is at least one selected from the group consisting of substituents including epoxy groups, phenylamino groups, and ureido groups, 22 Each of these is an alkyl group having 1 to 4 carbon atoms, and R 23 is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, d is an integer from 1 to 3, and m4 is an integer from 1 to 6.

[0067] In general formula (9), d is not limited to any integer from 1 to 3, but from the viewpoint of adhesion to the metal redistribution layer, 2 or 3 is preferred, and 3 is more preferred. m4 is not limited to any integer from 1 to 6, but from the viewpoint of adhesion to the metal redistribution layer, 1 to 4 is preferred. From the viewpoint of developability, 2 to 5 is preferred.

[0068] R 21 The substituent is not limited to any substituent that includes any structure from the group consisting of an epoxy group, a phenylamino group, a ureido group, an isocyanate group, or an isocyanuric group. Among these, from the viewpoint of developability and adhesion of the metal redistribution layer, it is preferable that it be at least one selected from the group consisting of substituents containing a phenylamino group and substituents containing a ureido group, and more preferably substituents containing a phenylamino group. 22 The alkyl group is not limited to any group having 1 to 4 carbon atoms. Examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and t-butyl groups. 23 This is not limited to a hydroxyl group or an alkyl group having 1 to 4 carbon atoms. Examples of alkyl groups having 1 to 4 carbon atoms include R 22 Similar alkyl groups can be given as examples.

[0069] Examples of silane coupling agents containing epoxy groups include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane. An example of a silane coupling agent containing a phenylamino group is N-phenyl-3-aminopropyltrimethoxysilane. An example of a silane coupling agent containing a ureido group is 3-ureidopropyltrialkoxysilane. An example of a silane coupling agent containing an isocyanate group is 3-isocyanatetopropyltriethoxysilane.

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

[0071] (E) Radical polymerizable compounds To improve the resolution of the relief pattern and suppress curing shrinkage during thermal curing, the photosensitive resin composition may optionally contain (E) a radical polymerizable compound. Preferred such compounds are (meth)acrylic compounds that undergo radical polymerization with a photopolymerization initiator, and are not limited to the following, but include diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, di(meth)acrylates of ethylene glycol or polyethylene glycol, di(meth)acrylates of propylene glycol or polypropylene glycol, di(meth)acrylate or tri(meth)acrylate of glycerol, cyclohexane di(meth)acrylate, and di(meth)acrylate of 1,4-butanediol. Examples of compounds that can be used include acrylates, di(meth)acrylate of 1,6-hexanediol, di(meth)acrylate of neopentyl glycol, di(meth)acrylate of bisphenol A, (meth)acrylamide, its derivatives, 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, and ethylene oxide or propylene oxide adducts of these compounds. Among these radical polymerizable compounds, it is preferable to have three or more radical polymerizable groups from the viewpoint of suppressing curing shrinkage. Furthermore, these monomers may be used individually or as a mixture of two or more.

[0072] The content of the (E) radical polymerizable compound in the resin composition is 0.5% to 50% by mass per 100 parts by mass of the copolymer containing (A) polyimide and polyimide precursor, more preferably 5% to 40% by mass, and even more preferably 10% to 30% by mass, from the viewpoint of resolution and suppression of curing shrinkage.

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

[0074] (F) A thermal crosslinking agent refers to a compound that undergoes an addition reaction or condensation polymerization reaction upon heating. These reactions occur in combination with a copolymer resin containing (A) polyimide and a polyimide precursor, with (F) a thermal crosslinking agent, with other (F) thermal crosslinking agents, and with other components described later. The reaction temperature is preferably 150°C or higher.

[0075] Examples of (F) thermal crosslinking agents include alkoxymethyl compounds, epoxy compounds, oxetane compounds, bismaleimide compounds, allyl compounds, and blocked isocyanate compounds. From the viewpoint of suppressing curing shrinkage, (F) thermal crosslinking agents are preferably those containing nitrogen atoms.

[0076] Examples of alkoxymethyl compounds include, but are not limited to, the following compounds. [ka] [ka]

[0077] Examples of epoxy compounds include epoxy compounds containing a bisphenol A type group and hydrogenated bisphenol A diglycidyl ether (for example, Epolite 4000 manufactured by Kyoeisha Chemical Co., Ltd.). Examples of oxetane compounds include 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, bis[1-ethyl(3-oxetanyl)]methyl ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methyl]biphenyl, 4,4'-bis(3-ethyl-3-oxetanylmethoxy)biphenyl, ethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, diethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, and bis(3-ethyl-3-oxetanylmethyl) Examples include diphenoates, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, poly[[3-[(3-ethyl-3-oxetanyl)methoxy]propyl]silasesquioxane] derivatives, oxetanyl silicates, phenol novolac type oxetanes, 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene, OXT121 (manufactured by Toagosei, trade name), OXT221 (manufactured by Toagosei, trade name), etc. Examples of bismaleimide compounds include 1,2-bis(maleimide)ethane, 1,3-bis(maleimide)propane, 1,4-bis(maleimide)butane, 1,5-bis(maleimide)pentane, 1,6-bis(maleimide)hexane, 2,2,4-trimethyl-1,6-bis(maleimide)hexane, N,N'-1,3-phenylenebis(maleimide), and 4-methyl-N,N'-1,3-phenylenebis(maleimide). Examples include 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-maleimidephenoxy)phenyl]propane.Examples of allyl compounds include allyl alcohol, allylanisole, allyl benzoate, allyl cinnamate, N-alyloxyphthalimide, allylphenol, allylphenylsulfone, allylurea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl isocyanurate, triallyamine, triallyl isocyanurate, triallyl cyanurate, triallyamine, 1,3,5-benzenetricarboxylic acid triallyl, trimellitate triallyl, triallyl phosphate, triallyl phosphite, and triallyl citrate. Examples of blocked isocyanate compounds 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 from Asahi Kasei Corporation, Takenate B-882N from Mitsui Chemicals, Inc., and 7960, 7961, 7982, 7991, and 7992 from Baxenden, etc.), tolylene diisocyanate-based blocked isocyanates (e.g., Takenate B-830 from Mitsui Chemicals, Inc.), 4 Examples include ,4'-diphenylmethane diisocyanate-based blocked isocyanates (e.g., Takenate B-815N manufactured by Mitsui Chemicals, Inc., Bronate PMD-OA01 and PMD-MA01 manufactured by Daiei Sangyo Co., Ltd.), 1,3-bis(isocyanatemethyl)cyclohexane-based blocked isocyanates (e.g., Takenate B-846N manufactured by Mitsui Chemicals, Inc., Coronate BI-301, 2507 and 2554 manufactured by Tosoh Corporation), and isophorone diisocyanate-based blocked isocyanates (e.g., 7950, 7951 and 7990 manufactured by Baxenden). Among these, blocked isocyanates and bismaleimide compounds are preferred from the viewpoint of storage stability. (F) The thermal crosslinking agent may be used alone or in combination of two or more types.

[0078] The content of (F) the thermal crosslinking agent in the resin composition is 0.2% to 40% by mass per 100 parts by mass of the copolymer containing (A) polyimide and polyimide precursor, more preferably 1% to 20% by mass, and even more preferably 2% to 10% by mass, from the viewpoint of suppressing curing shrinkage of low dielectric properties.

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

[0080] From the viewpoint of suppressing the increase in viscosity when used in a resin composition, the filler is preferably in particulate form. Examples of particulate form include needle-shaped, plate-shaped, and spherical, but from the viewpoint of suppressing the increase in viscosity when used in a resin composition, the filler is preferably spherical.

[0081] Needle-shaped fillers include wollastonite, potassium titanate, xonotlite, aluminum borate, and needle-shaped calcium carbonate.

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

[0083] Examples of spherical fillers include calcium carbonate, silica, alumina, titanium dioxide, clay, hydrotalcite, magnesium hydroxide, zinc oxide, and barium titanate. Among these, silica, alumina, titanium dioxide, and barium titanate are preferred from the viewpoint of electrical properties and storage stability when used in resin compositions, with silica and alumina being more preferred.

[0084] For filler size, the primary particle diameter is defined as the size for spherical fillers, and the length of the longer side is defined as the size for plate-shaped or needle-shaped fillers. A size of 5 nm to 1000 nm is preferred, and 10 nm to 1000 nm is more preferred. A size of 10 nm or more tends to result in a sufficiently uniform resin composition, and a size of 1000 nm or less can impart photosensitivity. From the viewpoint of imparting photosensitivity, a size of 800 nm or less is preferred, 600 nm or less is more preferred, and 300 nm or less is particularly preferred. From the viewpoint of adhesion and uniformity of the resin composition, a size of 15 nm or more is preferred, 30 nm or more is more preferred, and 50 nm or more is particularly preferred.

[0085] The content of (G) filler in the resin composition is 1 vol% to 20 vol% per 100 parts by mass of the copolymer containing (A) polyimide and 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.

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

[0087] The photosensitive resin composition may further contain resin components other than the copolymer containing (A) polyimide and polyimide precursor. Examples of resin components that can be included in the photosensitive resin composition include polyimide, polyoxazole, polyoxazole precursor, phenol resin, polyamide, epoxy resin, siloxane resin, and acrylic resin. The amount of these resin components blended is preferably in the range of 0.01 parts by mass to 20 parts by mass per 100 parts by mass of the copolymer containing (A) polyimide and polyimide precursor.

[0088] The photosensitive resin composition may contain an organic compound containing a metal element. Preferably, the organic compound containing the metal element contains at least one metal element selected from the group consisting of titanium and zirconium in one molecule. Preferably, the organic group contains a hydrocarbon group or a hydrocarbon group containing a heteroatom. The inclusion of the organic compound increases the imidization rate of the polyimide precursor contained in the photosensitive resin composition, and reduces the dielectric loss tangent of the cured film. Examples of usable organotitanium or zirconium compounds include those in which an organic group is bonded to a titanium atom or zirconium atom via covalent or ionic bonds.

[0089] Specific examples of organotitanium or zirconium compounds are shown in I) to VII) below: I) As chelating compounds, compounds having two or more alkoxy groups are more preferred because they provide good storage stability and a good pattern for the photosensitive resin composition. Specific examples of chelating compounds include, but are not limited to, titanium bis(triethanolamine)diisopropoxide, titanium di(n-butoxide)bis(2,4-pentanedione), titanium diisopropoxidebis(2,4-pentanedione), titanium diisopropoxidebis(tetramethylheptanedione), titanium diisopropoxidebis(ethylacetoacetate), and compounds in which the titanium atoms of these compounds are substituted with zirconium atoms.

[0090] II) Examples of tetraalkoxy compounds include, but are not limited to, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearaloxide, titanium tetrakis[bis{2,2-(alyloxymethyl)butoxide}], and compounds in which the titanium atoms of these compounds are substituted with zirconium atoms.

[0091] III) Examples of titanocene or zirconocene compounds include pentamethylcyclopentadienyltitanium trimethoxide, bis(η 5 -2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium, bis(η 5 Examples include, but are not limited to, -2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium and compounds in which the titanium atoms of these compounds are substituted with zirconium atoms.

[0092] IV) Examples of monoalkoxy compounds include, but are not limited to, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, and compounds obtained by substituting the titanium atoms of these compounds with zirconium atoms.

[0093] V) Examples of titanium oxide or zirconium oxide compounds include, but are not limited to, titanium oxide bis(pentanedione), titanium oxide bis(tetramethylheptanedione), phthalocyanine titanium oxide, and compounds in which the titanium atoms of these compounds are substituted with zirconium atoms.

[0094] VI) Examples of titanium tetraacetylacetonate or zirconium tetraacetylacetonate compounds include, but are not limited to, titanium tetraacetylacetonate and compounds obtained by substituting the titanium atoms of these compounds with zirconium atoms.

[0095] VII) Examples of titanate coupling agents include, but are not limited to, isopropyltridodecylbenzenesulfonyl titanate.

[0096] Among the above I) to VII), it is preferable from the viewpoint of achieving a better dielectric loss tangent that the organotitanium compound is at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds. In particular, titanium diisopropoxide bis(ethyl acetate), titanium tetra(n-butoxide), and bis(η 5 -2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium is preferred.

[0097] When incorporating an organotitanium or zirconium compound, the amount is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, relative to the copolymer containing (A) polyimide and polyimide precursor. If the amount is 0.01 parts by mass or more, a good imidization rate of the resin composition and dielectric loss tangent of the cured film are obtained, while if it is 10 parts by mass or less, excellent storage stability is obtained, which is preferable.

[0098] The photosensitive resin composition can improve the imidation rate of the polyimide precursor contained in the resin composition and reduce the dielectric loss tangent of the cured film using the resin composition by containing an organic compound containing the above-mentioned metal element. Although not bound by theory, the reason for improving the imidation rate of the polyimide precursor is thought to be that the metal element contained in the organic compound containing the metal element coordinates to the carbonyl group derived from the ester group, amide group, and / or carboxyl group of the polyimide precursor, thereby reducing the electron density of the carbon atom of the carbonyl group and promoting the ring-closing reaction.

[0099] The photosensitive resin composition may optionally contain a sensitizer to improve photosensitivity. Examples of sensitizers include Michla's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylaminocinnamyridane indano n, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetone Examples include ethyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazol, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, and 2-(p-dimethylaminobenzoyl)styrene. These can be used individually or in combination of several types (e.g., 2 to 5 types). The amount of sensitizer added is preferably 0.1 to 25 parts by mass per 100 parts by mass of copolymer containing (A) polyimide and polyimide precursor.

[0100] The photosensitive resin composition may optionally contain a thermal polymerization inhibitor to improve the viscosity and photosensitivity stability of the photosensitive resin composition, especially when stored in a solvent-containing solution. Examples of thermal polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt. These thermal polymerization inhibitors may be used individually or as a mixture of two or more. The amount of thermal polymerization inhibitor added is preferably in the range of 0.005 parts by mass to 12 parts by mass per 100 parts by mass of the copolymer containing (A) polyimide and polyimide precursor.

[0101] When using a substrate made of copper or a copper alloy, the photosensitive resin composition may optionally contain an azole compound to suppress discoloration of the substrate. 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-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, and 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benz Examples include zotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazol, 5-methyl-1H-tetrazol, 5-phenyl-1H-tetrazol, 5-amino-1H-tetrazol, 1-methyl-1H-tetrazol, etc. Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. Furthermore, these azole compounds may be used individually or as a mixture of two or more.

[0102] The amount of azole compound blended is preferably 0.1 to 20 parts by mass per 100 parts by mass of copolymer containing (A) polyimide and polyimide precursor, and more preferably 0.5 to 5 parts by mass from the viewpoint of photosensitivity characteristics. If the amount of azole compound blended is 0.1 parts by mass or more per 100 parts by mass of copolymer containing (A) polyimide and polyimide precursor, discoloration of the copper or copper alloy surface is suppressed when the photosensitive resin composition is formed on copper or a copper alloy, while if it is 20 parts by mass or less, it is preferable because it has excellent photosensitivity.

[0103] When a photosensitive resin composition is used with a substrate made of copper or a copper alloy, it may contain a hindered phenol compound to suppress discoloration of the substrate. Examples of hindered phenol compounds include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), and 4,4'-butylidene-bis(3-methyl-6 -t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-cinnamamide), 2,2'-methylene-bis(4-methyl Tris-(3,5-di-t-butyl-4-hydroxybenzyl)-, 2,2'-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)- 1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy C-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)- Trione, 1,3,5-Tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3 Examples include, but are not limited to, 5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione. Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione is particularly preferred.

[0104] The amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass per 100 parts by mass of the copolymer containing (A) polyimide and polyimide precursor, and more preferably 0.5 to 10 parts by mass from the viewpoint of photosensitivity characteristics. If the amount of the hindered phenol compound is 0.1 parts by mass or more per 100 parts by mass of the copolymer containing (A) polyimide and polyimide precursor, for example, when a photosensitive resin composition is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented, while if it is 20 parts by mass or less, it is preferable because it has excellent photosensitivity.

[0105] <Polyimide cured film and method for producing the same> This disclosure also provides a method for producing a polyimide-cured film, which includes a step of converting a photosensitive resin composition into a polyimide. The method for producing a polyimide-cured film according to this disclosure includes, for example, the following steps (1) to (5): (1) A step of applying the photosensitive resin composition of the present disclosure onto a substrate to form a photosensitive resin layer on the substrate; (2) A step of heating and drying the obtained photosensitive resin layer; (3) Exposing the photosensitive resin layer after heating and drying; (4) A step of developing the photosensitive resin layer after exposure; and (5) A step of heat-treating the photosensitive resin layer after development to form a polyimide cured film; Includes.

[0106] The photosensitive resin composition used in the method for producing a cured film preferably contains a copolymer comprising 100 parts by mass of polyimide and a polyimide precursor, 0.5 to 30 parts by mass of a photosensitive agent, and 100 to 1000 parts by mass of a solvent. It is more preferable that the photosensitive agent contains a photoradical polymerization initiator, and it is even more preferable that the photosensitive resin composition is of the negative type.

[0107] The specific steps in the method for manufacturing a cured film can be carried out according to steps (1) to (5) of the method for manufacturing a cured film described above. A typical embodiment of each step will be described below.

[0108] (1) Photosensitive resin layer formation process In this process, the photosensitive resin composition of the present disclosure is applied to a substrate and, if necessary, subsequently dried to form a photosensitive resin layer. Conventional application methods for photosensitive resin compositions can be used, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, or spray application using a spray coater.

[0109] (2) Heating and drying process If necessary, the photosensitive resin composition film can be heated and dried. Drying methods include air drying, heating and drying in an oven or on a hot plate, and vacuum drying. Furthermore, it is desirable to dry the coating film under conditions that prevent imidization of the polyimide precursor portion (polyamic acid ester) of the (A) copolymer in the photosensitive resin composition. Specifically, when air drying or heating and drying is performed, drying can be carried out at 20°C to 140°C for 1 minute to 1 hour. By doing so, a photosensitive resin layer can be formed on the substrate.

[0110] (3) Exposure process In this step, the photosensitive resin layer formed above is exposed to light. Exposure devices such as contact aligners, mirror projection machines, and steppers are used. Exposure can be performed via a patterned photomask or reticle, or directly. The light source used for exposure is, for example, an ultraviolet light source.

[0111] After exposure, post-exposure baking (PEB) and / or pre-development baking may be performed as needed, using any combination of temperature and time, for purposes such as improving photosensitivity. The preferred baking conditions are a temperature of 40 to 120°C and a time of 10 to 240 seconds, but are not limited to this range as long as they do not impair the properties of the negative-type photosensitive resin composition of this embodiment.

[0112] (4)Developing process In this step, the photosensitive resin layer after exposure is developed to form a relief pattern. If the photosensitive resin composition is of the negative type, the unexposed portion of the photosensitive resin layer after exposure is developed and removed. As a development method for developing the photosensitive resin layer after exposure (irradiation), any method can be selected and used from conventionally known photoresist development methods, such as the rotary spray method, the paddle method, and the immersion method with ultrasonic treatment. In addition, after development, if necessary, a post-development bake may be performed using any combination of temperature and time for purposes such as adjusting the shape of the relief pattern. As the developer used for development, for example, a good solvent for the negative type photosensitive resin composition, or a combination of the good solvent and a poor solvent is preferred. As good solvents, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. Suitable poor solvents include, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When mixing a good solvent and a poor solvent, it is preferable to adjust the ratio of the poor solvent to the good solvent based on the solubility of the polymer in the negative-type photosensitive resin composition. It is also possible to use two or more of each solvent, for example, in combination with several types. In the process of developing the photosensitive resin layer after exposure, it is preferable to perform the above coating to developing steps so that a photosensitive resin layer with a thickness of 10 μm to 15 μm is obtained.

[0113] (5) Polyimide cured film formation process In this process, the relief pattern obtained by the above development is heated to disperse the photosensitive component, and (A) the copolymer is imidized to be converted into a cured relief pattern made of polyimide. As the method of heat curing, various methods can be selected, such as those using a hot plate, those using an oven, and those using a temperature-programmable heating oven. The heating can be carried out, for example, under the conditions of 160 °C to 400 °C for 30 minutes to 5 hours. As the atmosphere gas during heat curing, air may be used, or an inert gas such as nitrogen or argon may be used. In the above manner, a cured relief pattern (polyimide cured film) can be manufactured.

[0114] The method for manufacturing a polyimide cured film of the present disclosure is, for example, a method for manufacturing a cured film including applying the photosensitive resin composition of the present disclosure on a substrate, performing an exposure process, a development process, and then a heat treatment, and the dielectric tangent of the cured film is preferably 0.003 to 0.011 when measured at 40 GHz by the perturbation method split cylinder resonator method. The dielectric tangent can be measured by the perturbation method split cylinder resonator method shown in the examples described later.

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

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

[0117] 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): [Chemical formula] {In 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.}

[0118] <Display device> This disclosure also provides a display device comprising a display element and a cured film provided on the upper part of the display element, wherein the cured film is the cured relief pattern described above, using the photosensitive resin composition of this disclosure. Here, the cured relief pattern may be laminated in direct contact with the display element, or it may be laminated with another layer in between. For example, the cured film can be a surface protective film, insulating film, and planarization film for TFT liquid crystal display elements and color filter elements, a projection for an MVA type liquid crystal display device, and a partition for the cathode of an organic EL element.

[0119] In addition to applications in semiconductor devices as described above, the photosensitive resin composition of this disclosure is also useful for applications such as interlayer insulation of multilayer circuits, cover coatings for flexible copper-clad sheets, solder resist films, and liquid crystal alignment films.

[0120] <Method for producing a photosensitive resin composition> The method for producing the photosensitive resin composition of this disclosure comprises the steps of: (A) producing a copolymer resin by the method of this disclosure as described in "(A) Method for producing a copolymer resin containing a polyimide and a polyimide precursor" above; and (C) mixing 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. Optionally, the (D) silane coupling agent, (E) radical polymerizable compound, (F) thermal crosslinking agent, (G) filler, and (H) other components described above may be added. [Examples]

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

[0122] <Measurement and Evaluation Methods> (1) Weight average molecular weight The weight-average molecular weight (Mw) of diamine oligomers and copolymer resins was measured by gel permeation chromatography (on a standard polystyrene basis). The columns used for the measurement were Showa Denko Corporation's Shodex 805M / 806M in series. The standard monodisperse polystyrene used was Showa Denko Corporation's Shodex STANDARD SM-105. The developing solvent was N-methyl-2-pyrrolidone, and the detector used was Showa Denko Corporation's Shodex RI-930.

[0123] (2) Measurement of the imide structure introduction rate of copolymer resin A polymer solution was prepared by dissolving 10 g of copolymer resin in a mixed solvent consisting of γ-butyrolactone and DMSO (weight ratio 90:10) and adjusting the amount of solvent so that the viscosity was approximately 25 poise. The polymer solution was rotate-coated onto a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625 ± 25 μm) using a coater developer (D-Spin 60A, manufactured by SOKUDO Co., Ltd.) and heated and dried on a hot plate at 110°C for 3 minutes to form a photosensitive resin layer approximately 10 μm thick. The above photosensitive resin layer was measured using an ATR-FTIR measuring device (Nicolet Continuum, manufactured by Thermo Fisher Scientific) with a Si prism, with a measurement range of 4000 cm². -1 ~700cm -1 Measurements were taken 50 times. The cured film measured 1380 cm². -1 Nearby (1350cm) -1 ~1450cm -1 (If there are multiple peaks, the peak height of the one with the highest peak intensity) and 1500cm -1 Nearby (1460cm) -1 ~1550cm -1 The imidation index of 1 was calculated by dividing the result by the peak height of the peak with the highest peak intensity (if there were multiple peaks). The imidation structure introduction rate was calculated by dividing the result by the imidation index of 2 of a cured film cured separately at 350°C under the same conditions.

[0124] (3) Resolution and development time of cured relief pattern on Cu substrate On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industries, Ltd., thickness 625±25μm), 200nm thick Ti and 400nm thick Cu were sputtered in that order using a sputtering apparatus (L-440S-FHL model, manufactured by Canon Anelva Corporation). Subsequently, a photosensitive resin composition prepared by the method described later was rotary coated onto this wafer using a coater developer (D-Spin60A model, manufactured by SOKUDO Corporation), and heated and dried on a hot plate at 110°C for 3 minutes to form a photosensitive resin layer approximately 13.5μm thick. This photosensitive resin layer was subjected to a 600mJ / cm² test using a Prisma GHI (manufactured by Ultratech Corporation) equipped with an i-line filter, using a test pattern mask. 2 The photosensitive resin layer was irradiated with energy. Next, this photosensitive resin layer was spray-developed using cyclopentanone as the developer in a coater developer (D-Spin 60A, SOKUDO Corporation) and rinsed with propylene glycol methyl ether acetate to obtain a relief pattern on Cu. The spray development time was defined as the development time. The wafer on which the relief pattern was formed on Cu was heat-treated in a temperature-boosting programmable curing furnace (VF-2000, Koyo Lindbergh Corporation) at 230°C for 2 hours under a nitrogen atmosphere to obtain a cured relief pattern made of resin approximately 10 μm thick on Cu. The fabricated relief pattern was observed under an optical microscope to determine the size of the minimum aperture pattern. At this time, if the area of ​​the aperture of the obtained pattern was 1 / 2 or more of the corresponding pattern mask aperture area, it was considered resolved, and the resolution was determined according to the following evaluation criteria based on the length of the mask aperture side (size of the aperture pattern) corresponding to the smallest area of ​​the resolved aperture. (Evaluation Criteria) A: Minimum aperture pattern size is less than 10 μm B: Minimum aperture pattern size is 10 μm or more and less than 15 μm C: Minimum aperture pattern size is 15 μm or more and less than 20 μm. D: Minimum aperture pattern size is 20 μm or larger In this disclosure, results of C or higher are considered preferable.

[0125] (4) Measurement of dielectric properties (relative permittivity: Dk, dielectric loss tangent: Df) A 100 nm thick layer of aluminum (Al) was sputtered onto a 6-inch silicon wafer (manufactured by Fujimi Electronics Industries, Ltd., thickness 625 ± 25 μm) using a sputtering apparatus (L-440S-FHL model, manufactured by Canon Anelva Corporation) to prepare a sputtered Al wafer substrate. The photosensitive resin composition prepared by the method described below was spin-coated onto the sputtered Al wafer substrate using a spin-coating apparatus (D-spin60A model, manufactured by SOKUDO Corporation), and heated and dried at 110°C for 180 seconds to form a photosensitive resin layer approximately 13.5 μm thick. Subsequently, exposure at 600 mJ / cm² was applied using an aligner (PLA-501F, manufactured by Canon Corporation). 2 The entire surface was exposed using the GHz line, and a cured resin film approximately 10 μm thick was fabricated on an Al wafer by heat curing treatment at 230°C for 2 hours under a nitrogen atmosphere using a vertical curing furnace (Koyo Lindbergh, model VF-2000B). This cured film was cut into 80 mm x 62 mm (for 10 GHz measurement) and 40 mm x 30 mm (for 40 GHz measurement) sections using a dicing saw (Disco, model DAD-2H / 6T), and peeled off from the silicon wafer by immersion in a 10% hydrochloric acid aqueous solution to obtain film samples. The relative permittivity (Dk) and dielectric loss tangent (Df) of the film samples at 10 GHz and 40 GHz were measured, respectively, using the resonator perturbation method. Details of the measurement method are as follows. (Measurement method) Perturbation-type split-cylinder resonator method (Measurement sample humidity control) 23℃ / 50%RH for 24 hours (Measurement conditions) 23℃ / 50%RH (Device configuration) Network analyzer: PNA Network analyzer N5224B (Manufactured by KEYSIGHT) Split-cylinder resonator: CR-710 (manufactured by Kanto Electronics Applied Development Co., Ltd., measurement frequency: approximately 10 GHz) CR-740 (manufactured by Kanto Electronics Applied Development Co., Ltd., measurement frequency: approximately 40 GHz)

[0126] (5) Measurement of residual film rate after curing On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industries, Ltd., thickness 625±25μm), 200nm thick Ti and 400nm thick Cu were sputtered in that order using a sputtering apparatus (L-440S-FHL model, manufactured by Canon Anelva Corporation). Subsequently, a photosensitive resin composition prepared by the method described later was rotary coated onto this wafer using a coater developer (D-Spin60A model, manufactured by SOKUDO Corporation), and heated and dried on a hot plate at 110°C for 3 minutes to form a photosensitive resin layer approximately 13.5μm thick. After that, exposure at 800mJ / cm² was applied using an aligner (PLA-501F, manufactured by Canon Corporation). 2 Full-surface exposure was performed using the ghi line. Subsequently, the coating film formed on the wafer was spray-developed using cyclopentanone in a developing machine (D-SPIN636 model, manufactured by Dainippon Screen Mfg. Co., Ltd., Japan). After rinsing with propylene glycol methyl ether acetate, it was dried by spin-drying. The film thickness after development was measured and designated as film thickness 1. This developed film was further heat-cured in a vertical curing furnace (Koyo Lindbergh, model VF-2000B) under a nitrogen atmosphere at 230°C for 2 hours. The film thickness after this heat treatment was measured and designated as film thickness 2. Using these film thicknesses, the residual film percentage (percentage and %) after curing was calculated using the following formula. Percentage of residual film after curing = Film thickness 2 / Film thickness 1 Percentage of residual film after curing (%) = Film thickness 2 / Film thickness 1 × 100 Furthermore, the residual film rate (percentage) after curing and the dielectric loss tangent (tanδ) 40 ) quotient (RFA (ratio) / tanδ 40 ) was calculated.

[0127] (6) Evaluation of copper adhesion On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industries, Ltd., thickness 625±25μm), 200nm thick Ti and 400nm thick Cu were sputtered in that order using a sputtering apparatus (L-440S-FHL model, manufactured by Canon Anelva Corporation). Subsequently, a photosensitive resin composition prepared by the method described later was rotary coated onto this wafer using a coater developer (D-Spin60A model, manufactured by SOKUDO Corporation), and heated and dried on a hot plate at 110°C for 3 minutes to form a photosensitive resin layer approximately 13.5μm thick. After that, exposure at 800mJ / cm² was applied using an aligner (PLA-501F, manufactured by Canon Corporation). 2 The entire surface was exposed using the ghi line, and a heat curing treatment was performed at 230°C for 2 hours under a nitrogen atmosphere using a vertical curing furnace (Koyo Lindbergh, model VF-2000B) to fabricate a cured film of resin approximately 10 μm thick on a Cu wafer. The adhesion characteristics between the copper substrate and the cured resin coating were evaluated on the heat-treated film according to the cross-cut method of JIS K 5600-5-6 standard, based on the following criteria. (Evaluation Criteria) A: The number of grid cells in the cured resin coating adhered to the substrate is 80 or more to 100. B: The number of grid cells in the cured resin coating adhered to the substrate is 60 or more but less than 80. C: The number of grid cells in the cured resin coating adhered to the substrate is 40 or more but less than 60. D: The number of grid cells in the cured resin coating adhered to the substrate is less than 40. In this disclosure, a result of B or higher is considered preferable.

[0128] (7) Storage stability The photosensitive resin composition described later was prepared and allowed to stand at room temperature for 24 hours. Viscosity was then measured at 23°C using an E-type viscometer (Viscomate VM-150III, manufactured by Toki Sangyo). This initial viscosity was defined as viscosity 1. The photosensitive resin composition was then stored at 40°C for 3 days, and viscosity was measured again under the same conditions. This post-heat-treated viscosity was defined as viscosity 2. Using these viscosities, storage stability was calculated using the following formula. Viscosity change rate (%) = (|Viscosity 2 - Viscosity 1| / Viscosity 1) × 100 (Evaluation Criteria) A: Viscosity change rate is less than 3% B: Viscosity change rate is 3% or more but less than 5% C: Viscosity change rate is 5% or more but less than 10% D: Viscosity change rate is 10% or more In this disclosure, results of C or higher are considered preferable.

[0129] <Manufacturing of Diamine X-1> A 5L four-necked flask was purged with Ar, and 172.02 g of 4,4'-butylindenbis(6-tert-butyl-m-cresol), 155.84 g of 4-chloronitrobenzene, and 1.5 L of DMF were added and stirred. 186.42 g of K2CO3 was added, and the mixture was heated at 150°C for 5 hours. The disappearance of the starting materials and intermediates was confirmed by TLC. After cooling to room temperature, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure at 80°C. The concentrated residue was poured into 1.6 L of deionized water, and then further purified by adding 2.5 L of ethyl acetate in three separate steps. The organic layer was collected and dried with MgSO4. After drying, it was filtered to remove impurities, dissolved in 800 mL of toluene, and then added to 4.0 L of methanol and stirred for 30 minutes. After stirring, the filtrate was collected and dried at 80°C for 12 hours. The dried reaction product was placed in a 5L four-necked flask purged with Ar, and then 19.04g of 5% Pd / C(EA) and 1.9L of THF were added and the mixture was stirred. The flask was heated to 40°C and H2 bubbling (10mL / min) was performed to carry out the reduction reaction for 24 hours. The reaction mixture was filtered through Celite, the fraction of the target product was recovered by silica gel chromatography, and concentrated under reduced pressure to obtain diamine X-1.

[0130] <(A) Production of diamine compounds having repeating units of polyimide structure> Synthesis of polyimide (diamine oligomer W-1): In a 0.5-liter separable flask equipped with a Dean-Stark tube and a condenser, 41.6 g of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride (BPADA) as the acid component, 34.0 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) as the diamine component, and 176.4 g of N-methylpyrrolidone (NMP) as the solvent were added and dissolved with stirring. Further stirring was performed by adding 42.3 g of toluene, and the mixture was then heated to 185°C under a nitrogen atmosphere. After stirring at 185°C for 2.5 hours, the toluene and water produced by imidization were removed from the system over 1.5 hours. The mixture was then cooled to room temperature to obtain a solution of diamine oligomer W-1 having repeating polyimide units. The weight-average molecular weight (Mw) of this diamine oligomer W-1 was measured to be 3,000. 1 ¹H-NMR measurements were performed, and the imide cyclization rate was confirmed by comparing the peaks originating from the amide bond with those originating from the aromatic ring of the polyimide. The imide cyclization rate was over 99%.

[0131] Synthesis of polyimide (diamine oligomer W-2): Diamine oligomer W-2 was obtained by carrying out the reaction in the same manner as described in the method for synthesizing 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, 220 g of NMP was used as the solvent, and 52.8 g of toluene was used. The weight-average molecular weight (Mw) of this diamine oligomer W-2 was measured to be 5,000. 1 The imide ring closure rate obtained from 1H-NMR measurements was over 99%.

[0132] Synthesis of polyimide (diamine oligomer W-3): Diamine oligomer W-3 was obtained by carrying out the reaction in the same manner as described in the method for synthesizing diamine oligomer W-1, except that 24.8 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) was used instead of 41.6 g of BPADA, 65.7 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) was used instead of 34.0 g of m-TB, 211 g of NMP was used as the solvent, and 50.7 g of toluene was used. The weight-average molecular weight (Mw) of this diamine oligomer W-3 was measured to be 2,700. 1 The imide ring closure rate obtained from 1H-NMR measurements was over 99%.

[0133] Synthesis of polyimide (diamine oligomer W-4): Diamine oligomer W-4 was obtained by carrying out the reaction in the same manner as described in the method for synthesizing 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, 222 g of NMP was used as the solvent, and 53.0 g of toluene was used. The weight-average molecular weight (Mw) of this diamine oligomer W-4 was measured to be 3,000. 1 The imide ring closure rate obtained from 1H-NMR measurements was over 99%.

[0134] Synthesis of polyimide (diamine oligomer W-5): Diamine oligomer W-5 was obtained by carrying out the reaction in the same manner as described in the method for synthesizing 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, 269 g of NMP was used as the solvent, and 64.5 g of toluene was used. The weight-average molecular weight (Mw) of this diamine oligomer W-5 was measured to be 3,500. 1The imide ring closure rate obtained from 1H-NMR measurements was over 99%.

[0135] Synthesis of polyimide (diamine oligomer W-6): Diamine oligomer W-6 was obtained by carrying out the reaction in the same manner as described in the method for synthesizing 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, 188 g of NMP was used as the solvent, and 45.1 g of toluene was used. The weight-average molecular weight (Mw) of this diamine oligomer W-6 was measured to be 2,900. 1 The imide ring closure rate obtained from 1H-NMR measurements was over 99%.

[0136] Synthesis of polyimide (diamine oligomer W-7): Diamine oligomer W-7 was obtained by carrying out the reaction in the same manner as described in the method for synthesizing diamine oligomer W-1, except that 37.2 g of BAFL was used instead of 34.0 g of m-TB, 145 g of NMP was used as the solvent, and 34.7 g of toluene was used. The weight-average molecular weight (Mw) of this diamine oligomer W-7 was measured to be 8,200. 1 The imide ring closure rate obtained from 1H-NMR measurements was over 99%.

[0137] Synthesis of polyimide (diamine oligomer W-8): Diamine oligomer W-8 was obtained by carrying out the reaction in the same manner as described in the method for synthesizing 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 this diamine oligomer W-8 was measured to be 2,500. 1 The imide ring closure rate obtained from 1H-NMR measurements was over 99%.

[0138] Synthesis of polyimide (diamine oligomer W-9): Diamine oligomer W-9 was obtained by carrying out the reaction in the same manner as described in the method for synthesizing diamine oligomer W-1, except that 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, 236 g of NMP was used as the solvent, and 56.7 g of toluene was used. The weight-average molecular weight (Mw) of this diamine oligomer W-9 was measured to be 3,200. 1 The imide ring closure rate obtained from 1H-NMR measurements was over 99%.

[0139] Synthesis of polyimide (diamine oligomer W-10): Diamine oligomer W-10 was obtained by carrying out the reaction in the same manner as described in the method for synthesizing 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 this diamine oligomer W-10 was measured to be 3,700. 1 The imide ring closure rate obtained from 1H-NMR measurements was over 99%.

[0140] <(A) Production of copolymer resins containing polyimide and polyimide precursors> Synthesis of polymer A-1: As the acid component, 20.9 g of BPADA was placed in 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 the mixture was heated at 50°C for 4 hours. After the exothermic reaction was complete, the mixture was allowed to cool to room temperature. After standing for another 16 hours, the reaction mixture was obtained.

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

[0142] The resulting reaction solution was added to 1000 g of ethyl alcohol to produce a precipitate consisting of crude polymer. The crude polymer was filtered and dissolved in 270 g of γ-butyrolactone to obtain a crude polymer solution. The obtained crude polymer solution was then dissolved in an anion exchange resin (Organo Corporation's "Amberlist"). TM The polymer solution was purified using "15JWET" to obtain a polymer solution. The obtained polymer solution was added dropwise to 3800 g of water to precipitate the polymer, and the resulting precipitate was filtered and then vacuum dried to obtain powdered polymer A-1. The weight-average molecular weight (Mw) of polymer A-1 was 30,000, and the imide group introduction rate was 0.43. Furthermore, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-1 was 16.0 wt%. Note that the "imide group concentration U" was calculated by converting it to the polyimide of the polyimide-cured film obtained by heating and curing at 350°C (the same applies below).

[0143] Synthesis of polymer A-2: As the acid component, 15.2 g of BPADA was placed in 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 exothermic reaction was complete, the mixture was allowed to cool to room temperature. After standing for another 16 hours, the reaction mixture was obtained.

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

[0145] The subsequent purification process was carried out in the same manner as described in the synthesis method for polymer A-1 to obtain polymer A-2. The weight-average molecular weight (Mw) of polymer A-2 was 24,000, and the imide group introduction rate was 0.58. Furthermore, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-2 was 20.1 wt%.

[0146] Synthesis of polymer A-3: As the acid component, 15.2 g of BPADA was placed in a 1-liter separable flask, and 7.9 g of HEMA (the first substituent compound) and 30.8 g of GBL were added. While stirring at room temperature, 4.6 g of pyridine was added, and the mixture was heated at 50°C for 4 hours. After the exothermic reaction was complete, it was allowed to cool to room temperature. After standing for another 16 hours, the reaction mixture was obtained (first reaction).

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

[0148] In parallel with the second reaction described above, under ice cooling, a solution of 11.9 g of DCC dissolved in 20 g of GBL was added to the reaction mixture from the first reaction over 40 minutes while stirring. Subsequently, a reaction mixture solution of diamine oligomer W-1 obtained in the second reaction was added as the diamine component over 60 minutes while stirring. After further stirring at room temperature for 4 hours, 49.0 g of GBL was added. The precipitate formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0149] The subsequent purification process was carried out in the same manner as described in the synthesis method for polymer A-1 to obtain polymer A-3. The weight-average molecular weight (Mw) of polymer A-3 was 18,000, and the imide group introduction rate was 0.58. Furthermore, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-3 was 20.1 wt%.

[0150] Synthesis of polymer A-4: Polymer A-3 was obtained by carrying out the reaction in the same manner as the method for synthesizing polymer A-1, except that 17.0 g of BPADA was used instead of 20.9 g of BPADA, 8.8 g of HEMA was used instead of 10.9 g of HEMA, 13.3 g of DCC was used instead of 16.3 g of DCC, and 127.2 g of NMP solution of diamine oligomer W-2 was used instead of 101.7 g of NMP solution of diamine oligomer W-2 and 2.4 g of mTB. The weight-average molecular weight (Mw) of polymer A-3 was 35,000, and the imide group introduction rate was 0.53. Furthermore, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-4 was 15.2 wt%.

[0151] Synthesis of polymer A-5: Polymer A-5 was obtained by carrying out the reaction in the same manner as the method for synthesizing polymer A-2, except that 8.1 g of ODPA was used instead of 15.2 g of BPADA, 7.1 g of HEMA was used instead of 7.9 g, 10.7 g of DCC was used instead of 11.9 g, and 169.6 g of NMP solution of diamine oligomer W-3 was used instead of 111.5 g of NMP solution of diamine oligomer W-1. The weight-average molecular weight (Mw) of polymer A-5 was 22,000, and the imide group introduction rate was 0.63. Furthermore, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-4 was 20.5 wt%.

[0152] Synthesis of polymer A-6: Polymer A-6 was obtained by carrying out the reaction in the same manner as the method for synthesizing polymer A-2, except that 8.1 g of ODPA was used instead of 15.2 g of BPADA, 7.1 g of HEMA was used instead of 7.9 g, 10.7 g of DCC was used instead of 11.9 g, and 176.7 g of NMP solution of diamine oligomer W-4 was used instead of 111.5 g of NMP solution of diamine oligomer W-1. The weight-average molecular weight (Mw) of polymer A-6 was 23,000, and the imide group introduction rate was 0.63. Furthermore, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-6 was 19.6 wt%.

[0153] Synthesis of polymer A-7: Polymer A-7 was obtained by carrying out the reaction in the same manner as the method for synthesizing polymer A-1, except that 12.4 g of ODPA was used instead of 20.9 g of BPADA, and 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. The weight-average molecular weight (Mw) of polymer A-7 was 21,000, and the imide group introduction rate was 0.43. Furthermore, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-7 was 16.7 wt%.

[0154] Synthesis of polymer A-8: As the acid component, 12.4 g of ODPA was placed in a 1-liter separable flask, and 10.8 g of HEMA (the first substituent compound) and 26.0 g of GBL were added. The reaction mixture was obtained by adding 6.3 g of pyridine while stirring at room temperature (first reaction). After the exothermic reaction was complete, the mixture was allowed to cool to room temperature and then left to stand for another 16 hours.

[0155] Next, under ice cooling, a solution of 16.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 16.3 g of GBL was added to the reaction mixture of the first reaction over 40 minutes with stirring. Subsequently, 1.1 g of allylamine (the second substituent compound) was dissolved in 5.5 g of GBL, and this GBL solution was added over 5 minutes with stirring (second reaction). To the reaction mixture of the second reaction, a solution of 143.1 g of NMP solution of diamine oligomer W-5 dissolved in 93.6 g of GBL was added as the diamine component over 60 minutes with stirring. After further stirring at room temperature for 4 hours, 6.4 g of ethyl alcohol was added and stirred for 30 minutes, after which 49.0 g of GBL was added. The precipitate formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0156] The subsequent purification steps were carried out in the same manner as described in the synthesis method for polymer A-1 to obtain 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. Furthermore, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-8 was 16.7 wt%.

[0157] Synthesis of polymer A-9: Polymer A-9 was obtained by carrying out the reaction in the same manner as the method for synthesizing polymer A-1, except that 105.6 g of NMP solution of diamine oligomer W-6 was used instead of 101.7 g of NMP solution of diamine oligomer W-2 and 2.4 g of m-TB in the above synthesis method for polymer A-1. The weight-average molecular weight (Mw) of polymer A-9 was 29,000, and the imide group introduction rate was 0.43. Furthermore, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-9 was 16.8 wt%.

[0158] Synthesis of polymer A-10: Polymer A-10 was obtained by carrying out the reaction in the same manner as the method for synthesizing polymer A-2, except that 4.6 g of BPADA was used instead of 15.2 g, 2.4 g of HEMA was used instead of 7.9 g, 3.6 g of DCC was used instead of 11.9 g, and 174.4 g of NMP solution of diamine oligomer W-7 was used instead of 111.5 g of NMP solution of diamine oligomer W-1. The weight-average molecular weight (Mw) of polymer A-10 was 40,000, and the imide group introduction rate was 0.88. Furthermore, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-10 was 16.8 wt%.

[0159] Synthesis of polymer A-11: Polymer A-11 was obtained by carrying out the reaction in the same manner as described in the synthesis method for polymer A-3, except that 4.6 g of BPADA was used instead of 15.2 g, 2.4 g of HEMA was used instead of 7.9 g, 3.6 g of DCC was used instead of 11.9 g, 174.4 g of NMP solution of diamine oligomer W-7 was used instead of 111.5 g of NMP solution of diamine oligomer W-1, and 2.1 g of methacrylate chloride and 1.4 g of pyridine were used instead of 3.1 g of 2-isocyanatoethyl methacrylate. The weight-average molecular weight (Mw) of polymer A-11 was 36,000, and the imide group introduction rate was 0.88. Furthermore, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-11 was 16.8 wt%.

[0160] Synthesis of polymer A-12: Polymer A-12 was obtained by carrying out the reaction in the same manner as the method for synthesizing polymer A-1, except that 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. The weight-average molecular weight (Mw) of polymer A-12 was 26,000, and the imide group introduction rate was 0.58. Furthermore, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-12 was 23.6 wt%.

[0161] Synthesis of polymer A-13: Polymer A-13 was obtained by carrying out the reaction in the same manner as the method for synthesizing polymer A-1, except that 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 weight-average molecular weight (Mw) of polymer A-13 was 28,000, and the imide group introduction rate was 0.44. Furthermore, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-13 was 17.1 wt%.

[0162] Synthesis of polymer A-14: Polymer A-14 was obtained by carrying out the reaction in the same manner as the method for synthesizing polymer A-2, except that 7.7 g of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) was used instead of 15.2 g of BPADA, 7.1 g of HEMA was used instead of 7.9 g, 10.7 g of DCC was used instead of 11.9 g, and 150.1 g of NMP solution of diamine oligomer W-4 was used instead of 111.5 g of NMP solution of diamine oligomer W-1. The weight-average molecular weight (Mw) of polymer A-14 was 21,000, and the imide group introduction rate was 0.63. Furthermore, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-14 was 19.8 wt%.

[0163] Synthesis of polymer A-15: Polymer A-15 was obtained by carrying out the reaction in the same manner as the method for synthesizing polymer A-1, except that 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 weight-average molecular weight (Mw) of polymer A-15 was 28,000, and the imide group introduction rate was 0.16. Furthermore, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-15 was 15.8 wt%.

[0164] Synthesis of polymer A-16: Polymer A-16 was obtained by carrying out the reaction in the same manner as the method for synthesizing polymer A-1, except that 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 weight-average molecular weight (Mw) of polymer A-16 was 26,000, and the imide group introduction rate was 0.44. Furthermore, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-16 was 21.1 wt%.

[0165] Synthesis of polymer A-17: Polymer A-17 was obtained by carrying out the reaction in the same manner as described in the synthesis method for polymer A-2, except that 13.9 g of glycerol dimethacrylate was used instead of 7.9 g of HEMA. The weight-average molecular weight (Mw) of polymer A-17 was 24,000, and the imide group introduction rate was 0.58. Furthermore, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-17 was 20.1 wt%.

[0166] Synthesis of polymer A-18: Polymer A-18 was obtained by carrying out the reaction in the same manner as described in the synthesis method for polymer A-2, except that 7.8 g of 2-aminoethyl methacrylate was used instead of 7.9 g of HEMA. The weight-average molecular weight (Mw) of polymer A-18 was 24,000, and the imide group introduction rate was 0.58. Furthermore, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-18 was 20.1 wt%.

[0167] Synthesis of polymer A-19: Polymer A-19 was obtained by carrying out the reaction in the same manner as described in the synthesis method for polymer A-2, except that 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 weight-average molecular weight (Mw) of polymer A-19 was 24,000, and the imide group introduction rate was 0.58. Furthermore, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-19 was 20.1 wt%.

[0168] Synthesis of polyimide precursor (polymer A-20): As the acid component, 60.2 g of ODPA was placed in a 1-liter separable flask, and 54.2 g of HEMA and 137.5 g of GBL were added. The reaction mixture was obtained by adding 31.6 g of pyridine while stirring at room temperature. After the exothermic reaction was complete, the mixture was allowed to cool to room temperature and then left to stand for another 16 hours.

[0169] Next, under ice cooling, a solution of 81.3 g of DCC dissolved in 81.3 g of GBL was added to the reaction mixture over 40 minutes with stirring. Further, as the diamine component, a solution of 36.4 g of m-TB dissolved in 109.2 g of GBL was added over 60 minutes with stirring. After further stirring at room temperature for 2.5 hours, 15 g of ethyl alcohol was added and stirred for 30 minutes, then 150 g of γ-butyrolactone was added and stirred at 50 °C for 0.5 hour. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0170] The obtained reaction solution was added to 2700 g of ethyl alcohol to form a precipitate consisting of a crude polymer. The formed crude polymer was collected by filtration and dissolved in 1000 g of γ-butyrolactone to obtain a crude polymer solution. The obtained crude polymer solution was purified using an anion exchange resin ("Amberlyst TM 15" manufactured by Organo Corporation) to obtain a polymer solution. The obtained polymer solution was dropped into 8000 g of water to precipitate the polymer, and the obtained precipitate was collected by filtration and then vacuum dried to obtain powdery Polymer A-20. The weight average molecular weight (Mw) of this Polymer A-20 was 19,000 and the imide group introduction rate was 0. Also, the imide group concentration U per repeating unit of the polyimide obtained from Polymer A-20 was 28.8 wt%.

[0171] Synthesis of polyimide precursor (Polymer A-21): In the synthesis method of the above Polymer A-20, Polymer A-21 was obtained by carrying out the reaction in the same manner as the method described in the synthesis method of Polymer A-20, except that 63.3 g of BAPP was used instead of 36.4 g of m-TB. The weight average molecular weight (Mw) of this Polymer A-21 was 21,000 and the imide group introduction rate was 0. Also, the imide group concentration U per repeating unit of the polyimide obtained from Polymer A-21 was 20.5 wt%.

[0172] Synthesis of polyimide precursor (Polymer A-22): In the method for synthesizing the above polymer A-20, the reaction was carried out in the same manner as described in the method for synthesizing polymer A-20, except that 58.8 g of BPDA was used instead of 62.0 g of ODPA, and 34.3 g of 4,4'-diaminodiphenyl ether (DADPE) was used instead of 36.4 g of m-TB, to obtain polymer A-22. The weight average molecular weight (Mw) of this polymer A-22 was 22,000, and the imide group introduction rate was 0. Also, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-22 was 30.5 wt%.

[0173] Synthesis of polyimide precursor (polymer A-23): In the method for synthesizing the above polymer A-20, the reaction was carried out in the same manner as described in the method for synthesizing polymer A-20, except that 81.3 g of BAPP was used instead of 36.4 g of m-TB, to obtain polymer A-23. The weight average molecular weight (Mw) of this polymer A-23 was 16,000, and the imide group introduction rate was 0. Also, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-23 was 20.5 wt%.

[0174] Synthesis of polyimide (polymer A-24): 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 to a 1-liter separable flask equipped with a Dean-Stark tube and a condenser tube, and dissolved with stirring. Further, 126.9 g of toluene was added and stirred, and then the temperature was raised to 185 °C under a nitrogen 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. Then, it was cooled to room temperature to obtain a polyimide solution. The obtained polyimide solution was added to 1000 g of methyl alcohol to form a precipitate composed of a crude polymer. The generated crude polymer was collected by filtration and washed again with methyl alcohol. The washed polymer was vacuum dried at 50 °C to obtain powdery polymer A-24. The weight average molecular weight (Mw) of this polymer A-24 was 25,000.1 ¹H-NMR measurements were performed, and the imide cyclization rate was confirmed by comparing the peaks derived from amide bonds with those derived from aromatic rings of the polyimide. The imide cyclization rate was over 99%. Furthermore, the imide group concentration U per repeating unit of the polyimide obtained from polymer A-24 was 19.2 wt%.

[0175] <Ingredients (B)~(G)> Photopolymerization initiator B1: 3-Cyclopentyl-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]propanone-1-(O-acetyloxime) (Trade name: PBG-304, manufactured by Changzhou Strong Electronics Co., Ltd.) Photopolymerization initiator B2: 1,2-propanedione-3-cyclopentyl-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime) (Trade name: PBG-305, manufactured by Changzhou Strong Electronics Co., Ltd.) Photopolymerization initiator B3: 1-[4-(phenylthio)phenyl]-3-propane-1,2-dione-2-(O-acetyloxime) (Trade name: PBG-3057, manufactured by Changzhou Strong Electronics Co., Ltd.) Solvent C1: γ-butyrolactone Solvent C2: Dimethyl sulfoxide (DMSO) Solvent C3: 3-Methoxy-N,N-dimethylpropanamide Silane coupling agent D-1: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) Silane coupling agent D-2: N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) Silane coupling agent D-3: (3-triethoxysilylpropyl)-tert-butylcarbamate Silane coupling agent D-4: Uleidopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) Silane coupling agent D-5: X-12-1214A (product name manufactured by Shin-Etsu Chemical Co., Ltd.) Silane coupling agent D-6: Tris(-trimethoxysilylpropyl) isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd.) Radical polymerizable compound E-1: 1,6-Hexanediol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) Radical polymerizable compound E-2: Pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) Radical polymerizable compound E-3: (PO-modified) trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) Radical polymerizable compound E-4: Dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) Thermal crosslinking agent F-1: Bismaleimide compound (manufactured by Yamato Chemical Industries, Ltd., BMI-5100) Thermal crosslinking agent F-2: Blocked isocyanate (manufactured by Asahi Kasei Corporation, SBB70P) Thermal crosslinking agent F-3: Alkoxymethyl compound with the following structure (manufactured by Daito Chemix, CROLIN-318) [ka] Filler G-1: Spherical silica (Admatex Co., Ltd., K180SP-CY1)

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

[0177] <Examples 2-37, Comparative Examples 1-9> Except for adjusting the types and amounts of components to the proportions shown in Tables 3 to 6, the photosensitive resin composition solutions were prepared and evaluated in the same manner as in Example 1. Only in Comparative Example 8, the prepared photosensitive resin composition solution was allowed to stand at 40°C for 240 hours. Using the photosensitive resin composition after standing, the imidization rate as a photosensitive resin composition layer was measured using the method for measuring the imid structure introduction rate described above, and it was found to be 0.45. The characteristics and evaluation results are shown in Tables 7 to 10.

[0178] [Table 1]

[0179] Table 2

[0180] Table 3

[0181] Table 4

[0182] Table 5

[0183] Table 6

[0184] As is clear from Tables 1-10, the examples showed that by introducing a polyimide block structure in a specific ratio, a photosensitive resin composition was provided that had low dielectric properties, low curing shrinkage, and good storage stability, reduced phase separation during coating, and capable of forming a cured relief pattern with high resolution and high copper adhesion. On the other hand, Comparative Examples 1-6, which did not have a polyimide structure, showed high dielectric loss tangents and low residual film rates after curing. In Comparative Example 7, in which polyimide was blended with a polyimide precursor with an imide group introduction rate of 0, poor compatibility prevented uniform coating, making resolution evaluation difficult. It is also thought that the high dielectric loss tangent and low copper adhesion were due to phase separation. In Comparative Example 8, which used a partially imidized polyimide precursor, the dielectric loss tangent was low, but it is thought that the film after coating was cloudy and had poor resolution due to the difficulty in controlling imidization. In Comparative Example 9, which used 100% imide polymer, a radically polymerizable monomer was required for patterning, and although the residual film rate after curing was high, the dielectric loss tangent was high and the resolution was low. Based on these results, none of the comparative examples yielded satisfactory results. [Industrial applicability]

[0185] The photosensitive resin composition of this disclosure can be suitably used in the field of photosensitive materials useful for the manufacture of electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

1. A method for producing a copolymer resin containing polyimide and a polyimide precursor, the method comprising the following steps: (i) A diamine oligomer having repeating units of a polyimide structure is obtained by condensing and imidizing a first tetracarboxylic dianhydride or its acid / substituted adduct with a first diamine compound; (ii) The diamine oligomer is subjected to a condensation reaction with a second tetracarboxylic dianhydride or its acid / substituent adduct to obtain a polyimide-imide precursor moiety having a polyimide block moiety (n ２ Combining units; (iii) The polyimide-imide precursor portion is subjected to a condensation reaction with a third tetracarboxylic dianhydride or its acid / substituted adduct and a second diamine compound to obtain the polyimide precursor portion (n ３ Combining units Includes, A method for producing a copolymer resin, wherein 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 / substituted 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.

2. The polyimide-imide precursor portion (n ２ units) and the polyimide precursor portion (n ３ units), the total number of moles (n ２ + n ３ ), the ratio of the number of moles of the polyimide-imide precursor portion (n ２ ) is 0.10 < n ２ / (n ２ + n ３ ) < 0.90, the method according to claim 1.

3. The aforementioned n ２ / (n ２ +n ３ ) is 0.40 < n ２ / (n ２ +n ３ The method according to claim 2, satisfying < 0.

90.

4. The method according to claim 1 or 2, wherein at least one of the second tetracarboxylic dianhydride and the third tetracarboxylic dianhydride is in the form of an acid / ester having a photopolymerizable functional group.

5. The method according to claim 1 or 2, wherein step (i) is to obtain a diamine oligomer having repeating units of a polyimide structure by condensing the first tetracarboxylic dianhydride with the first diamine compound and imidizing it.

6. The method according to claim 1 or 2, wherein the second tetracarboxylic dianhydride (or its acid / substituted adduct) and the third tetracarboxylic dianhydride (or its acid / substituted adduct) are identical to each other, and an excess amount of the second tetracarboxylic dianhydride (or its acid / substituted adduct) present in the reaction solvent after the synthesis of the polyimide-imide precursor portion is used as the third tetracarboxylic dianhydride (or its acid / substituted adduct).

7. The method according to claim 1 or 2, wherein the first diamine compound and the second diamine compound are identical to each other, and an excess amount of the first diamine compound present in the reaction solvent after the synthesis of the diamine oligomer is used as the second diamine compound.

8. The copolymer resin has a structure represented by the following general formula (1), 【Chemistry 1】 In the above formula (1), X １ , X ２ and X ３ Each of these is independently a tetravalent organic group having 6 to 40 carbon atoms, Y １ and Y ２ These are, independently, divalent organic groups having 6 to 40 carbon atoms, and n １ n is an integer between 2 and 30. ２ and n ３ Each of these is an integer between 2 and 150, and Z ３ Z ４ Z ５ , and Z ６ These are each independently monovalent organic groups, Z ３ Z ４ Z ５ , and Z ６ Of these, at least one is a photopolymerizable functional group, The copolymer resin containing the polyimide and the polyimide precursor has a coefficient of 0.10 < n ２ / (n ２ +n ３ The method according to claim 1 or 2, satisfying < 0.

90.

9. The method according to claim 1 or 2, wherein the photopolymerizable functional group includes a structure represented by the following general formula (2). 【Chemistry 2】 (In formula (2), R ５ , R ６ and R ７ Each is independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m １ (This is an integer between 2 and 10.)

10. The copolymer resin comprising the polyimide and the polyimide precursor is halogen-free, according to claim 1 or 2.

11. The method according to claim 1 or 2, wherein, based on a polyimide obtained by 100% imidizing the copolymer resin, the imide group concentration U, which is the ratio of the molecular weight of the imide group to the molecular weight of the repeating unit containing a structure derived from tetracarboxylic dianhydride and diamine, is 12 wt% to 26 wt%.

12. In the above formula (1), X １ , X ２ and X ３ However, it includes the structure shown in the following general formula (4), 【Transformation 3】 In formula (4), R ８ , R ９ These are each an organic group having 1 to 10 carbon atoms, and m ２ , m ３ m is an integer selected from 0 to 4. ２ +m ３ Satisfying ≥ 1, Z １ is selected from the group consisting of single bonds, organic groups having 1 to 30 carbon atoms, and organic groups containing heteroatoms, where two of the *s represent bonds to the main chain of the resin, and the other two represent bonds to the side chains in the general formula (1) above; and / or, Y １ and / or Y ２ However, it includes the structure shown in the following general formula (7), 【Chemistry 4】 In formula (7), R ８ , R ９ These are each an organic group having 1 to 10 carbon atoms, and m ２ , m ３ m is an integer selected from 0 to 4. ２ +m ３ Satisfying ≥ 1, Z １ The method according to claim 9, wherein is selected from the group consisting of single bonds, organic groups having 1 to 30 carbon atoms, and organic groups containing heteroatoms, and * means that it is bonded to the main chain of the resin.

13. The method according to claim 1 or 2, wherein the copolymer resin comprising the polyimide and the polyimide precursor has at its resin ends a reactive substituent that polymerizes with heat or light, which is different from the photopolymerizable functional group contained in its repeating unit.

14. The method according to claim 1 or 2, comprising introducing other reactive substituents that polymerize by heat or light, different from the photopolymerizable functional groups contained in the repeating units of the copolymer resin, to the ends of the main chain, in accordance with (1), (2), and (3). (1) Prepare an acid / substituted adduct having a photopolymerizable functional group and a reactive substituent by reacting the second tetracarboxylic dianhydride and / or the third tetracarboxylic dianhydride with a first substituent-introduced compound having a photopolymerizable functional group, and then reacting it with a second substituent-introduced compound having a reactive substituent that reacts with heat or light different from that of the first substituent-introduced compound; or obtain an acid / substituted 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-introduced compound, and then reacting it with the first substituent-introduced compound; and / or (2) To prepare a diamine oligomer having a second reactive substituent by reacting the diamine oligomer with a second substituent-introduced compound; (3) Using the acid / substituted adduct having a photopolymerizable functional group and a reactive substituent obtained in (1) above, and / or the diamine oligomer having a reactive substituent obtained in (2) above, steps (ii) and (iii) of the method for producing the copolymer resin.

15. A method for producing a photosensitive resin composition, wherein the method is: A copolymer resin comprising a polyimide and a polyimide precursor is produced by the method described in claim 1 or 2; (A) A copolymer resin containing 100 parts by mass of the 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 to obtain a photosensitive resin composition. A method for producing a photosensitive resin composition containing [the specified substance].

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