Method for producing a negative-type photosensitive resin composition and a cured relief pattern

Abstract

The present disclosure aims to provide a negative-type photosensitive resin composition that exhibits high in-plane uniformity of the film and excellent resolution performance, and to provide a method for manufacturing a cured relief pattern, a method for manufacturing polyimide, a cured polyimide product, a method for manufacturing a cured polyimide product, and a semiconductor device using the negative-type photosensitive resin composition. [Solution] A negative-type photosensitive resin composition is provided comprising (A) (A1) polyimide or (A2) polyimide precursor, (B) photopolymerization initiator, and (C) a compound represented by the following general formula (1): TIFF0007863246000095.tif22169{In the formula, R1 represents an alkyl group having 1 to 10 carbon atoms}.

Description

[Technical Field]

[0001] This disclosure relates to a negative-type photosensitive resin composition and a method for producing a cured relief pattern, etc. [Background technology]

[0002] Conventionally, polyimide resins, polybenzoxazole resins, phenolic resins, and the like, which possess excellent heat resistance, electrical properties, and mechanical properties, have been used as insulating materials for electronic components, passivation films and surface protective films for semiconductor devices, and interlayer insulating films. Among these resins, those provided in the form of photosensitive resin compositions allow for the easy formation of heat-resistant relief pattern films by coating, exposure, development, and curing treatment of the composition.

[0003] Photosensitive resin compositions can be classified into negative-type compositions that develop, dissolve, or remove unexposed areas and positive-type compositions that develop, dissolve, or remove exposed areas in processes such as photoresistography, cured relief pattern manufacturing or development processes, or semiconductor device or display device manufacturing processes. Such photosensitive resin compositions have the advantage of enabling a significant reduction in process steps compared to conventional non-photosensitive materials. For example, Patent Document 1 examines the amount of each component to be blended in a photosensitive resin composition containing a polyimide precursor and / or polyimide, a surfactant, and a photopolymerization initiator, from the viewpoint of thermosetting temperature, chemical resistance, and suppression of clouding during coating.

[0004] Traditionally, improvements in semiconductor performance have been primarily driven by miniaturization in the front-end process. However, in recent years, attention has been focused on improving semiconductor performance through back-end packaging technology. In particular, a technology called 2.5D packaging is attracting attention in semiconductors for servers and high-performance computing (HPC). This technology involves arranging multiple processors and memory on a silicon or organic interposer and connecting them closely to shorten the communication distance between chips and improve data transfer speed. In this technology, there is a tendency to pack more processors and memory into a single package in order to further improve computing power, resulting in increased package dimensions and a tendency for redistribution layers (RDLs) to become more multilayered. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2022-91355 [Overview of the project] [Problems that the invention aims to solve]

[0006] With the advancements in semiconductor performance improvement technologies described above, the interlayer insulating films forming the redistribution layers require high glass transition temperatures to enhance stress resistance, and also high resolution and film flatness to form denser wiring. Generally, increasing the concentration of imide groups is effective in raising the glass transition temperature of heat-resistant resins such as polyimide. However, this tends to increase the absorbance of the polyimide resin, worsening its resolution performance, and furthermore, the low fluidity during the drying process after coating tends to worsen the in-plane uniformity of the film. Generally, the application of surfactants such as fluorine-based surfactants, as described in Patent Document 1, can be considered to improve the in-plane uniformity of the film. However, further investigation is needed before its practical application from the standpoint of storage stability and environmental regulations.

[0007] Therefore, one of the objectives of this disclosure is to provide a negative-type photosensitive resin composition (hereinafter also simply referred to as "photosensitive resin composition") that exhibits high in-plane uniformity of the film and excellent resolution performance. Another objective of the present invention is to provide a method for manufacturing a cured relief pattern, a method for manufacturing polyimide, a cured polyimide product, a method for manufacturing a cured polyimide product, and a semiconductor device, all realized using the negative-type photosensitive resin composition. [Means for solving the problem]

[0008] Examples of embodiments of this disclosure are listed below. [1] (A)(A1) polyimide or (A2) polyimide precursor; (B) Photopolymerization initiator; and (C) General formula (1): [ka] {In the formula, R1 represents an alkyl group having 1 to 10 carbon atoms.} A compound represented by; A negative-type photosensitive resin composition containing [a specific compound / substance]. [2] The negative-type photosensitive resin composition according to item 1, wherein R1 is an alkyl group having 1 to 4 carbon atoms. [3] The negative-type photosensitive resin composition according to [1] or [2], wherein the (C) compound is N-methylsuccinimide and / or N-ethylsuccinimide. [4] The negative-type photosensitive resin composition according to any one of [1] to [3], wherein the (C) compound is N-ethylsuccinimide. [5] (D) A negative-type photosensitive resin composition according to any one of [1] to [4], further comprising N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone as a solvent. [6] The negative-type photosensitive resin composition according to [5], comprising N-ethyl-2-pyrrolidone as the solvent (D). [7] The negative photosensitive resin composition according to any one of [1] to [6], wherein the (B) photoinitiator is an oxime compound. [8] The negative photosensitive resin composition according to any one of [1] to [7], further comprising an (E) radically polymerizable compound. [9] The (A1) polyimide has the structure represented by the following general formula (2):

Chemical formula

[10] X1 is represented by the following general formulas (3) to (8):

Chemical formula

[12] The (A2) polyimide precursor is given by the following general formula (13): [ka] {In the formula, X2 is a tetravalent organic group, Y2 is a divalent organic group, m is a positive integer, and R2 and R3 are each independently selected from the group consisting of a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms.} A negative-type photosensitive resin composition according to any one of [1] to

[11] , having a structure represented by [1].

[13] At least one of R2 and R3 in the above general formula (13) is given by the following general formula (14): [ka] {In the formula, R4, R5, and R6 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and p is an integer selected from 1 to 10.} The negative-type photosensitive resin composition described in

[12] , wherein the monovalent organic group is represented by .

[14] In the above general formula (13), X2 is given by the following general formulas (15)~(17): [ka] [ka] [ka] The negative-type photosensitive resin composition according to

[12] , having at least one selected from the group consisting of structures represented by .

[15] In the above general formula (13), Y2 is given by the following general formulas (19) to (21): [ka] [ka] [ka] The negative-type photosensitive resin composition according to

[12] , having at least one selected from the group consisting of structures represented by .

[16] A method for producing a cured film, comprising the step of curing a negative-type photosensitive resin composition described in any of [1] to

[15] to form a cured film containing polyimide.

[17] The following steps: (1) A step of applying a negative-type photosensitive resin composition described in any of [1] to

[15] onto a substrate to form a photosensitive resin layer on the substrate, (2) A step of exposing the photosensitive resin layer, (3) A step of developing the photosensitive resin layer after exposure to form a relief pattern, (4) A step of heat-treating the relief pattern to form a hardened relief pattern. A method for manufacturing a hardened relief pattern, including [the specified element]. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a negative-type photosensitive resin composition that has high in-plane uniformity of the film and excellent resolution performance. Furthermore, according to the present invention, it is also possible to provide a method for manufacturing a cured relief pattern, a method for manufacturing the negative-type photosensitive resin composition, a method for manufacturing a cured film and a cured relief pattern using the negative-type photosensitive resin composition, and a pre-baked film, etc. [Brief explanation of the drawing]

[0010] [Figure 1] This is a focused ion beam (FIB) photograph of the pattern cross-sectional shape obtained in Example 4. [Modes for carrying out the invention]

[0011] The following describes in detail embodiments for carrying out the present invention (hereinafter referred to as "this embodiment"). The present invention is not limited to the following embodiments and can be implemented in various ways within the scope of its gist.

[0012] In this specification, "(meth)acrylic" means "methacrylic" and / or "acrylic." In this specification, "organic group" means a hydrocarbon group comprising carbon and hydrogen, and derivatives thereof. The derivatives may contain atoms other than carbon and hydrogen (e.g., nitrogen, oxygen, sulfur, or silicon).

[0013] In this specification, if there are multiple parts in a molecule whose structures are represented by the same symbol in a formula, they may be identical or different from one another.

[0014] In this specification, in numerical ranges described in stages, the upper or lower limit stated in one numerical range may be replaced by the upper or lower limit of another numerical range described in stages. In this specification, the upper or lower limit stated in one numerical range may be replaced by the value described in the example.

[0015] In this specification, the term "process" includes not only independent processes but also any process that achieves its function, even if it cannot be clearly distinguished from other processes. In the drawings, scale, shape, and length may be exaggerated for clarity.

[0016] Negative-type photosensitive resin composition The negative-type photosensitive resin composition according to this embodiment is: (A)(A1) Polyimide or (A2) Polyimide precursor resin; (B) Photopolymerization initiator; and (C) General formula (1): [ka] {In the formula, R1 represents an alkyl group having 1 to 10 carbon atoms.} A compound represented by; The composition is characterized by including the above. According to the above composition, it is possible to provide a negative-type photosensitive resin composition that has high in-plane uniformity of the film and excellent resolution performance.

[0017] (A1) Polyimide The (A1) polyimide used in this embodiment will now be described. The (A1) polyimide in this embodiment is not limited as long as it can be dissolved in a general organic solvent, but it is preferable that it does not contain fluorine atoms from the viewpoint of chemical resistance and elongation.

[0018] In this embodiment, the (A1) polyimide preferably has photopolymerizable functional groups at the ends of the main chain and / or the side chains, from the viewpoint of chemical resistance. The presence of photopolymerizable functional groups in the (A1) polyimide can improve resolution.

[0019] Here, the term "photopolymerizable functional group" is not limited to any functional group that can be polymerized by light irradiation. Examples of such functional groups include methacryloyl groups, acryloyl groups, methacrylamide groups, acrylamide groups, and styryl groups. From the viewpoint of resolution, at least one selected from methacryloyl groups, acryloyl groups, and styryl groups is preferred.

[0020] In this embodiment, the main chain end refers to the terminal structure of a polyimide main chain composed of an acidic dianhydride and a diamine. The method for introducing photopolymerizable functional groups to the polyimide main chain ends is not particularly limited. For example, the photopolymerizable functional groups can be introduced to the acidic dianhydride and / or diamine before polycondensation of the acidic dianhydride and diamine, or the photopolymerizable functional groups can be introduced to the main chain end structure after obtaining the polyimide.

[0021] The side chain terminus in this embodiment refers to the side chain structure of a polyimide main chain composed of an acidic dianhydride and a diamine. The method for introducing photopolymerizable functional groups to the polyimide side chain terminus is not particularly limited. For example, the photopolymerizable functional groups can be introduced to the acidic dianhydride and / or diamine before polycondensation of the acidic dianhydride and diamine, or the photopolymerizable functional groups can be introduced to the side chain structure after obtaining the polyimide.

[0022] The polyimide (A1) according to this embodiment is given by the following general formula (2): [ka] {In the formula, X1 is a tetravalent organic group, Y1 is a divalent organic group, and n is a positive integer.} It can have a structure represented by [this].

[0023] In general formula (2), X1 is not limited to any tetravalent organic group, but from the viewpoint of chemical resistance, its carbon number is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, and particularly preferably 10 or more. From the viewpoint of resolution, the carbon number of X1 is preferably 32 or less, more preferably 30 or less, even more preferably 28 or less, and particularly preferably 26 or less.

[0024] In general formula (2), Y1 is not limited to any divalent organic group, but from the viewpoint of chemical resistance, its carbon number is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, and particularly preferably 10 or more. From the viewpoint of resolution, the carbon number of Y1 is preferably 40 or less, more preferably 30 or less, even more preferably 28 or less, and particularly preferably 26 or less.

[0025] In this embodiment, X1 preferably contains an aromatic group from the viewpoint of physical properties after heat curing or resolution, and is based on the following general formulas (3) to (8): [ka] [ka] [ka] [ka] [ka] [ka] It is more preferable to include at least one selected from the structures represented by the formulas (4) and (5). From the viewpoint of the glass transition temperature (Tg) after heat curing, X1 in this embodiment is preferably selected from the group consisting of the structures represented by the formulas (4) and (5), and from the viewpoint of the elongation after heat curing, it is preferably selected from the group consisting of the structures represented by the formulas (3) and (8). From the viewpoint of resolution, X1 in this embodiment is preferably selected from the group consisting of the structures represented by the formulas (6) and (7). In the formulas, Me represents a methyl group.

[0026] In this embodiment, Y1 preferably has an aromatic group from the viewpoint of physical properties after heat curing or resolution, and is based on the following general formulas (9) to (12): [ka] [ka] [ka] [ka] It is more preferable to include at least one selected from the structures represented by the formulas (10 and 12). From the viewpoint of the glass transition temperature (Tg) after heat curing, Y1 in this embodiment preferably includes the structure represented by formula (10), and from the viewpoint of the elongation after heat curing, it is preferable to include at least one selected from the group consisting of structures represented by formulas (9) and (12). From the viewpoint of resolution, it is preferable to include the structure represented by formula (11).

[0027] (A1) Method for preparing polyimide (A1) A method for preparing polyimide is, for example, to obtain polyamic acid by polycondensing a tetracarboxylic dianhydride containing the aforementioned tetravalent organic group X1 with a diamine containing the aforementioned divalent organic group Y1, and then heat-treating the resulting polyimide.

[0028] (Preparation of polyamic acid) (A1) A tetracarboxylic dianhydride containing a tetravalent organic group X1 that is suitable for preparing polyamic acid, which is a precursor of polyimide, is given by the following formula (1T): [ka] {In the above equation (1T), X1 is defined in the above general equation (2).} Compounds represented by are preferred.

[0029] Examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride (also known as oxydiphthalic acid dianhydride, abbreviated as "ODPA"), benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride (abbreviated as "BPDA"), diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane.

[0030] Preferred examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride which can be represented by the following formula (7T), benzophenone-3,3',4,4'-tetracarboxylic dianhydride and biphenyl-3,3',4,4'-tetracarboxylic dianhydride, and tetracarboxylic dianhydrides represented by the following general formulas (2T) to (6T), but are not limited to these. [ka] [ka] [ka] [ka] [ka] [ka] These may be used individually or in combination of two or more. Among these, tetracarboxylic dianhydrides represented by the general formulas (2T) to (7T) are preferred.

[0031] Diamines containing a divalent organic group Y1 include those with the following formula (1D): H2N-Y1-NH2(1D) {In the formula, Y1 is defined in the general formula (2) above.} Compounds represented by are preferred.

[0032] Examples of diamines include p-phenylenediamine (abbreviated as "pPD"), m-phenylenediamine, 4,4'-diaminodiphenyl ether (abbreviated as "4,4'-DADPE", also known as 4,4'-oxydianiline, abbreviated as "ODA"), 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, and 3,3'-diamine Nodiphenylsulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diamino-2,2'-dimethylbiphenyl (abbreviated as "m-TB"), 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3 -aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4- (Aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone and 9,9-bis(4-aminophenyl)fluorene, etc., and those in which some of the hydrogen atoms on the benzene ring are substituted with methyl groups, ethyl groups, hydroxymethyl groups, hydroxyethyl groups, halogens, etc., for example, 3,Examples include, but are not limited to, 3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethylthoxy-4,4'-diaminobiphenyl, and 3,3'-dichloro-4,4'-diaminobiphenyl, as well as diamines represented by the following general formulas (2D) to (5D). [ka] [ka] [ka] [ka] These can be used individually or mixed together. Among these, diamines represented by the above formulas (2D) to (5D) are preferred.

[0033] Polyamic acid can be obtained by dissolving and mixing the above-mentioned tetracarboxylic dianhydride and the above-mentioned diamine in a solvent described later. For example, the reaction conditions involve continuous stirring for 4 to 10 hours at a temperature of 10°C to 50°C. The obtained polyamic acid can be isolated and then subjected to an imidation reaction, or it can be subjected to the next imidation reaction without isolation.

[0034] (Preparation of polyimide) The polyamic acid obtained above can be reacted at high temperature with an imidation catalyst added as needed to obtain polyimide. Preferably, this can be carried out in a glass container equipped with a Dean-Stark apparatus, by mixing toluene or xylene, which are azeotropic solvents with water. The reaction conditions are not limited as long as the desired polyimide is obtained, but for example, stirring is continued for 4 to 10 hours at a reaction temperature of 150°C to 230°C.

[0035] After the polyimide reaction is complete and the mixture has cooled to near room temperature, the resulting polymer component can be added to a poor solvent to precipitate it. Further purification of the polymer can be achieved by repeating redissolution and reprecipitation operations. After purification of the polymer, the target polyimide can be isolated by vacuum drying. To improve the degree of purification, the solution of this polymer may be passed through a column packed with an anion exchange resin, a cation exchange resin, or both of these swollen with a suitable organic solvent, to remove ionic impurities.

[0036] The molecular weight of (A1) polyimide is preferably 8,000 to 150,000, and more preferably 9,000 to 50,000, when measured by weight-average molecular weight in terms of polystyrene equivalent using gel permeation chromatography. When the weight-average molecular weight is 8,000 or higher, the mechanical properties are good, and when it is 150,000 or lower, the dispersibility in the developer is good and the relief pattern resolution is good. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as the developing solvents for gel permeation chromatography. The weight-average molecular weight of (A1) polyimide is measured by the method described in the examples.

[0037] The polyimide according to this embodiment is defined by the following formulas (1PI) to (5PI): [ka] [ka] [ka] [ka] [ka] Examples include structures that include at least one of the structures represented by {(1PI) to (5PI) {wherein n is a positive integer which can be determined according to the structure and molecular weight of the polyimide described above} as a repeating unit.

[0038] (A2) Polyimide precursor The (A2) polyimide precursor used in this embodiment will be described. The resin component in the photosensitive resin composition of this embodiment is the following general formula (13): [ka] {In the formula, X2 is a tetravalent organic group, Y2 is a divalent organic group, m is a positive integer, and R2 and R3 are each independently selected from the group consisting of a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms.} It is preferable that the polyimide precursor has a structural unit represented by (A2). The polyimide precursor is converted to polyimide by heat cyclization treatment.

[0039] The organic group in the above general formula (13) may be an organic group containing heteroatoms other than carbon and hydrogen, or an organic group consisting of carbon and hydrogen atoms. Examples of heteroatoms in this disclosure include nitrogen atoms, oxygen atoms, and sulfur atoms.

[0040] Preferably, at least one of R2 and R3 in general formula (13) is a group further comprising at least one polymerizable group selected from an acid polymerizable group, a base polymerizable group, and a radical polymerizable group. In this disclosure, an acid polymerizable group, a base polymerizable group, and a radical polymerizable group refer to a group that can be polymerized by the action of an acid, a base, or a radical, respectively. At least one of R2 and R3 in general formula (13) is the following general formula (14): [ka] {In the formula, R4, R5, and R6 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and p is an integer selected from 1 to 10.} It is preferable from the viewpoint of photosensitive properties that the group is represented by [formula].

[0041] In the above general formula (14), R4, R5, and R6 are monovalent organic groups having 1 to 3 carbon atoms, and specifically include methyl, ethyl, n-propyl, and isopropyl groups. R4 is preferably a hydrogen atom or a methyl group, and R5 and R6 are preferably hydrogen atoms.

[0042] In general formula (13), the proportion of hydrogen atoms in R2 and R3 may be 0% or more, preferably 10% or less, more preferably 5% or less, and even more preferably 1% or less, relative to the total number of moles of R2 and R3. The proportion of groups represented by formula (14) in general formula (13) may be 100% or less, preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, relative to the total number of moles of R2 and R3. Having the proportion of hydrogen atoms and / or the proportion of organic groups of formula (14) within the above ranges is preferable from the viewpoint of photosensitive properties and storage stability.

[0043] In general formula (13), m is not limited to any integer between 2 and 150, but from the viewpoint of the photosensitive properties and mechanical properties of the photosensitive resin composition, an integer between 3 and 100 is preferred, and an integer between 5 and 70 is more preferred.

[0044] In general formula (13), the tetravalent organic group represented by X2 is, for example, the following general formula (I): [ka] {In the formula, R6 is independently selected from the group consisting of a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a monovalent fluorine-containing hydrocarbon group having 1 to 10 carbon atoms; l is independently selected from 0 to 2; m is independently selected from 0 to 3; and n is independently selected from 0 to 4.} Examples of groups having a structure selected from the group consisting of the following are, but are not limited to, these. Furthermore, these may be used individually or in combination of two or more. Among these, X2 is selected from the viewpoint of physical properties or resolution performance after heat curing using the following general formulas (15) to (18): [ka] [ka] [ka] [ka] It is preferable that the structure is selected from the structures represented by the formulas (15) above. From the viewpoint of the glass transition temperature (Tg) after heat curing and resolution performance, it is preferable that X2 in this embodiment includes the structure represented by formula (15) above, and from the viewpoint of elongation after heat curing, it is preferable that it includes at least one selected from the group consisting of structures represented by formulas (16) to (18). Furthermore, from the viewpoint of resolution performance, it is more preferable that X2 is at least one selected from the group consisting of structures represented by formulas (15) to (17).

[0045] In general formula (13), the divalent organic group represented by Y2 is, for example, the following general formulas (II) and (II-1): [ka] [ka] {In formulas (II) and (II-1), R6 is at least one independently selected from the group consisting of a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a monovalent fluorine-containing hydrocarbon group having 1 to 10 carbon atoms; n is an integer independently selected from 0 to 4; and p is an integer selected from 1 to 20.} Examples of groups having a structure selected from the group consisting of the following are, but are not limited to, these. Furthermore, these may be used individually or in combination of two or more. Among these, Y2 is selected from the viewpoint of physical properties or resolution performance after heat curing using the following general formulas (19) to (22): [ka] [ka] [ka] [ka] It is preferable that Y2 is selected from the structures represented by the formulas (19) and (21). From the viewpoint of the glass transition temperature (Tg) after heat curing and resolution performance, it is preferable that Y2 in this embodiment includes at least one selected from the group consisting of structures represented by the formulas (21) and (21), and from the viewpoint of elongation after heat curing, it is preferable that it includes at least one selected from the group consisting of structures represented by the formulas (19) and (22). In particular from the viewpoint of resolution performance, it is more preferable that Y2 is selected from at least one of the structures represented by the formulas (19) to (21).

[0046] (A2) Method for preparing polyimide precursors (A2) The polyimide precursor is obtained by reacting a tetracarboxylic dianhydride containing the aforementioned tetravalent organic group X2 with photopolymerizable alcohols having an unsaturated double bond and optionally alcohols without an unsaturated double bond to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as the acid / ester), and then performing amide polycondensation with the aforementioned diamines containing the divalent organic group Y2.

[0047] (Preparation of acid / ester compounds) In this embodiment, the tetracarboxylic dianhydride containing the tetravalent organic group X2, which is suitably used to prepare the (A2) polyimide precursor, is the aforementioned tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenyl sulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, and 2,2-bis(3 Examples of suitable dianhydrides include, but are not limited to, pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, and biphenyl-3,3',4,4'-tetracarboxylic dianhydride.

[0048] In this embodiment, suitable photopolymerizable alcohols having unsaturated double bonds for preparing the (A2) polyimide precursor include, for example, 2-hydroxyethyl methacrylate, 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 acrylate. Examples include 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 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 above-mentioned photopolymerizable alcohols having unsaturated double bonds, alcohols without unsaturated double bonds, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, and benzyl alcohol, can also be used in combination with a portion of these alcohols.

[0050] Furthermore, as a polyimide precursor, a non-photosensitive polyimide precursor prepared solely from alcohols that do not have the above-mentioned unsaturated double bonds may be used in combination with the photosensitive polyimide precursor. From the viewpoint of resolution, it is preferable that the non-photosensitive polyimide precursor be 200 parts by mass or less, based on 100 parts by mass of the photosensitive polyimide precursor.

[0051] By stirring and dissolving the above-mentioned suitable tetracarboxylic dianhydride and the above-mentioned alcohols in a solvent as described later, in the presence of a basic catalyst such as pyridine, at a temperature of 20°C to 50°C for 4 to 10 hours, the esterification reaction of the acid anhydride proceeds, and the desired acid / ester product can be obtained.

[0052] (Preparation of polyimide precursors) To the above acid / ester mixture (typically a solution in a solvent described later), a suitable dehydrating condensation agent, such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, or N,N'-disuccinimidyl carbonate, is added and mixed under ice cooling to form a polyacid anhydride from the acid / ester mixture. Then, a diamine containing a divalent organic group Y2, which is preferably used in this embodiment, is dissolved or dispersed separately in a solvent and added dropwise to this mixture to perform amide polycondensation, thereby obtaining the desired polyimide precursor. Alternatively, the above acid / ester mixture can be acid-chlorinated using thionyl chloride or the like, and then reacted with a diamine compound in the presence of a base such as pyridine to obtain the desired polyimide precursor.

[0053] Examples of diamines containing a divalent organic group Y2 that are preferably used in this embodiment include the aforementioned diamines. Examples of diamines containing a divalent organic group Y2 include p-phenylenediamine (abbreviated as "pPD"), m-phenylenediamine, 4,4'-diaminodiphenyl ether (abbreviated as "4,4'-DADPE"), 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, and 3,4'-diaminodiphenyl Nylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diamino-2,2'-dimethylbiphenyl (m-TB), 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminopheno Xy)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-amino Phenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone and 9,Examples include, but are not limited to, 9-bis(4-aminophenyl)fluorene, and those in which some of the hydrogen atoms on the benzene ring are substituted with methyl groups, ethyl groups, hydroxymethyl groups, hydroxyethyl groups, halogens, etc., such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethitoxy-4,4'-diaminobiphenyl, and 3,3'-dichloro-4,4'-diaminobiphenyl, as well as mixtures thereof.

[0054] 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 poor solvent such as water, aliphatic lower alcohol, or a mixture thereof is added to the obtained polymer component to precipitate it. Further purification of the polymer is performed by repeating the redissolution and reprecipitation operations. After the purification of the polymer, the target polyimide precursor is isolated by vacuum drying. To improve the degree of purification, the solution of this polymer may be passed through a column packed with anion and / or cation exchange resin swollen with a suitable organic solvent to remove ionic impurities.

[0055] The molecular weight of the (A2) polyimide precursor is preferably 8,000 to 150,000, and more preferably 9,000 to 50,000, when measured by weight-average molecular weight in terms of polystyrene equivalent using gel permeation chromatography. When the weight-average molecular weight is 8,000 or higher, the mechanical properties are good, and when it is 150,000 or lower, the dispersibility in the developer and the resolution performance of the relief pattern are good. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as the developing solvents for gel permeation chromatography. The weight-average molecular weight of the (A2) polyimide precursor is measured by the method described in the examples.

[0056] (B) Photopolymerization initiator Examples of photopolymerization initiators include, Benzophenone derivatives such as benzophenone, o-methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; Acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone; Thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, and other thioxanthone derivatives; benzyl, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal, and other benzyl derivatives; Benzoin, benzoin methyl ether, and other benzoin derivatives; Oximes such as 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, and 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime; N-arylglycines such as N-phenylglycine; Peroxides such as benzoyl perchloride; Aromatic biimidazoles, titanocenes; Photoacid generators such as α-(n-octanesulfonyloxyimino)-4-methoxybenzylcyanide; The following are preferred. Among the above photopolymerization initiators, photoradical polymerization initiators are preferred, and oximes (oxime compounds) are more preferred in terms of photosensitivity.

[0057] Oxime photopolymerization initiators are defined by the following general formula (23) from the viewpoint of photosensitivity: [ka] {where, R 26 , R 27and R 28 is a monovalent organic group, and R 26 and R 27 may be connected to each other to form a ring structure} Preferably, it has a structure (oxime ester structure) represented by .

[0058] Among the compounds having the oxime ester structure of the above formula (23), from the viewpoint of photosensitivity, the following formulas (B1), (B2) and (B3): [Chemical formula] {In the formula, R b1 is a monovalent organic group, R b2 is a hydrogen atom or a monovalent organic group having 1 to 12 carbon atoms, and R b3 is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a phenyl group} [Chemical formula] {In the formula, Z is a sulfur or oxygen atom, and R b4 represents a methyl group or a phenyl group, and R b5 to R b7 each independently represents a hydrogen atom or a monovalent organic group} [Chemical formula] {In the formula, R b8 is an aromatic group having 6 to 20 carbon atoms or a monovalent organic group containing a heterocyclic compound having 5 to 20 carbon atoms, R b9 is an alkyl group having 1 to 5 carbon atoms, R b10 is an alkyl group having 1 to 10 carbon atoms or a monovalent organic group having a saturated alicyclic structure having 3 to 10 carbon atoms, and R b11 represents a methyl group, an ethyl group, a propyl group, or a phenyl group} More preferably, it is at least one compound selected from the group consisting of .

[0059] The amount of (B) photopolymerization initiator in the photosensitive resin composition of this embodiment is preferably 0.1 parts by mass or more and 30 parts by mass or less per 100 parts by mass of (A1) polyimide or (A2) polyimide precursor as component (A). From the viewpoint of ensuring the photosensitivity or patternability of the resulting photosensitive resin composition, the amount of (B) photopolymerization initiator is preferably 0.1 parts by mass or more per 100 parts by mass of (A1) polyimide or (A2) polyimide precursor as component (A), and from the viewpoint of improving the physical properties of the resulting cured film, it is preferably 30 parts by mass or less per 100 parts by mass of (A1) polyimide or (A2) polyimide precursor as component (A). The amount of (B) photopolymerization initiator is more preferably 0.5 parts by mass or more and 20 parts by mass or less, even more preferably 1 part by mass or more and 15 parts by mass or less, and particularly preferably 1 part by mass or more and 8 parts by mass or less per 100 parts by mass of (A1) polyimide or (A2) polyimide precursor as component (A).

[0060] (C) Compound represented by general formula (1) The photosensitive resin composition in this embodiment has the following general formula (1) as component (C): [ka] {In the formula, R1 represents an alkyl group having 1 to 10 carbon atoms.} The present invention contains a compound represented by (hereinafter also referred to as a succinimide compound). By including a compound represented by general formula (1) in the photosensitive resin composition, a film with excellent in-plane uniformity, focus margin after development, and taper shape of aperture diameter can be obtained. In this disclosure, an ideal taper shape refers to a shape in which the wall angle of the pattern is approximately 75° to 85°. If the wall angle is 75° or more, the coverage of the underlying wiring of the polyimide (PI) cured film is improved, and the risk of the underlying wiring being exposed is reduced. If the wall angle is 85° or less, the sputtering of the seed layer formed on the upper layer of the PI cured film is improved, and the risk of defects in wiring formation is reduced.

[0061] The inventors speculate that the following effects can be obtained: In the pre-bake process, the succinimide compound represented by general formula (1) forms electrostatic interactions and dipole-dipole interactions between its own imide moiety and the imide moiety of (A)(A1) polyimide or the amide moiety of (A2) polyimide precursor. Furthermore, hydrogen bonding interactions are also formed between the succinimide compound and the amide moiety of (A2) polyimide precursor. The succinimide compound represented by general formula (1) functions as a spacer between (A1) polyimide molecules or (A2) polyimide precursor molecules, suppressing polymer aggregation, thereby promoting the fluidity of the film during pre-bake and enabling the acquisition of a pre-bake film with excellent in-plane uniformity. In addition, the succinimide compound represented by general formula (1) present between the molecules of (A)(A1) polyimide or (A2) polyimide precursor functions as a dissolution accelerator in the development process. This is because the succinimide compound represented by general formula (1), which is present between polymer molecules, preferentially dissolves in the developer, creating voids in the polymer network and promoting the penetration of the developer. As a result, the formation of residue at the bottom of the unexposed area is suppressed, and good resolution performance can be achieved even when the exposure focus is outside the optimal position. Furthermore, when the succinimide compound represented by general formula (1) remaining in the film after development volatilizes during the post-development bake (PDB) or curing process, the (A)(A1) polyimide or (A2) polyimide precursor flows, causing the film to shrink, and a cured film with a good tapered shape can be obtained. The tapered shape is particularly effective in systems using the (A)(A1) polyimide or (A2) polyimide precursor, which has a rigid main chain structure and high absorbance.

[0062] Examples of C1-C10 alkyl groups in R1 of general formula (1) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. By having C1-C10 alkyl groups in general formula (1), a decrease in thermal properties can be suppressed by ensuring reliable volatilization from the film during the curing process. The number of C1-C1 in R1 was determined from the viewpoint of in-plane uniformity of the film, volatilization during the curing process, and suppression of the decrease in thermal properties. From the same viewpoint as above, the number of C1 in R1 is preferably in the range of 1-8, more preferably in the range of 1-6, even more preferably in the range of 1-4, and particularly preferably 1 or 2.

[0063] (C) Among the compounds represented by general formula (1), N-methylsuccinimide and / or N-ethylsuccinimide are preferred from the viewpoint of in-plane uniformity of the film. The fact that the number of carbon atoms in R1 in general formula (1) is 1 or 2 reduces steric hindrance, allowing (A) to interact well between (A1) polyimides or between (A2) polyimide precursors, and a remarkable effect can be obtained.

[0064] Furthermore, N-ethylsuccinimide is the most preferred compound represented by general formula (1) (C). The fact that R1 in the compound represented by general formula (1) (C) is an ethyl group increases the solubility of the residue components at the bottom of the unexposed area, and particularly good resolution performance can be obtained.

[0065] The content of the compound represented by (C) general formula (1) in the polyimide precursor resin composition according to this embodiment is preferably 0.001 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, even more preferably 0.03 to 8 parts by mass, particularly preferably 0.1 to 5 parts by mass, and most preferably 0.5 to 2 parts by mass, per 100 parts by mass of (A1) polyimide or (A2) polyimide precursor as component (A). Having the compound represented by (C) general formula (1) within this range makes it easier to obtain a film with excellent in-plane uniformity of the pre-baked film and excellent focus margin and aperture diameter cross-section after development. Having the content of the compound represented by (C) general formula (1) within the above upper limit suppresses swelling of the film during development and excessive shrinkage of the film during curing, making it easier to obtain better resolution performance. The compound represented by (C) general formula (1) may be used alone or in combination of two or more types.

[0066] (D) Solvent The photosensitive resin composition may optionally contain a solvent. Examples of solvents that can be used in this embodiment include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and alcohols. One solvent may be used alone, or two or more solvents may be used in combination.

[0067] Examples of solvents include N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone (GBL), propylene glycol monomethyl ether acetate, ethyl acetoacetate, dimethyl succinate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, ε-caprolactone, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dimethyl malonate, dichloromethane, 3-Methoxy-N,N-dimethylpropanamide, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene, N-ethyl-2-pyrrolidone (NEP), N-acetyl-2-pyrrolidone, N-butyl-2-pyrrolidone, N-(3-hydroxypropyl)-2-pyrrolidone, 2-oxo-1- Examples include methyl pyrrolidine acetate, N-cyclohexyl-2-pyrrolidone, 2-(2-oxopyrrolidine-1-yl)ethyl methacrylate, Nn-octyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-dipropyl-2-imidazolidinone, 1,3-diisopropyl-2-imidazolidinone, and 1,3-dibutyl-2-imidazolidinone.

[0068] Among these (D) solvents, amide solvents are preferred, and among them, N-methyl-2-pyrrolidone (NMP) or N-ethyl-2-pyrrolidone (NEP) are more preferred, with N-ethyl-2-pyrrolidone (NEP) being the most preferred. The inventors believe the reason for this is as follows: In the pre-baking process, the amide moiety of the amide solvent interacts with the imide moiety or amide moiety in (A)(A1) polyimide or (A2) polyimide precursor and (C) the compound represented by general formula (1) through electrostatic interactions, hydrogen bonding interactions, or dipole-dipole interactions, thereby suppressing aggregation of each medium and promoting the effect of the compound represented by general formula (1), resulting in a film with excellent in-plane uniformity. Furthermore, N-ethyl-2-pyrrolidone (NEP) has a boiling point of 218°C, which is higher than that of N-methyl-2-pyrrolidone (NMP) at 202°C. Therefore, it volatilizes slowly during the pre-baking process, maintaining convection for a long time during the pre-baking process, and as a result, a film with excellent in-plane uniformity can be obtained. In addition, because amide solvents such as NEP and NMP have a slow volatilization rate, they suppress the uneven distribution of the compound represented by (C) general formula (1) on the pre-baked film surface and allow for uniform dispersion within the film. As a result, a significant effect in promoting the dissolution of residue at the bottom of the unexposed area can be achieved. (D) When using other solvents in addition to N-methyl-2-pyrrolidone (NMP) or N-ethyl-2-pyrrolidone (NEP) as the solvent, the proportion of the mass of N-methyl-2-pyrrolidone (NMP) or N-ethyl-2-pyrrolidone (NEP) to the total mass of the solvent (D) is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, particularly preferably 70% by mass or more, and most preferably 80% by mass or more.

[0069] The amount of solvent (D) in the photosensitive resin composition of this embodiment is preferably 10 parts by mass or more and 1,000 parts by mass or less, more preferably 100 parts by mass or more and 700 parts by mass or less, and even more preferably 125 parts by mass or more and 500 parts by mass or less, per 100 parts by mass of polyimide (A1) or polyimide precursor (A2) as component (A).

[0070] (E) Radical polymerizable compounds (polymerizable monomers) The photosensitive resin composition may optionally further contain a radical polymerizable compound. A radical polymerizable compound is a monomer that has a radically polymerizable unsaturated bond and can assist in the crosslinking of the polyimide precursor upon exposure. As such monomers, (meth)acrylic compounds that undergo radical polymerization reactions with a photopolymerization initiator are preferred.

[0071] Examples of radical polymerizable compounds include mono- or di(meth)acrylates of ethylene glycol or polyethylene glycol, mono- or di(meth)acrylates of propylene glycol or polypropylene glycol, mono, di, or tri(meth)acrylates of glycerol, cyclohexanedi(meth)acrylate, di(meth)acrylate of 1,4-butanediol, di(meth)acrylate of 1,6-hexanediol, di(meth)acrylate of neopentyl glycol, mono- or di(meth)acrylate of bisphenol A, benzenetri(meth)acrylate, isobornyl(meth)acrylate, (meth)acrylamide and its derivatives, trimethylolpropanetri(meth)acrylate, di or tri(meth)acrylate of glycerol, di, tri, or tetra(meth)acrylate of pentaerythritol, tris-(2-acryloxyethyl)isocyanurate, and ethylene oxide or propylene oxide adducts of these compounds. The radical polymerizable compound may be used alone or in combination of two or more types.

[0072] Among these radical polymerizable compounds, it is particularly preferable that they have three or more radical polymerizable groups from the viewpoint of mechanical properties and resolution performance.

[0073] When the polyimide precursor contains the above-mentioned monomer having a radically polymerizable unsaturated bond, the amount of monomer having a radically polymerizable unsaturated bond is preferably 1 to 80 parts by mass per 100 parts by mass of the (A2) polyimide precursor. If the amount of monomer is 1 part by mass or more per 100 parts by mass of the (A2) polyimide precursor, good sensitivity is easily obtained during exposure, and if it is 80 parts by mass or less, excellent in-plane uniformity of the coating film is easily obtained. From the viewpoint of resolution performance, adhesion performance, and thermophysical properties, it is more preferable that the amount of monomer having a photopolymerizable unsaturated bond is 5 to 40 parts by mass per 100 parts by mass of the (A2) polyimide precursor.

[0074] (F) Sensitizer The photosensitive resin composition may 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, p-dimethylaminocinnamyrideneindanone, p -Dimethylaminobenzylideneindanone, 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-acetyl Examples include -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. A single sensitizer may be used, or two or more sensitizers may be used in combination.

[0075] The amount of sensitizer added to the photosensitive resin composition is preferably 0.1 to 25 parts by mass per 100 parts by mass of (A1) polyimide or (A2) polyimide precursor as component (A).

[0076] (G) Organometallic complexes The photosensitive resin composition may optionally contain an organometallic complex. The metal contained in the organometallic complex is not particularly limited, but is preferably at least one metal selected from the group consisting of titanium, zirconium, and aluminum, more preferably at least one metal selected from the group consisting of titanium and zirconium from the viewpoint of the glass transition temperature of the cured film, and is particularly preferably titanium from the viewpoint of room temperature storage stability and solubility.

[0077] Suitable organotitanium compounds include those in which an organic chemical substance is bonded to a titanium atom via covalent or ionic bonds. Specific examples of organotitanium compounds are shown in I) to VII) below: I) Titanium chelate compounds: Among these, titanium chelates having two or more alkoxy groups are more preferred because they provide good storage stability and a good pattern for the polyimide precursor. Specific examples include titanium bis(triethanolamine)diisopropoxide, titanium di(n-butoxide)bis(2,4-pentanedione), titanium diisopropoxidebis(2,4-pentanedione), titanium diisopropoxidebis(tetramethylheptanedione), and titanium diisopropoxidebis(ethylacetoacetate). II) Tetraalkoxy titanium compounds: For example, 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, and titanium tetrakis[bis{2,2-(alyloxymethyl)butoxide}]. III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, etc. IV) Monoalkoxy titanium compounds: For example, titanium tris(dioctyl phosphate) isopropoxide and titanium tris(dodecylbenzenesulfonate) isopropoxide. V) Titanium oxide compounds: For example, titanium oxide bis(pentanedione), titanium oxide bis(tetramethylheptanedione), and phthalocyanine titanium oxide. VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate. VII) Titanate coupling agent: For example, isopropyltridodecylbenzenesulfonyl titanate. These organotitanium compounds may be used individually or in combination of two or more.

[0078] Among the above compounds, the organotitanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, with I) titanium chelate compounds being particularly preferred. Among I) titanium chelate compounds, titanium diisopropoxide bis(ethylacetoacetate) is the most preferred.

[0079] When the photosensitive resin composition contains an organotitanium compound, the amount blended is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of (A1) polyimide or (A2) polyimide precursor as component (A). When the amount of organotitanium compound blended is 0.05 parts by mass or more per 100 parts by mass of component (A), good heat resistance and chemical resistance are easily exhibited, and when it is 10 parts by mass or less, excellent storage stability is easily exhibited.

[0080] (H) Nitrogen-containing heterocyclic compound When forming a cured film on a substrate made of copper or a copper alloy using polyimide or a polyimide precursor, the photosensitive resin composition may optionally contain a nitrogen-containing heterocyclic compound as component (H) to suppress discoloration on the copper. Examples of nitrogen-containing heterocyclic compounds for (H) include azole compounds and purine derivatives. Only one nitrogen-containing heterocyclic compound may be used, or two or more may be used in combination.

[0081] 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, and 1-methyl-1H-tetrazol.

[0082] Among the above azole compounds, preferably, at least one selected from the group consisting of toltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, and 5-amino-1H-tetrazole.

[0083] Specific examples of purine derivatives include, for example, purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8 Examples include -aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine, and their derivatives.

[0084] When the photosensitive resin composition contains the above-mentioned azole compound or purine derivative, the amount blended is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of (A1) polyimide or (A2) polyimide precursor as component (A), from the viewpoint of photosensitivity characteristics. When the amount of azole compound blended per 100 parts by mass of (A)(A1) polyimide or (A2) polyimide precursor is 0.1 parts by mass or more, discoloration of the copper or copper alloy surface by the polyimide precursor or the layer or film containing it is easily suppressed, while when it is 20 parts by mass or less, excellent photosensitivity is easily obtained.

[0085] <Other compounds> The photosensitive resin composition may further contain compounds other than those listed above. Examples of other compounds are given below.

[0086] (Thermal crosslinking agent) The photosensitive resin composition may further contain a thermal crosslinking agent. This makes it easier to improve elongation and chemical resistance.

[0087] A thermal crosslinking agent is a compound that undergoes an addition reaction or condensation polymerization reaction upon exposure to heat. These reactions readily occur between (A)(A1) polyimide or (A2) polyimide precursors and thermal crosslinking agents, as well as between thermal crosslinking agents themselves. The reaction temperature is preferably 150°C or higher.

[0088] Examples of thermal crosslinking agents include alkoxymethyl compounds, epoxy compounds, oxetane compounds, bismaleimide compounds, allyl compounds, and blocked isocyanate compounds. A single thermal crosslinking agent may be used, or two or more may be used in combination.

[0089] Examples of alkoxymethyl compounds include the following compounds: [ka] [ka]

[0090] 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.).

[0091] 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 diphenoate, 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 silicate, phenol novolac type oxetane, 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene, OXT121 (manufactured by Toagosei, trade name), OXT221 (manufactured by Toagosei, trade name), etc.

[0092] 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- 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.

[0093] 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, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallylamine, 1,3,5-benzenetricarboxylic acid triallyl, trimellitate triallyl, triallyl phosphate, triallyl phosphite, and triallyl citrate.

[0094] 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.) and tolylene diisocyanate-based blocked isocyanates (e.g., Takenate B-830 from Mitsui Chemicals, Inc.). Examples include 4,4'-diphenylmethane diisocyanate-based blocked isocyanates (e.g., Takenate B-815N manufactured by Mitsui Chemicals, Inc., Bronate PMD-OA01 and PMD-MA01 manufactured by Daiei Sangyo Co., Ltd.), 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).

[0095] Among the thermal crosslinking agents listed above, alkoxymethyl compounds are preferred from the viewpoint of storage stability and chemical resistance of the photosensitive resin composition.

[0096] (Thermobase generator) If the photosensitive resin composition contains a (A2) polyimide precursor as the resin, the photosensitive resin composition may contain a thermal base generator. A thermal base generator is a compound that generates a base when heated. Including a thermal base generator makes it easier to further promote the imidization of the polyimide precursor.

[0097] Examples of thermal base generators include amine compounds protected by a tert-butoxycarbonyl group, or thermal base generators disclosed in International Publication No. 2017 / 038598. Other known thermal base generators can also be used. A single thermal base generator may be used, or two or more may be used in combination.

[0098] Examples of amine compounds protected by the tert-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, 2-amino-1,3- Propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzylal Coal, diethanolamine, diisopropanolamine, 3-pyrrolidinel, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidyl)-2-propanol, 1,4-butanolbis Examples include (3-aminopropyl) ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown 5-ether, diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxaundecane, or compounds in which the amino group of an amino acid or its derivative is protected by a tert-butoxycarbonyl group.

[0099] The content of the thermal base generator in the photosensitive resin composition is preferably 0.1 parts by mass to 30 parts by mass, more preferably 1 part by mass to 20 parts by mass, per 100 parts by mass of (A1) polyimide or (A2) polyimide precursor as component (A). From the viewpoint of the imidization promoting effect, the above content is 0.1 parts by mass or more, and from the viewpoint of the physical properties of the photosensitive resin layer after curing of the polyimide precursor, 20 parts by mass or less is preferred.

[0100] (Hindered phenol compounds) To suppress discoloration on the copper surface, the photosensitive resin composition may contain a hindered phenol compound.

[0101] 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), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], and 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4- Examples include hydroxyphenyl)propionate, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, and 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene.

[0102] Furthermore, examples of hindered phenol compounds include 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-H Droxy-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-di Methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,Examples include 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.

[0103] Among the above hindered phenol compounds, 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. The hindered phenol compound may be used alone or in combination of two or more.

[0104] The content of the hindered phenol compound in the photosensitive resin composition is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of (A1) polyimide or (A2) polyimide precursor as component (A), from the viewpoint of photosensitivity characteristics. When the content of the hindered phenol compound per 100 parts by mass of (A)(A1) polyimide or (A2) polyimide precursor is 0.1 parts by mass or more, discoloration and corrosion by the polyimide precursor formed on copper or a copper alloy or a layer or film containing it is easily prevented, while when it is 20 parts by mass or less, excellent photosensitivity is easily obtained. The hindered phenol compound may be one type or a combination of two or more types.

[0105] (Adhesive enhancer) To improve the adhesion between the polyimide film and the substrate, the photosensitive resin composition may contain an adhesive aid. Examples of adhesive aids include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamidoic acid, and benzophenone-3,3'-bis(N-[3-triethoxysilyl]propyl Examples include silane coupling agents such as propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and 3-(trialkoxysilyl)propylsuccinic anhydride, as well as aluminum-based adhesive aids such as aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0106] If the photosensitive resin composition contains an adhesive aid, the content of the adhesive aid is preferably 0.5 to 25 parts by mass per 100 parts by mass of (A1) polyimide or (A2) polyimide precursor as component (A). The adhesive aid may be one type or a combination of two or more types.

[0107] From the viewpoint of adhesive strength, silane coupling agents are preferred as adhesive aids. Suitable silane coupling agents include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: product name KBM803, manufactured by Chisso Corporation: product name Cyra Ace S810), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Co., Ltd.: product name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: product name LS1375, manufactured by Azmax Co., Ltd.: product name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Co., Ltd.: product name SIM6473.5C), and mercaptomethylmethyldimethoxysilane (manufactured by Azmax Co., Ltd.: product name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldieth Examples include xymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, and 4-mercaptobutyltripropoxysilane.

[0108] Furthermore, as silane coupling agents, there are N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: product name LS3610, manufactured by Azmax Co., Ltd.: product name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Co., Ltd.: product name SIU9058.0), N-(3-diethoxymethoxysilylpropyl)urea, N-(3-ethoxydimethoxysilylpropyl)urea, N-(3-tripropoxysilylpropyl)urea, N-(3-diethoxypropoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-dimethoxypropoxysilylpropyl)urea, N-(3-methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea, N-(3-ethoxydimethoxysilylethyl) Examples include urea, N-(3-tripropoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-tripropoxysilylbutyl)urea, 3-(m-aminophenoxy)propyltrimethoxysilane (manufactured by Azmax Co., Ltd.: product name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: product name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: product name SLA0599.1), aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: product name SLA0599.2), etc.

[0109] Furthermore, as silane coupling agents, there are 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax Co., Ltd.: product name SIT8396.0), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylmethylethyl)pyridine, (3-triethoxysilylpropyl)-t-butylcarbamate, (3-glycidoxypropyl)triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, and tetrakis(methoxy) Ethoxysilane), tetrakis(methoxy-n-propoxysilane), tetrakis(ethoxyethoxysilane), tetrakis(methoxyethoxyethoxysilane), bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane, bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane, bis(triethoxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide, bis[3-(triethoxysilyl) Xysilyl)propyl]tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylsiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyln-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol,Examples include ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, and triphenylsilanol. The silane coupling agent may be used alone or in combination of two or more.

[0110] In particular, from the viewpoint of storage stability, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and the following formula: [ka] A silane coupling agent having at least one structure represented by is preferred.

[0111] When using a silane coupling agent, the preferred content is 0.01 to 20 parts by mass per 100 parts by mass of (A1) polyimide or (A2) polyimide precursor as component (A).

[0112] (Polymerization inhibitor) The photosensitive resin composition may contain polymerization inhibitors to improve the viscosity and photosensitivity stability of the polyimide precursor, particularly when stored in a solvent solution. Examples of 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. The polymerization inhibitors may be present individually or in combination of two or more.

[0113] Method for manufacturing hardened relief patterns The method for manufacturing the cured relief pattern of this embodiment is: (1) A step of applying the negative-type photosensitive resin composition of this embodiment described above onto a substrate to form a photosensitive resin layer on the substrate (resin layer formation step), (2) A step of exposing the above photosensitive resin layer (exposure step), (3) A step of developing the photosensitive resin layer after exposure to form a relief pattern (relief pattern formation step), (4) A step of forming a hardened relief pattern by heat-treating the above relief pattern (hardened relief pattern formation step) Includes.

[0114] (1) Resin layer formation process In this process, the negative-type photosensitive resin composition of this embodiment is applied to a substrate and, if necessary, subsequently dried to form a photosensitive resin layer. The application method may include conventional methods used for applying photosensitive resin compositions, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., or spray application using a spray coater.

[0115] If necessary, the coating containing the photosensitive resin composition can be dried. Examples of drying methods include air drying; heating and drying using an oven or hot plate; and vacuum drying. Specifically, in the case of air drying or heating and drying, drying can be carried out at a temperature of 20°C to 150°C for 1 minute to 1 hour. In this manner, a photosensitive resin layer can be formed on the substrate.

[0116] (2) Exposure process In this process, the photosensitive resin layer formed above is exposed to ultraviolet light or the like, either through a patterned photomask or reticle, or directly, using an exposure device such as a contact aligner, mirror projection, or stepper. This exposure causes the polymerizable groups of (A)(A1) polyimide or (A2) polyimide precursor, and the polymerizable groups of (E) radical polymerizable compound contained in the negative-type photosensitive resin composition to crosslink due to the action of (B) photopolymerization initiator. This crosslinking makes the exposed area insoluble in the developer solution described later, thus enabling the formation of a relief pattern.

[0117] Subsequently, if necessary, post-exposure baking (PEB), pre-development baking, or both may be performed using any combination of temperature and time, for purposes such as improving photosensitivity. The baking conditions are preferably a temperature of 40°C to 120°C and a time of 10 to 300 seconds, but are not limited to this range as long as they do not impair the properties of the photosensitive resin composition of this embodiment.

[0118] (3) Relief pattern formation process In this step, 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 from conventionally known photoresist development methods, such as the rotary spray method, the paddle method, or the immersion method with ultrasonic treatment. After development, post-development baking (PDB) may be performed using any combination of temperature and time, if necessary, from the viewpoint of adjusting the shape of the relief pattern, improving in-plane uniformity, or resolving performance. The baking conditions are preferably a temperature of 40°C to 150°C and a time of 10 to 300 seconds, but are not limited to this range as long as they do not impair the various properties of the photosensitive resin composition of this embodiment. From the viewpoint of good tapered shape in terms of resolving performance, it is more preferable to perform PDB at a temperature of 120°C to 150°C for 1 to 3 minutes. Furthermore, from the viewpoint of good tapered shape, it is preferable to perform PDB at a predetermined temperature rather than gradually increasing the temperature.

[0119] As the developer used for development, for example, a good solvent for the negative-type photosensitive resin composition of this embodiment, or a combination of the good solvent and a poor solvent is preferred. Preferred good solvents include, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Preferred poor solvents include, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When using a mixture of a good solvent and a poor solvent, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the negative-type photosensitive resin composition. Two or more solvents, for example, can be used in combination. The negative-type photosensitive resin composition of this embodiment is preferably used for development using a developer containing 90% by mass or more of an organic solvent.

[0120] (4) Hardened relief pattern formation process In this process, the relief pattern obtained by the above development is heat-treated to dilute the photosensitive component and imidize the imide precursor portion of the (A2) polyimide precursor, thereby converting it into a cured relief pattern containing polyimide. Various methods can be selected for the heat treatment, such as using a hot plate, using an oven, or using a heating oven or heating curing furnace with a temperature programmable. The heat treatment can be carried out, for example, at 150°C to 350°C for 30 minutes to 5 hours. The heat treatment temperature is 150°C to 250°C, preferably 150°C to 230°C, and more preferably 170°C to 230°C. Air may be used as the atmospheric gas during heat curing, or an inert gas such as nitrogen or argon may be used.

[0121] <Method for producing a cured film containing polyimide> Another aspect of the present disclosure provides a method for producing a polyimide-containing cured film, comprising the step of curing the photosensitive resin composition described above to form a cured film containing polyimide. The curing conditions for the photosensitive resin composition in this embodiment may be, for example, the same as the baking conditions included in the method for producing a cured relief pattern described above, or the conditions for the cured relief pattern formation step (4).

[0122] <Semiconductor device> This disclosure also provides a semiconductor device having a cured relief pattern obtained from the above-described photosensitive resin composition. More specifically, a semiconductor device is provided having a substrate which is a semiconductor element and a cured relief pattern. The cured relief pattern may be manufactured using the above-described photosensitive resin composition by the above-described method for manufacturing a cured relief pattern.

[0123] This disclosure can also be applied to a method for manufacturing a semiconductor device, which uses a semiconductor element as a substrate and includes the method for manufacturing the cured relief pattern described above as part of the process. In this case, the cured relief pattern formed by the method for manufacturing the cured relief pattern of this disclosure can be formed as a surface protective film for a semiconductor device, an interlayer insulating film, an insulating film for redistribution, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure, and can be manufactured by combining it with a known method for manufacturing a semiconductor device.

[0124] <Display device> This disclosure 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. 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. The cured film can be applied, for example, to surface protective films, insulating films, planarization films, etc., of TFT liquid crystal display elements and color filter elements; protrusions for MVA type liquid crystal display devices; partitions for the cathodes of organic EL elements; etc.

[0125] 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. [Examples]

[0126] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0127] Measurement and Evaluation Methods The physical properties of polyimides, polyimide precursors, or negative-type photosensitive resin compositions were measured and evaluated according to the following methods.

[0128] <Weight average molecular weight> The weight-average molecular weight (Mw) of each resin was measured using gel permeation chromatography (on a standard polystyrene basis) under the following conditions. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Columns: Showa Denko Corporation Shodex KD-805 / KD-804 / KD-803 in series Standard monodisperse polystyrene: Shodex STANDARD SM-105, manufactured by Showa Denko Corporation. Mobile phase: 0.1 mol / L LiBr / N-methyl-2-pyrrolidone (NMP) Flow rate: 1mL / min

[0129] <Evaluation of in-plane uniformity of pre-baked films> A photosensitive resin composition prepared by the method described below was rotary coated onto a 6-inch silicon wafer (manufactured by Fujimi Electronics Industries, Ltd., thickness 625 ± 25 μm) using a coater developer (D-Spin 60A type, manufactured by SOKUDO Corporation). Then, pre-baking was performed on a hot plate at 110°C for 240 seconds to form a coating film approximately 10.0 μm thick. The film thickness was measured at 50 points within the surface of this coating using a VM-2110 manufactured by Dainippon Screen Manufacturing Co., Ltd., and the difference between the maximum and minimum values ​​was defined as the uniformity of the film thickness within the surface, which was evaluated according to the following criteria. <Evaluation Criteria> "A": Less than 0.1 μm "B": 0.1 μm or more and less than 0.3 μm "C": 0.3 μm or more and less than 0.5 μm "D": 0.5 μm or more and less than 1.0 μm "E": 1.0μm or more

[0130] <Evaluation of resolution performance> Manufacturing and evaluation of relief pattern films A 6-inch wafer (manufactured by Fujimi Electronics Industries, Ltd., thickness 625±25μm) was prepared by sputtering 200nm thick Ti and 400nm thick Cu in that order using a sputtering apparatus (L-440S-FHL model, manufactured by Canon Anelva Corporation) to create a sputtered Cu wafer substrate. A photosensitive resin composition was spin-coated onto the 6-inch silicon wafer using a spin coater (D-SPIN60A model, manufactured by SOKUDO Corporation), and dried on a hot plate at 100°C for 240 seconds to create a pre-baked film with a film thickness of 5.0μm after heat curing. This spin-coated film was irradiated using an FPA-3030iWa (manufactured by Canon Corporation) with a test pattern reticle having a circular pattern with a mask size of 5μm in diameter to determine the exposure dose that yielded the best resolution (optimal exposure dose). In this process, using the spin-coated film surface as a reference, the focus was moved 1 μm towards the top and bottom of the film for each exposure dose, and exposure was performed accordingly. Next, the coating film formed on the sputtered Cu wafer was spray-developed using cyclopentanone in a developer (D-SPIN636, manufactured by Dainippon Screen Co., Ltd.), and rinsed with propylene glycol methyl ether acetate to obtain a circular recessed relief pattern of the photosensitive resin composition. The development time for spray development was defined as 1.4 times the minimum time required for the unexposed areas of the photosensitive resin composition to develop in the spin-coated film. Using a temperature-boosting programmable curing furnace (VF-2000, manufactured by Koyo Lindbergh), the sputtered Cu wafer substrate with the circular recessed relief pattern was heat-treated in a nitrogen atmosphere by raising the temperature to 230°C at a heating rate of 5°C / min and holding it at 230°C for 2 hours to obtain a circular recessed cured relief pattern of polyimide on the sputtered Cu wafer substrate. Each of the obtained patterns was evaluated using the following method.

[0131] 《Evaluation of the tapered shape of the pattern》 The cross-section of the circular recessed pattern with a diameter of 5 μm obtained above was milled using a FIB apparatus (JIB-4000, JEOL Ltd.), and the cross-sectional shape of the pattern was observed. The taper angle of the pattern relative to the substrate was determined by measuring the inclination at the midpoint of the taper. The pattern cross-sectional shape was evaluated according to the following criteria. <Evaluation Criteria> "A": Taper angle is 75° or more and less than 85° "B": Taper angle is 70° or more but less than 75°, and 85° or more but less than 90°. "C": Taper angle other than those specified above, and undercuts or bridging are observed in the pattern cross-section. Figure 1 shows a FIB photograph of the pattern cross-sectional shape obtained in Example 4. Figure 1 also shows an auxiliary line (1) indicating the inclination at the midpoint of the pattern. The taper angle of the pattern obtained in Example 4 relative to the substrate (auxiliary line (2)) was 83°.

[0132] <Evaluation Criteria for Focus Margin (Depth of Focus)> Regarding the apertureability of the circular recessed 5μm diameter patterns obtained above, focus patterns that met both of the following criteria (I) and (II) were judged to be acceptable, and resolution evaluation was performed. (I) The area of ​​the pattern opening is at least half the area of ​​the corresponding pattern mask opening. (II) The pattern cross section does not have a tapered base, and there is no undercutting, swelling, or bridging. The focus margin (depth of focus) that met the above criteria was evaluated according to the following criteria. <Evaluation Criteria> "A": Focus margin of 8 μm or more "B": Focus margin is 6 μm or more and less than 8 μm "C": Focus margin is 4μm or more and less than 6μm "D": Focus margin is 2 μm or more and less than 4 μm "E": Focus margin less than 2 μm

[0133] <Synthesis Example 1> Synthesis of Polymer A-1 In a flask equipped with a stirrer and a condenser, within the range of 20 °C to 30 °C, 35.19 g (0.0857 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) was dissolved in 200 g of N-methyl-2-pyrrolidone. Subsequently, 52.05 g (0.1 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (BPADA) was added and stirred for 1 hour. Subsequently, while flowing nitrogen, the temperature was raised to 190 °C, stirred for 5 hours, and cooled to 30 °C or below. Subsequently, after diluting with 100 g of tetrahydrofuran, it was precipitated in 2 L of methanol, filtered, and this was recovered and vacuum dried at 45 °C for 1 day to obtain a polyimide resin (A-1). The weight average molecular weight of the obtained polyimide (A-1) was 17,000.

[0134] <Synthesis Example 2> Synthesis of Polymer A-2 31.02 g (0.1 mol) of 4,4'-oxydiphthalic anhydride (ODPA) was placed in a 2 L separable flask, 27.33 g (0.21 mol) of 2-hydroxyethyl methacrylate (HEMA) and 65 mL of γ-butyrolactone were added, and stirred at room temperature. While stirring, 15.82 g (0.20 mol) of pyridine was added to obtain a reaction mixture. After the heat generation by the reaction ended, it was allowed to cool to room temperature and left for 16 hours.

[0135] Next, under ice cooling, a solution of 40.44 g (0.196 mol) of dicyclohexylcarbodiimide (DCC) dissolved in 40 mL of γ-butyrolactone was added to the reaction mixture over 30 minutes while stirring. Subsequently, a solution of 17.16 g (0.0857 mol) of 4,4'-diaminodiphenyl ether (DADPE) dissolved in 50 mL of γ-butyrolactone was added over 60 minutes while stirring. After mixing 150 mL of γ-butyrolactone, the reaction mixture was further stirred at room temperature for 4 hours, then 10 mL of ethyl alcohol was added and stirred for 10 minutes. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0136] The resulting reaction solution was added to 1 L of ethyl alcohol to form a precipitate consisting of a crude polymer. The formed crude polymer was filtered off, dissolved in 300 mL of γ-butyrolactone to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 5 L of water to precipitate the polymer. After the obtained precipitate was filtered off, it was dried under vacuum to obtain a powdery polyimide precursor resin A-2. The vacuum drying was carried out until the water content in the polyimide precursor resin A-2 was less than 1.0%. When the molecular weight of the polyimide precursor resin A-2 was measured by gel permeation chromatography (in terms of standard polystyrene conversion), the weight average molecular weight (Mw) was 22,000.

[0137] <Synthesis Example 3> Synthesis of Polymer A-3 The reaction was carried out in the same manner as the method described in Synthesis Example 2 above, except that 29.42 g (0.10 mol) of 4,4'-biphthalic anhydride (BPDA) was used instead of 31.02 g (0.1 mol) of 4,4'-oxydiphthalic anhydride (ODPA) in Synthesis Example 2, to obtain a polyimide precursor resin A-3. The weight average molecular weight (Mw) of the polyimide precursor resin A-3 was 27,000.

[0138] <Synthesis Example 4> Synthesis of Polymer A-4 The reaction was carried out in the same manner as the method described in Synthesis Example 2 above, except that 9.27 g (0.0857 mol) of 1,4-phenylenediamine (pPD) was used instead of 17.16 g (0.0857 mol) of 4,4'-diaminodiphenyl ether (DADPE) in Synthesis Example 2, to obtain a polyimide precursor resin A-4. The weight average molecular weight (Mw) of the polyimide precursor resin A-4 was 20,500.

[0139] <Synthesis Example 5> Synthesis of Polymer A-5 Polyimide precursor resin A-5 was obtained by carrying out the reaction in the same manner as described in Synthesis Example 2, except that 13.09 g (0.05 mol) of pyromellitic dianhydride (PMDA) and 12.41 g (0.05 mol) of 4,4'-oxydiphthalic anhydride (ODPA) were used instead of 31.02 g (0.1 mol) of 4,4'-oxydiphthalic anhydride (ODPA) in Synthesis Example 2, and 18.20 g (0.0857 mol) of m-tolidine (mTB) was used instead of 17.16 g (0.0857 mol) of 4,4'-diaminodiphenyl ether (DADPE) to obtain polyimide precursor resin A-5. The weight-average molecular weight (Mw) of polyimide precursor resin A-5 was 23,000.

[0140] <Synthesis Example 6> Synthesis of Polymer A-6 The reaction was carried out in the same manner as described in Synthesis Example 2, except that 18.20 g (0.0808 mol) of m-tolidine (mTB) was used instead of 17.16 g (0.0857 mol) of 4,4'-diaminodiphenyl ether (DADPE) in Synthesis Example 2, to obtain polyimide precursor resin A-6. The weight-average molecular weight (Mw) of polyimide precursor resin A-6 was 26,000.

[0141] <Synthesis Example 7> Synthesis of Polymer A-7 20.80 g (40 mmol) of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride was dissolved in 70 g of N-methylpyrrolidone (NMP). Subsequently, 9.08 g (35.2 mmol) of 4,4'-isopropylidene bis(2-aminophenol) (BHAPP) was dissolved in 50 g of NMP and added dropwise over 1 hour at a temperature of 10°C to 25°C. After stirring at 25°C for 30 minutes, 10 g of toluene was added, and the mixture was reacted at 200°C for 4 hours under nitrogen flow, and then cooled to 25°C. Next, 15.3 g (100 mmol) of 4-(chloromethyl)styrene, 16.6 g (120 mmol) of potassium carbonate, 1.66 g (12 mmol) of potassium iodide, and 0.08 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical were added, and the mixture was reacted at 95°C for 15 hours. After cooling to 25°C, the mixture was diluted with 120 g of tetrahydrofuran. Subsequently, the reaction mixture was added dropwise to a mixture of 1.8 liters of methanol and 0.6 L of water, stirred for 15 minutes, and the polyimide resin was filtered. Next, the resin was re-slurred with 1 L of water, filtered, re-slurred again with 1 L of methanol, filtered, and dried under reduced pressure at 40°C for 8 hours. Next, the dried resin was dissolved in 250 g of tetrahydrofuran, and 40 g of ion exchange resin (MB-1: Organo) was added. The mixture was stirred for 4 hours, and after filtering out the ion exchange resin, the polyimide resin was precipitated in 2 liters of methanol and stirred for 15 minutes. The polyimide resin was filtered to obtain it, and dried under reduced pressure at 45°C for 1 day to obtain polyimide resin A-7. The weight-average molecular weight (Mw) of polyimide resin A-7 was 16,000.

[0142] <Synthesis Example 8> Synthesis of Polymer A-8 A Dean-Stark extractor was attached, and 200.0 g of NMP and 22.1 g (0.08 mol) of 4,4'-diamino-2-phenyldiphenyl ether (PDPE) were added to a nitrogen-purged three-necked flask and dissolved. Then, 10.9 g (0.05 mol) of PMDA, 19.2 g (0.05 mol) of norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride (CpODA) and 48.4 g of toluene were added and the mixture was heated to 180°C.

[0143] After confirming that the theoretical amount of water (1.80 g) and the added toluene (48.4 g) had been extracted using the Dean-Stark extractor, heating was stopped and the mixture was allowed to cool to room temperature. This yielded the reaction solution.

[0144] The resulting reaction solution was added to 800 g of ethyl alcohol, which produced a precipitate consisting of crude polymer. The crude polymer was filtered off and dissolved in 300 g of GBL to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 3 kg of water to precipitate the polymer, and the resulting precipitate was filtered off and then vacuum dried to obtain a powdered polymer (polyimide resin A-8). The average polymerization molecular weight (Mw) of the obtained polyimide A-8 was 16,000.

[0145] Examples 1-8 of the synthesis are summarized in Table 1 below. [Table 1]

[0146] Preparation of resin compositions <Examples 1-25 and Comparative Examples 1-5> A resin composition solution was obtained by mixing (A) (A1) polyimide or (A2) polyimide precursor, (B) photopolymerization initiator, (C) compound represented by the above general formula (1), (D) solvent, (E) radical polymerizable compound, (F) sensitizer, (G) organometallic complex, and (H) rust inhibitor as a nitrogen-containing heterocyclic compound, in the amounts shown in Tables 2, 3, or 4 below. The amounts in Tables 2, 3, or 4 below are parts by mass of each component when component (A) is 100 parts by mass. The obtained solution was filtered through a polyethylene filter with pores of 0.2 μm to obtain the resin compositions of Examples 1 to 25 and Comparative Examples 1 to 5. The symbols in Tables 2, 3, or 4 refer to the following components, respectively. The compositions were evaluated according to the method described above, and the evaluation results are shown in Tables 2, 3, or 4 below.

[0147] (A)(A1)Polyimide or (A2)Polyimide precursor, the above polymers (A-1) to (A-8) were used.

[0148] (B) The following (B-1) to (B-3) were used as photopolymerization initiators. (B-1): 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime (B-2): Ethyl-2,3-dioxo-3-phenylpropionate-2-(O-benzoyl)oxime (B-3): 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime) (Irgacure OXE-01, manufactured by BASF Japan)

[0149] (C) The following compounds (C-1) to (C-4) were used as compounds represented by the general formula (1) above. (C-1):N-methylsuccinimide (C-2):N-ethylsuccinimide (C-3): N-pentylsuccinimide (C-4): N-butylsuccinimide

[0150] (D) The following solvents (D-1) to (D-4) were used. (D-1): γ-butyrolactone (D-2): N-Ethyl-2-pyrrolidone (D-3): N-Methyl-2-pyrrolidone (D-4): Ethyl lactate

[0151] (E) As the radical polymerizable compound, the following (E-1) and (E-2) were used. (E-1): Tetraethylene glycol dimethacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) (E-2): Tris-(2-acryloxyethyl) isocyanurate (product name: A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0152] (F) As the sensitizer, the following (F-1) was used. (F-1): N-Phenyldiethanolamine

[0153] (G) As the organometallic complex, the following (G-1) was used. (G-1): TC-750 (manufactured by Matsumoto Fine Chemical)

[0154] (H) As the nitrogen-containing heterocyclic compound, the following (H-1) was used. (H-1): 8-Azaadenine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0155] [Table 2]

[0156] [[ID=!42]] [Table 3] !>

[0157] [Table 4]

[0158] From Table 2, Table 3 and Table 4, it can be seen that the examples are superior to the comparative examples in terms of the in-plane uniformity of the pre-baked film, the focus margin of the relief pattern, and the taper shape of the aperture diameter.

[0159] In particular, a comparison of Examples 4, 8, and 9 shows that the effect is high when an amide solvent is used as (D) solvent, and is especially pronounced when N-ethyl-2-pyrrolidone is used. Furthermore, a comparison of Examples 4 and 11 shows that when N-ethylsuccinimide is used as the compound represented by the above general formula (1) (C), both in-plane uniformity and resolution performance are superior. [Industrial applicability]

[0160] By using the photosensitive resin composition according to the present invention, it is possible to form a cured film with excellent in-plane uniformity and tapered shape of the relief pattern's focus margin and aperture diameter. Furthermore, the photosensitive resin composition according to the present invention can be suitably used in the fields of a method for manufacturing polyimide cured films using the same, the cured film itself, and photosensitive materials useful for the manufacture of electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

1. (A) (A1) polyimide or (A2) polyimide precursor; (B) Photopolymerization initiator; and (C) General formula (1) below: 【Chemistry 1】 {In the formula, R １ This represents an alkyl group having 1 to 10 carbon atoms. Compounds represented by; The (A1) polyimide is the following general formula (2): 【Chemistry 2】 {In the formula, X1 is a tetravalent organic group, Y1 is a divalent organic group, and n is a positive integer.} The structure is represented by the (A2) polyimide precursor, and the following general formula (13): 【Transformation 3】 {In the formula, X² is a tetravalent organic group, Y² is a divalent organic group, m is a positive integer, and R² and R³ are each independently selected from the group consisting of a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms.} A negative-type photosensitive resin composition having the structure represented by [the formula shown].

2. The aforementioned R １ The negative-type photosensitive resin composition according to claim 1, wherein the alkyl group has 1 to 4 carbon atoms.

3. The negative-type photosensitive resin composition according to claim 1, wherein the (C) compound is N-methylsuccinimide and / or N-ethylsuccinimide.

4. The negative-type photosensitive resin composition according to claim 1, wherein the (C) compound is N-ethylsuccinimide.

5. (D) The negative-type photosensitive resin composition according to claim 1 or 2, further comprising N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone as a solvent.

6. The negative-type photosensitive resin composition according to claim 5, wherein the solvent (D) comprises N-ethyl-2-pyrrolidone.

7. The negative-type photosensitive resin composition according to claim 1 or 2, wherein the (B) photopolymerization initiator is an oxime compound.

8. (E) The negative-type photosensitive resin composition according to claim 1 or 2, further comprising a radical polymerizable compound.

9. The aforementioned X １ However, the following general formulas (3) to (8): 【Chemistry 4】 【Transformation 5】 【Transformation 6】 【Transformation 7】 【Transformation 8】 【Chemistry 9】 A negative-type photosensitive resin composition according to claim 1 or 2, having at least one selected from the group consisting of structures represented by .

10. The aforementioned Y １ However, the following general formulas (9) to (12): 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 A negative-type photosensitive resin composition according to claim 1 or 2, having at least one selected from the group consisting of structures represented by .

11. In the above general formula (13), R ２ , and R ３ At least one of these is the following general formula (14): 【Chemistry 14】 {Wherein, R ４ , R ５ , and R ６ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and p is an integer selected from 1 to 10}{ The negative-type photosensitive resin composition according to claim 1 or 2, wherein the monovalent organic group is represented by .

12. X in the above general formula (13) ２ However, the following general formulas (15) to (17): 【Chemistry 15】 【Chemistry 16】 【Chemistry 17】 A negative-type photosensitive resin composition according to claim 1 or 2, having at least one selected from the group consisting of structures represented by .

13. In the above general formula (13), Y ２ However, the following general formulas (19) to (21): [Chemistry 18] 【Chemistry 19】 【Chemistry 20】 A negative-type photosensitive resin composition according to claim 1 or 2, having at least one selected from the group consisting of structures represented by .

14. A method for producing a cured film, comprising the step of curing the negative-type photosensitive resin composition according to claim 1 or 2 to form a cured film containing polyimide.

15. The following steps: (1) A step of applying the negative-type photosensitive resin composition according to claim 1 or 2 onto a substrate to form a photosensitive resin layer on the substrate, (2) A step of exposing the photosensitive resin layer, (3) A step of developing the photosensitive resin layer after exposure to form a relief pattern, (4) A step of heat-treating the relief pattern to form a hardened relief pattern. A method for manufacturing a hardened relief pattern, including [the specified element].

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