Negative photosensitive resin composition, method for producing cured relief pattern, and semiconductor device

Abstract

Provided is a negative photosensitive resin composition containing (A) a polyimide precursor or polyimide, (B) a photopolymerization initiator, (C) a radically polymerizable monomer having one photopolymerizable group, and (D) a nitrogen-containing heterocyclic compound, wherein the component (C) is a liquid at 25°C and 1 atm, the component (D) is a tetrazole derivative, a triazole derivative, a triazine derivative, or a purine derivative, and the purine derivative has an acyl group, an alkoxy group, an alkyl group, a hydroxyalkyl group, or a heteroaryl group.

Description

Negative photosensitive resin composition, method for producing cured relief pattern, and semiconductor device

[0001] The present disclosure relates to a negative photosensitive resin composition, a method for producing a cured relief pattern, and a semiconductor device.

[0002] Polyimide (PI) resins have excellent heat resistance, electrical properties, and chemical resistance, and are therefore used as insulating materials for electronic components, passivation films for semiconductor devices, surface protection films, interlayer insulating films, and the like.

[0003] In recent years, the mounting method (packaging structure) of semiconductor devices on printed wiring boards has been changing in view of improvements in integration density and computing functionality, as well as the miniaturization of chip sizes. Specifically, the conventional mounting method using metal pins and lead-tin eutectic solder has been replaced by structures in which a polyimide coating directly contacts solder bumps, such as BGA (ball grid array) and CSP (chip size packaging), which enable higher density mounting. Furthermore, structures such as FO (fan-out) have been proposed, in which the surface of a semiconductor chip has multiple rewiring layers with an area larger than the area of ​​the semiconductor chip (see, for example, Patent Documents 1 and 2).

[0004] As packages become more multi-layered and denser, fine patterning performance is required for the resin film that forms the rewiring layer.

[0005] Furthermore, as semiconductor devices become increasingly miniaturized, the wiring resistance of semiconductor devices becomes non-negligible, and therefore, the gold or aluminum wiring that has been used until now is being replaced by copper or copper alloy wiring, which has lower resistance. Therefore, the resin film that forms the rewiring layer is required to have high adhesion to the copper wiring.

[0006] As a means for solving the above problem, a method has been disclosed in which adhesion to copper or a copper alloy is improved by adding a specific purine derivative to a composition containing a specific resin and a photosensitizer (see Patent Document 3).

[0007] JP 2005-167191 A JP 2011-129767 A International Publication No. 2018 / 021262 Pamphlet

[0008] However, when a rust inhibitor such as a heterocyclic compound is used to improve adhesion to copper or a copper alloy, there is a problem that foreign matter aggregates in the varnish, causing defects due to the foreign matter after the coating.

[0009] Therefore, an object of the present invention is to provide a photosensitive resin composition that exhibits high adhesion without generating foreign matter even on copper or copper alloys and gives a cured film with good patterning performance, a method for producing a cured relief pattern that forms a pattern using the photosensitive resin composition, and a semiconductor device.

[0010] In view of the problems of the above-mentioned conventional techniques, the present inventors have conducted extensive research and experiments and have found that the above-mentioned problems can be solved by combining a radical polymerizable monomer having one photopolymerizable group with a specific nitrogen-containing heterocyclic compound in a negative-type photosensitive resin composition containing a polyimide precursor, a polyimide, and a photopolymerization initiator, thereby completing the present invention.

[0011] (1) A negative-tone photosensitive resin composition comprising: (A) a polyimide precursor or polyimide, (B) a photopolymerization initiator, (C) a radically polymerizable monomer having one photopolymerizable group, and (D) a nitrogen-containing heterocyclic compound, wherein the (C) radically polymerizable monomer is liquid under conditions of a temperature of 25°C and a pressure of 1 atm, and the (D) component is at least one selected from the group consisting of a tetrazole derivative, a triazole derivative, a triazine derivative, and a purine derivative, and the purine derivative has an acyl group, an alkoxy group, an alkyl group, a hydroxyalkyl group, or a heteroaryl group. (2) The (A) polyimide precursor is a compound represented by the following general formula (1): {In the formula, X １ is a tetravalent organic group having 6 to 40 carbon atoms, and Y １ is a divalent organic group having 6 to 40 carbon atoms, n is an integer of 2 to 150, and R １ and R ２ are each independently a hydrogen atom, a photopolymerizable group, or a saturated aliphatic group having 1 to 4 carbon atoms. １ and R ２and both of these cannot be hydrogen atoms at the same time.} and / or the polyimide (A) is a polyamic acid ester represented by the following general formula (3): {In the formula, X ２ is a tetravalent organic group having 6 to 40 carbon atoms, and Y ２ is a divalent organic group having 6 to 40 carbon atoms, and n is an integer of 2 to 50.}. (3) The negative photosensitive resin composition according to item 1, wherein the (B) photopolymerization initiator is represented by the following general formula (4): {In the formula, R ６ is a hydrogen atom, or an alkyl group, alkoxy group, aryl group, ester group, or acyl group having 3 to 10 carbon atoms, and R ７ is a hydrogen atom, or an alkyl group, alkoxy group, aryl group, ester group, or acyl group having 1 to 10 carbon atoms.}. (4) In the general formula (1) and the general formula (3), Y １ and Y ２ is represented by the following general formula (5): {In the formula, R ８ ~R １５ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aromatic group, or a hydroxyl group, and may be different from each other or the same as each other.} or a group represented by the following general formula (6): {In the formula, R １６ ~R １９ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aromatic group, or a hydroxyl group, and may be different from each other or the same.}. (5) The negative photosensitive resin composition according to item 2, wherein the (B) photopolymerization initiator is a divalent organic group represented by the following general formula (7): {In the formula, R ６is a hydrogen atom, or an alkyl group, alkoxy group, aryl group, ester group, or acyl group having 1 to 10 carbon atoms.} (6) The negative photosensitive resin composition according to any one of items 1 to 5, wherein the (B) photopolymerization initiator, when dissolved in N-methyl-2-pyrrolidone at a concentration of 0.1% by volume (vol), has an absorbance of 0.05 or less at a wavelength of 365 nm. (7) The negative photosensitive resin composition according to any one of items 1 to 6, wherein the photopolymerizable group of the (C) radical polymerizable monomer is a (meth)acrylic group or a (meth)acryloyl group. (8) The negative photosensitive resin composition according to any one of items 1 to 7, wherein the (C) radical polymerizable monomer has an alkylene oxide structure. (9) The negative photosensitive resin composition according to any one of items 1 to 8, wherein the (C) radical polymerizable monomer has a linear or cyclic alkyl structure. (10) The negative photosensitive resin composition according to any one of items 1 to 9, wherein the (C) radical polymerizable monomer has a molecular weight of 500 or less. (11) The negative photosensitive resin composition according to any one of items 1 to 10, wherein the (C) radical polymerizable monomer does not contain a urethane bond or a urea bond. (12) The negative photosensitive resin composition according to any one of items 1 to 11, wherein the (C) radical polymerizable monomer does not contain an azole group. (13) The negative photosensitive resin composition according to any one of items 1 to 12, wherein the (D) nitrogen-containing heterocyclic compound is the purine derivative and has an alkyl group having two or more carbon atoms. (14) The negative photosensitive resin composition according to any one of items 1 to 12, wherein the (D) nitrogen-containing heterocyclic compound is the purine derivative and has an acyl group, an alkoxy group, a hydroxyalkyl group, or a heteroaryl group. (15) The negative photosensitive resin composition according to any one of items 1 to 12, wherein the (D) nitrogen-containing heterocyclic compound is the purine derivative and has an acyl group or an alkoxy group. (16) The negative photosensitive resin composition according to item 15, wherein the acyl group is an aliphatic acyl group.(17) The negative photosensitive resin composition according to any one of items 1 to 16, wherein the (D) nitrogen-containing heterocyclic compound is the purine derivative, and the molecular weight of the (D) nitrogen-containing heterocyclic compound is 300 or less. (18) The negative photosensitive resin composition according to any one of items 1 to 17, further comprising an (E) organic acidic compound. (19) The negative photosensitive resin composition according to item 18, wherein the (E) organic acidic compound contains a sulfonic acid or a carboxylic acid. (20) The negative photosensitive resin composition according to item 1 or 2, wherein a cured film having a film thickness of about 7 μm obtained by heating at 230° C. for 2 hours under a nitrogen atmosphere has a Young's modulus of 4.0 GPa to 10 GPa when the film is subjected to a tensile test at a tensile speed of 50 mm / min. (21) The negative photosensitive resin composition according to any one of items 1 to 20, wherein the (A) polyimide precursor or polyimide, when dissolved in N-methyl-2-pyrrolidone at a concentration of 0.1% by volume (vol), has an absorbance of 0.8 or more at a wavelength of 365 nm. (22) A method for producing a cured relief pattern, comprising the following steps: (1) applying the negative photosensitive resin composition according to any one of items 1 to 21 onto a substrate to form a photosensitive resin layer on the substrate, (2) exposing the photosensitive resin layer to light, (3) developing the exposed photosensitive resin layer to form a relief pattern, and (4) heat-treating the relief pattern to form a cured relief pattern. (23) The method according to item 22, wherein the substrate is made of copper or a copper alloy. (24) A semiconductor device comprising a cured relief pattern formed using the negative photosensitive resin composition according to any one of items 1 to 21.

[0012] According to the present invention, it is possible to provide a photosensitive resin composition that exhibits good patterning performance and excellent adhesion even to copper or a copper alloy, a method for forming a cured relief pattern using the photosensitive composition, and a semiconductor device having the cured relief pattern.

[0013] Hereinafter, a mode for carrying out the present invention (hereinafter abbreviated as "embodiment") will be described in detail. Note that the present invention is not limited to the following embodiment, and various modifications can be made within the scope of the gist thereof.

[0014] <Photosensitive Resin Composition> The negative photosensitive resin composition of the present disclosure (hereinafter also simply referred to as "photosensitive resin composition") contains, as the resin component (A), a polyimide precursor, a polyimide, or both of these (in the present disclosure, these are also collectively referred to simply as "(A) resin"). The photosensitive resin composition contains a photopolymerization initiator (B), a radical polymerizable monomer (C) having one photopolymerizable group, and a nitrogen-containing heterocyclic compound (D). The component (C) according to the present disclosure is polymerized at a temperature of 25°C and a pressure of 1 atm (1.01325 x 10 ５ The component (D) according to the present disclosure may be at least one selected from the group consisting of tetrazole derivatives, triazole derivatives, triazine derivatives, and purine derivatives, and the purine derivative as component (D) may have an acyl group, an alkoxy group, an alkyl group, a hydroxyalkyl group, or a heteroaryl group. By having the above-described configuration, the photosensitive resin composition according to the present disclosure can provide a photosensitive resin composition that exhibits good patterning performance and has excellent adhesion even on copper or copper alloys.

[0015] Each component will be described in detail below. Throughout this specification, when a structure represented by the same symbol in a general formula is present in a molecule, the structures may be the same or different from each other.

[0016] (A) Polyimide Precursor The (A) polyimide precursor is preferably a polyamic acid ester having a structural unit represented by the following general formula (1): The (A) polyimide precursor is converted to a polyimide by heating (for example, at 200°C or higher) for cyclization. {In formula (1), X １ is a tetravalent organic group having 6 to 40 carbon atoms, and Y １ is a divalent organic group having 6 to 40 carbon atoms, n is an integer of 2 to 150, and R １ and R ２ are each independently a hydrogen atom, a photopolymerizable group, or a saturated aliphatic group having 1 to 4 carbon atoms. １ and R ２ Both cannot be hydrogen atoms at the same time.

[0017] In formula (1), R １ and R ２ At least one of the groups is preferably a photopolymerizable group.

[0018] The term "photopolymerizable group" refers to a functional group that polymerizes upon irradiation with light. The photopolymerizable group may be an ethylenically unsaturated bond, and specific examples include a (meth)acryloyl group, a vinyl group, and a styryl group. In this specification, the term "(meth)acryloyl group" refers to a methacryloyl group or an acryloyl group, and the term "(meth)acrylate" refers to a methacrylate or an acrylate.

[0019] R in formula (1) １ and R ２ may each independently be a monovalent organic group represented by the following general formula (2): {In formula (2), R ３ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R ４ and R ５ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10.

[0020] In general formula (2), R ３ More specifically, R includes a hydrogen atom, a methyl group, an ethyl group, and a propyl group, and is preferably a methyl group. ４ and R ５ More specifically, m is a hydrogen atom, a methyl group, an ethyl group, and a propyl group, and is preferably a hydrogen atom. In general formula (2), m is more preferably an integer of 2 to 5, and even more preferably 2 or 3.

[0021] R in general formula (1) １ and R ２ The proportion of hydrogen atoms in R １ and R ２ It is preferably 20% or less, more preferably 15% or less, and even more preferably 5% or less, based on the total number of moles. １ and R ２ is a monovalent organic group represented by the general formula (2), R１ and R ２ The proportion of hydrogen atoms and the proportion of the organic group of general formula (2) are preferably in the above ranges, based on the total number of moles, and more preferably in the above ranges, from the viewpoint of photosensitive properties and storage stability.

[0022] In general formula (1), n ​​is not limited as long as it is an integer of 2 to 150. From the viewpoint of the photosensitivity and mechanical properties of the negative photosensitive resin composition, n is preferably an integer of 3 to 100, and more preferably an integer of 5 to 70.

[0023] In the above general formula (1), X １ From the viewpoint of achieving both heat resistance and photosensitive properties, the tetravalent organic group represented by X is preferably an organic group having 6 to 40 carbon atoms, more preferably an organic group having 6 to 30 carbon atoms, and even more preferably an organic group having 6 to 20 carbon atoms. １ From the same viewpoint, the tetravalent organic group represented by the formula: is particularly preferably —COOR １ group or -COOR ２ The group and the —CONH— group are in the ortho position relative to each other, and are an aromatic group or an alicyclic aliphatic group.

[0024] In general formula (1), X １ Specific examples of the tetravalent organic group represented by the formula (I) include an aromatic ring-containing organic group having 6 to 40 carbon atoms, such as a tetravalent organic group represented by the formula (I) below: {wherein R6 is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a C1 to C10 monovalent hydrocarbon group, and a C1 to C10 monovalent fluorine-containing hydrocarbon group, l is an integer selected from 0 to 2, m is an integer selected from 0 to 3, and n is an integer selected from 0 to 4.} Examples of the group having a structure selected from the group consisting of, but not limited to, X １ The structure of X having the structure represented by the above formula (I) may be one type or a combination of two or more types. １ The group is particularly preferable from the viewpoint of achieving both heat resistance and photosensitive properties.

[0025] X １As the group, among the structures represented by the above formula (I), particularly, the group represented by the following formula: {wherein R6 is at least one selected from the group consisting of 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 an integer selected from 0 to 2, and m is an integer selected from 0 to 3.} When the polyimide precursor resin has such a structure, film strength and resolution can be improved.

[0026] Also, X １ The structure may be one type or a combination of two or more types, but from the viewpoint of improving resolution, a combination of two or more types is more preferred.

[0027] In the above general formula (1), Y １ From the viewpoint of achieving both heat resistance and photosensitive properties, the divalent organic group represented by the formula (II) below is preferably an aromatic group having 6 to 40 carbon atoms, for example. {wherein R6 is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 monovalent hydrocarbon group, and a C1-C10 monovalent fluorine-containing hydrocarbon group, and n is an integer selected from 0 to 4.} Examples of the structure include, but are not limited to, Y １ The structure represented by formula (II) may be one type or a combination of two or more types. １ The group is particularly preferable from the viewpoint of achieving both heat resistance and photosensitive properties.

[0028] From the viewpoint of film strength, in general formula (1), Y １ is represented by the following general formula (5): {In the formula, R ８ ~R １５ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aromatic group, or a hydroxyl group, and may be different from each other or the same.} and a group represented by the following general formula (6): {In the formula, R １６ ~R １９are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aromatic group, or a hydroxyl group, and may be different from each other or the same.}

[0029] (A) Polyimide The polyimide is represented by the following general formula (3): {In the formula, X ２ is a tetravalent organic group having 6 to 40 carbon atoms, and Y ２ is a divalent organic group having 6 to 40 carbon atoms, and n is an integer of 2 to 50.} It is particularly preferable that the photosensitive resin composition contains a resin represented by general formula (3), since sufficient film properties can be exhibited without requiring chemical changes in the heat treatment step, and therefore the composition is suitable for heat treatment at lower temperatures.

[0030] In general formula (3), X ２ From the viewpoint of heat resistance, the tetravalent organic group of X preferably contains an aromatic ring structure, and more preferably contains a benzene ring structure. ２ The tetravalent organic group preferably has a structure in which 2 to 6 benzene rings are bonded via a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, a fluorinated alkylene group, and an ether group. The alkylene group and the fluorinated alkylene group may be linear or branched.

[0031] X in general formula (3) ２ is the X described above in the description of the general formula (1) of the polyimide precursor. １ It may be the same as or different from the structure of X ２ is an organic group preferably having 6 to 40 carbon atoms, more preferably having 6 to 30 carbon atoms, and even more preferably having 6 to 20 carbon atoms.

[0032] Y in general formula (3) ２ is the Y described above in the description of the general formula (1) of the polyimide precursor. １ It may be the same as or different from the structure of Y ２is preferably at least one organic group selected from the general formula (II) described above in the description of the general formula (1) of the polyimide precursor, and specifically at least one organic group selected from the general formulas (5) and (6) is particularly preferred.

[0033] The (A) resin is preferably at least one resin selected from the group consisting of polyimide precursors and polyimides. The (A) resin may be a polyimide precursor alone, a polyimide alone, or a mixture of these. When the (A) resin is a mixture of a polyimide precursor and a polyimide, the polyimide precursor may be present in an amount of, for example, 50 to 90 parts by mass and 10 to 50 parts by mass, where the total mass of these is 100 parts by mass. It is preferable that the (A) resin contains a polyimide precursor from the viewpoint of improved photosensitivity.

[0034] The polyimide precursor (A) and / or the polyimide (A) preferably have an absorbance of 0.8 or more at a wavelength of 365 nm when dissolved in N-methyl-2-pyrrolidone at a concentration of 0.1% by volume (vol), and more preferably, the absorbance of both the polyimide precursor and the polyimide as component (A) is 0.8 or more. The absorbance at a wavelength of 365 nm can be measured using a UV-1800 ultraviolet-visible spectrophotometer manufactured by Shimadzu Corporation.

[0035] Polymers that have an absorbance of 0.8 or more at 365 nm when measured as described above, i.e., polymers whose absorption wavelength is shifted to longer wavelengths, have a small difference between the highest occupied molecular orbital (HOMO) of the diamine side and the lowest unoccupied molecular orbital (LUMO) of the acid anhydride side, forming strong aggregates due to charge transfer interactions, which improves the toughness of the film.

[0036] (A) Method for Preparing Polyimide Precursor A polyimide precursor resin is prepared by first preparing a polyimide precursor containing the above-mentioned tetravalent organic group X １A partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester) is prepared by reacting a tetracarboxylic acid dianhydride containing the compound represented by the formula (I) with a photopolymerizable alcohol having an unsaturated double bond and, optionally, an alcohol having no unsaturated double bond. Then, the partially esterified tetracarboxylic acid is reacted with a divalent organic group Y １ and diamines containing the same, by amide polycondensation.

[0037] (Preparation of Acid / Ester Form) A tetravalent organic group X that is preferably used to prepare a polyimide precursor resin is １ Examples of the tetracarboxylic dianhydride containing the formula (I) include tetracarboxylic dianhydrides having the structure represented by the above general formula (I), as well as, for example, pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'- Examples of suitable dianhydrides include tetracarboxylic acid dianhydrides, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, and preferably include pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic acid dianhydride, benzophenone-3,3',4,4'-tetracarboxylic acid dianhydride, and biphenyl-3,3',4,4'-tetracarboxylic acid dianhydride, but are not limited to these. These may be used alone or in combination of two or more.

[0038] Examples of alcohols having a photopolymerizable unsaturated double bond that are preferably used to prepare a polyimide precursor resin include 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, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-cyclopropyl acrylate, 2-hydroxy-3-methyl ... Examples of the methacryloyloxypropyl acrylate include 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.

[0039] The photopolymerizable alcohols having an unsaturated double bond can also be mixed with alcohols not having an unsaturated double bond, 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.

[0040] As the polyimide precursor resin, a non-photosensitive polyimide precursor resin prepared only from the above-mentioned alcohols having no unsaturated double bonds may be used by mixing with a photosensitive polyimide precursor resin. From the viewpoint of resolution, the amount of the non-photosensitive polyimide precursor resin is preferably 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor.

[0041] The esterification reaction of the acid anhydride can be carried out by stirring, dissolving, and mixing a tetracarboxylic dianhydride and an alcohol in a solvent as described below in the presence of a basic catalyst such as pyridine, thereby obtaining the desired acid / ester. The stirring, dissolving, and mixing are preferably carried out at a temperature of 20°C to 50°C for 4 to 24 hours, for example.

[0042] (Preparation of Polyimide Precursor Resin) The acid / ester compound (typically present as a solution in a solvent described below) can be converted into a polyacid anhydride by adding and mixing with an appropriate dehydration 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, under ice cooling. The polyacid anhydride of the acid / ester compound can be converted into a polyacid anhydride by adding a divalent organic group Y １ A polyimide precursor resin can be obtained by adding dropwise a solution or dispersion of a diamine containing the compound (I) dissolved or dispersed in a separate solvent and carrying out amide polycondensation. Alternatively, the acid moiety of the acid / ester compound can be converted into an acid chloride using thionyl chloride or the like, and then reacted with a diamine compound in the presence of a base such as pyridine to obtain a polyimide precursor resin.

[0043] As another synthesis method, a polyimide precursor resin can also be obtained by first reacting a tetracarboxylic dianhydride with a diamine compound to obtain a polyamic acid, and then using an appropriate dehydration condensation agent, for example, trifluoroacetic anhydride, to introduce the above-mentioned alcohol into the carboxylic acid moiety in the side chain of the obtained polyamic acid.

[0044] Divalent organic group Y１Examples of diamines containing the formula (5) include diamines having the structures shown in the above general formulas (5) and (6), as well as, for example, p-phenylenediamine, m-phenylenediamine, 2-methyl-1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 2-(trifluoromethyl)-1,4-phenylenediamine, 2,3,5,6-tetrafluoro-1,4-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3 '-Diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[ 4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,Examples of the amines include, but are not limited to, 4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, and 9,9-bis(4-aminophenyl)fluorene, 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'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-diaminooctafluorobiphenyl, and mixtures thereof.

[0045] After the amide polycondensation reaction is completed, the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction solution is filtered off as needed. Then, a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof is added to the resulting polymer component to precipitate the polymer component. The polymer is further purified by repeated redissolution and reprecipitation procedures, and then vacuum dried to isolate the desired polyimide precursor resin. To improve the degree of purification, the polymer solution may be passed through a column packed with anion and / or cation exchange resin swollen with an appropriate organic solvent to remove ionic impurities.

[0046] The molecular weight of the polyimide precursor resin, as measured by gel permeation chromatography in terms of polystyrene equivalent weight average molecular weight, is preferably 8,000 to 150,000, and more preferably 9,000 to 50,000. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, while when it is 150,000 or less, the dispersibility in the developer is good and the resolution performance of the relief pattern is good. Tetrahydrofuran and N-methyl-2-pyrrolidone are preferred as developing solvents for gel permeation chromatography. The weight average molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. The standard monodisperse polystyrene is preferably selected from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko K.K.

[0047] [Component (B); Photopolymerization Initiator] The component (B) is a photopolymerization initiator. The component (B) is, for example, a photopolymerization initiator for UV curing, and is preferably a photoradical polymerization initiator. When the component (B) is dissolved in N-methyl-2-pyrrolidone at a concentration of 0.1 vol%, the absorbance at a wavelength of 365 nm is preferably 0.05 or less. By making the absorbance of the component (B) 0.05 or less, radicals can be generated uniformly deep into the film during exposure, improving patterning properties.

[0048] Examples of component (B) include: benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone and 2-hydroxy-2-methylpropiophenone; thioxanthone derivatives such as 1-hydroxycyclohexylphenyl ketone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzyl derivatives such as benzil, benzil dimethyl ketal, and benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin methyl ether; azides such as 2,6-di(4'-diazidobenzal)-4-methylcyclohexanone and 2,6'-di(4'-diazidobenzal)cyclohexanone; Examples of compounds that can be used include oximes such as 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-ethoxycarbonyl)oxime, 1-phenylpropanedione-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 peroxide; aromatic biimidazoles; and titanocenes.

[0049] Among these, the component (B) is, from the viewpoint of patterning properties, a compound represented by the following general formula (4): {In the formula, R ６ is a hydrogen atom, or an alkyl group, alkoxy group, aryl group, ester group, or acyl group having 3 to 10 carbon atoms, and R ７ is a hydrogen atom, or an alkyl group, alkoxy group, aryl group, ester group, or acyl group having 1 to 10 carbon atoms, and / or is preferably represented by the following general formula (7): {In the formula, R ６ is a hydrogen atom, or an alkyl group, alkoxy group, aryl group, ester group, or acyl group having 1 to 10 carbon atoms.}

[0050] From the viewpoints of photosensitivity and thick-film curability, the blending amount of component (B) is preferably 0.1 to 20 parts by mass, and more preferably 2.0 to 15 parts by mass, per 100 parts by mass of component (A). The lower limit of the blending amount of component (B) may be 2.5 parts by mass or 3.0 parts by mass. Blending 0.1 part by mass or more of component (B) per 100 parts by mass of component (A) tends to improve the photosensitivity characteristics of the photosensitive resin composition, while blending 20 parts by mass or less tends to improve the thick-film curability of the photosensitive resin composition.

[0051] [Component (C): Radical Polymerizable Monomer Having One Photopolymerizable Group] Component (C) is a radical polymerizable monomer having one photopolymerizable group. When irradiated with light, component (C) reacts with other components (C) or with photopolymerizable groups that may be present in component (A) due to radicals generated from component (B). The polymers produced by this reaction tend to remain in the cured film after thermal curing and act as plastic components, impairing the tough film properties of the polyimide. Their presence at the interface between the copper substrate and the polyimide can impair adhesion, among other effects. In the present invention, the use of a radical polymerizable monomer having only one photopolymerizable group can suppress excessive polymerization reactions compared to radical polymerizable monomers having two or more photopolymerizable groups, thereby reducing the amount of polymers (polymers between components (C) or polymers between components (C) and (A)) remaining in the film after thermal curing, thereby achieving good film strength and copper adhesion. Furthermore, it is believed that the amount of radical polymerization reaction that occurs is optimized by suppressing the excessive polymerization reaction, thereby achieving good patterning performance. ５ It is liquid under the conditions of 0.1 Pa.

[0052] There are no particular restrictions on the type of photopolymerizable group in component (C), but it is preferably a (meth)acrylic group or a (meth)acryloyl group.

[0053] Examples of the component (C) include glycerin mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polybutylene glycol mono(meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cetyl (meth)acrylate, behenyl (meth)acrylate, cyclohexyl (meth)acrylate, hydroxyphenyl acrylate, benzyl (meth)acrylate, and methoxypolyethylene glycol mono(meth)acrylate. Examples of suitable components include acrylate, methoxypolypropylene glycol mono(meth)acrylate, lauroxypolyethylene glycol (meth)acrylate, stearoxypolyethylene glycol (meth)acrylate, (2-oxy-1,3-dioxolan-4-yl)methyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, ethoxy-o-phenylphenol (meth)acrylate, and 2-(meth)acroyloxyethyl succinate. These may be used alone or in combination of two or more. Among these, from the viewpoint of compatibility with the composition, it is particularly preferred that component (C) have an alkylene oxide structure or a linear or cyclic alkyl structure.

[0054] The molecular weight of component (C) is preferably 500 or less, more preferably 100 to 450, and even more preferably 150 to 400. When the molecular weight is 500 or less, the component (C) is easily volatilized during thermal curing and is less likely to remain in the film, which makes it easier to achieve good film properties and copper adhesion.

[0055] The component (C) preferably does not contain a urethane bond, a urea bond, or an azole group, more preferably does not contain a urethane bond or a urea bond, or does not contain an azole group, and even more preferably does not contain a urethane bond, a urea bond, or an azole group. Since urethane bonds, urea bonds, and azole groups generally have high affinity with copper, when the component (C) containing a photopolymerizable group contains these, a radical polymerization reaction is likely to proceed at the copper substrate interface. As a result, polymers remain near the interface, which is likely to impair copper adhesion.

[0056] From the viewpoint of achieving both patterning ability, film properties, and copper adhesion, the blending amount of component (C) is preferably 1 to 20 parts by mass, and more preferably 2 to 15 parts by mass, per 100 parts by mass of component (A). Blending 1 part by mass or more of component (C) makes it easier to achieve good patterning performance, while blending 20 parts by mass or less makes it easier to improve film properties and copper adhesion.

[0057] [Component (D): Nitrogen-Containing Heterocyclic Compound] Component (D) is at least one nitrogen-containing heterocyclic compound selected from the group consisting of tetrazole derivatives, triazole derivatives, triazine derivatives, and purine derivatives. The purine derivative according to one embodiment has an acyl group, an alkoxy group, an alkyl group, a hydroxyalkyl group, or a heteroaryl group. By including component (D) in the photosensitive resin composition, copper adhesion can be improved without generating foreign matter even on copper or copper alloys.

[0058] A tetrazole derivative refers to a compound comprising a tetrazole skeleton. The tetrazole derivative in the present disclosure may have a substituent, if necessary. Specific examples include 1H-tetrazole, 1-methyl-1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-benzyl-1H-tetrazole, 5-benzylthio-1H-tetrazole, 5-amino-1H-tetrazole, 5-amino-1-methyltetrazole, 1H-tetrazole-5-acetic acid, 1H-tetrazole-5-ethyl acetate, 1H-tetrazole-5-ethyl carboxylate, 5-(ethylthio)-1H-tetrazole, 1-(3-acetamidophenyl)-5-mercaptotetrazole, 1-(4-ethoxyphenyl)-5-mercapto-1H-tetrazole, 5-(4-carboxyphenyl)-1H-tetrazole, and 5-(4-methylphenyl)-1H-tetrazole.

[0059] The triazole derivative refers to a compound having a triazole skeleton, and examples thereof include a 1,2,4-triazole skeleton and a 1,2,3-triazole skeleton. The triazole derivative in the present disclosure may have a substituent, if necessary. Specific examples include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxyphenyl] ... hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]benzotriazole, 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, and 5-carboxy-1H-benzotriazole.

[0060] The triazine derivative refers to a compound having a triazine skeleton, such as a 1,2,3-triazine skeleton, a 1,2,4-triazine skeleton, a 1,3,5-triazine skeleton, etc. The triazine derivative in the present disclosure may have a substituent, if necessary. Specifically, 1,3,5-triazine, 2,4,6-trichloro-1,3,5-triazine, 1,3,5-triazine-2,4,6-triol, 1,3,5-triazolidine-2,4,6-trione, 2,4,6-triphenyl-1,3,5-triazine, 2,4,6-trimethoxy-1,3,5-triazine, 2,4-dimethoxy-1,3,5-triazine, methyl isocyanurate, 1,3,5-triazine-2,4,6-trithiol, 1,3,5-triazine-2,4,6-triamine, 2,4-diamino-1,3,5-triazine, 4,6-diamino-1,3,5-triazo Examples of the benzoguanamine include lysin-2-one, 6-amino-1,3,5-triazine-2,4-diol, 6-amino-1,3,5-triazine-2,4-dione, 2,4-diamino-6-butylamino-1,3,5-triazine, 2,4-diamino-6-diethylamino-1,3,5-triazine, benzoguanamine, 2,4,6-tri(4-pyridyl)-1,3,5-triazine, 2,4-diamino-6-methyl-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-hydroxy-1,3,5-triazine, and triallyl cyanurate.

[0061] The purine derivative refers to a compound consisting of a purine skeleton, such as an adenine skeleton, a guanine skeleton, a hypoxanthine skeleton, a xanthine skeleton, or an isoguanine skeleton.

[0062] By including an acyl group, an alkoxy group, an alkyl group, a hydroxyalkyl group, or a heteroaryl group as a substituent of the purine derivative, the solubility in organic solvents is improved, and aggregation in the varnish is prevented, thereby suppressing foreign matter defects in the coating film. In particular, it is more preferable to include an acyl group or an alkoxy group. From the same viewpoint, the acyl group of component (D) is preferably an aliphatic acyl group.

[0063] When the purine derivative has an alkyl group, the alkyl group preferably has two or more carbon atoms, from the viewpoint of further improving copper adhesion.

[0064] Specific examples of the purine derivatives include 3-methyladenine, N-methyl-7H-purin-6-amine, 6-methoxypurine, 6-ethoxypurine, 6-(dimethylamino)purine, 7-methylguanine, 6-O-methylguanine, 1-methylxanthine, 3-methylxanthine, 9-(2-hydroxyethyl)adenine, 1,3-dimethylxanthine, 1,7-dimethylxanthine, 3,7-dimethylxanthine, 2-acetamido-6-hydroxypurine, (R)-6-amino-9-(2-hydroxypropyl) purine, 6-(γ,γ-dimethylallylamino)purine, 9-(tetrahydro-2-furanyl)-9H-purin-6-amine, 6-(furfurylamino)purine, 6-(4-hydroxy-3-methyl-2-butenylamino)purine, 9-[(2-hydroxyethoxy)methyl]guanine, 6-benzylaminopurine, 6-benzoylpurine, 2-acetamido-9-acetyl-6-oxopurine, 1,3-dimethylxanthine-7-acetic acid, 7-(2-hydroxypropyl)-1,3-dimethylxanthine, O ６ -benzylguanine, N ６ -benzoyladenine, 9-[4-hydroxy-3-(hydroxymethyl)butyl]guanine, 7-(2,3-dihydroxypropyl)-1,3-dimethylxanthine, 9-[[2-hydroxy-1-(hydroxymethyl)ethoxy]methyl]guanine, 8-benzyltheophylline, 3,7-dimethyl-1-(5-oxohexyl)xanthine, and the like.

[0065] The molecular weight of component (D) is preferably not more than 300, and more preferably not more than 250. When the molecular weight of component (D) is not more than 300, the solubility in solvents is improved and aggregation in the varnish is prevented, thereby suppressing foreign matter defects in the coating film.

[0066] The blending amount of component (D) is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, per 100 parts by mass of component (A). Blending 0.01 part by mass or more of component (D) facilitates the development of good copper adhesion, while blending 10 parts by mass or less facilitates the suppression of precipitation in the varnish.

[0067] [Component (E): Organic Acidic Compound] The photosensitive resin composition of the present embodiment may contain an organic acidic compound as component (E). "Acidic" refers to a compound having a pKa of 10 or less. Use of component (E) can suppress the generation of foreign matter in the varnish and gelation due to an imidization reaction, improving storage stability over time.

[0068] The component (E) is not particularly limited as long as it has a pKa of 10 or less, but it is preferable that it contains a sulfonic acid or a carboxylic acid, and examples of such compounds include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, mandelic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, lactic acid, malonic acid, succinic acid, citric acid, glutaric acid, adipic acid, malic acid, ascorbic acid, tartaric acid, valeric acid, benzoic acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 4-nitrobenzoic acid, carbonic acid, boronic acid, phosphoric acid, phosphonic acid, phosphinic acid, camphor, and the like. Examples of suitable sulfonic acids include benzenesulfonic acid, p-toluenesulfonic acid, cyclohexanesulfonic acid, octanesulfonic acid, butanesulfonic acid, ethanesulfonic acid, methanesulfonic acid, dodecylbenzenesulfonic acid, dodecanesulfonic acid, mesitylenesulfonic acid, 2,4,6-triisopropylbenzenesulfonic acid, β-naphthylsulfonic acid, naphthalene-1,5-disulfonic acid, ethane-1,2-disulfonic acid, 2-hydroxyethanesulfonic acid, trifluoromethanesulfonic acid, perfluorobutanesulfonic acid, perfluorooctanesulfonic acid, nitric acid, and sulfuric acid. Among these, mandelic acid and p-toluenesulfonic acid are preferred from the viewpoint of storage stability.

[0069] From the viewpoints of heat resistance and adhesion to copper substrates, the content of component (E) is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 1 part by mass, per 100 parts by mass of component (A).

[0070] [Other Components] The photosensitive resin composition may further contain components (other components) other than the above components (A) to (E). Examples of other components include resin components other than component (A), sensitizers, photopolymerization inhibitors, adhesion aids, thermal crosslinking agents, plasticizers, nitrogen-containing heterocyclic compounds other than component (D), and solvents.

[0071] (Resin Components Other Than Component (A)) The photosensitive resin composition may further contain a resin component other than component (A). Examples of such a resin component include polyoxazole, polyoxazole precursor, phenolic resin, polyamide, siloxane resin, and acrylic resin. The blending amount of these resin components is preferably 0.01 to 20 parts by mass per 100 parts by mass of component (A).

[0072] (Sensitizer) The photosensitive resin composition may optionally contain a sensitizer to improve photosensitivity. Examples of sensitizers include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylaminocinnamylideneindano. p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl

[0039] Examples of the methylaminobenzoate include methylaminobenzoate, ... These may be used alone or in combination of two or more. A combination of two or more may be, for example, a combination of 2 to 5 types. The amount of sensitizer blended is preferably 0.1 to 25 parts by mass per 100 parts by mass of component (A).

[0073] (Photopolymerization Inhibitor) The photosensitive resin composition may optionally contain a photopolymerization inhibitor to appropriately control the photoradical crosslinking reaction. Examples of the photopolymerization inhibitor include a compound containing an aromatic hydroxyl group, a nitroso compound, an N-oxide compound, a quinone compound, an N-oxyl compound, a phenothiazine compound, and a hindered phenol compound.

[0074] Examples of compounds containing an aromatic hydroxyl group include 4-methoxyphenol (p-methoxyphenol), 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-hexane-1,6- Diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ester, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, catechol, tert-butyl-catechol, 4,4',4"-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol), 6,6'-di-tert-butyl-4,4'-butylidene-m-cresol phenol, 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, hydroquinone, methylhydroquinone, t-butylhydroquinone, di-t-butyl-p-cresol, pyrogallol, 4,4-thiobis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), phenol resins, and cresol resins.

[0075] Examples of nitroso compounds include nitrosobenzene, 2-nitrosotoluene, 1,2,4,5-tetramethyl-3-nitrosobenzene, 4-nitrosophenol, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 4-nitrosodiphenylamine, 3,5-dibromo-4-nitrosobenzenesulfonic acid, N-nitrosopyrrolidine, N-t-butyl-N-nitrosoaniline, N-nitrosodimethylamine, N-nitrosodiethylamine, 1-nitrosopiperidine, 4-nitrosomorpholine, N-nitroso-N-methylbutylamine, N-nitroso-N-ethylurea, N-nitrosohexamethyleneimine, N-nitrosophenylhydroxyamine cerous salt, N-nitrosophenylhydroxyamine aluminum salt, 2,4,6-Tris-t-butyl-nitrosobenzene, and N-nitrosodiphenylamine.

[0076] Examples of the N-oxide compounds include phenyl-t-butylnitrone, 3,3,5,5-tetramethyl-1-pyrroline-N-oxide, 5,5-dimethyl-1-pyrroline N-oxide, 4-methylmorpholine N-oxide, pyridine N-oxide, 4-nitropyridine N-oxide, 3-hydroxypyridine N-oxide, picolinic acid N-oxide, nicotinic acid N-oxide, and isonicotinic acid N-oxide.

[0077] Examples of quinone compounds include p-benzoquinone, p-xyloquinone, p-toluquinone, 2,6-dimethyl-1,4-benzoquinone, tetramethyl-1,4-benzoquinone, 2-tert-butyl-p-benzoquinone, 2,5-di-tert-butyl-1,4-benzoquinone, 2,6-di-tert-1,4-benzoquinone, thymoquinone, 2,5-di-tert-amylbenzoquinone, and 2-bromo-1,4-benzoquinone. 1,4-benzoquinone, 2,5-dibromo-1,4-benzoquinone, 2,5-dichloro-1,4-benzoquinone, 2,6-dichloro-1,4-benzoquinone, 2-bromo-5-methyl-1,4-benzoquinone, tetrafluoro-1,4-benzoquinone, tetrabromo-1,4-benzoquinone, 2-chloro-5-methyl-1,4-benzoquinone, tetrachloro-1,4-benzoquinone, methoxy-1,4-benzoquinone, 2,5-dihydroxy- 1,4-benzoquinone, 2,5-dimethoxy-1,4-benzoquinone, 2,6-dimethoxy-1,4-benzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, tetrahydroxy-1,4-benzoquinone, 2,5-diphenyl-1,4-benzoquinone, 1,4-naphthoquinone, 1,4-anthraquinone, 2-methyl-1,4-naphthoquinone, 5,8-dihydroxy-1,4-naphthoquinone, 2-hydroxy- Examples of the anthraquinone include 1,4-naphthoquinone, 5-hydroxy-1,4-naphthoquinone, 5-hydroxy-2-methyl-1,4-naphthoquinone, 1-nitroanthraquinone, anthraquinone, 1-aminoanthraquinone, 1,2-benzoanthraquinone, 1,4-diaminoanthraquinone, 2,3-dimethylanthraquinone, 2-ethylanthraquinone, 2-methylanthraquinone, and 5,12-naphthacenequinone.

[0078] Examples of N-oxyl compounds include 2,2,6,6-tetramethylpiperidine 1-oxyl, 4-cyano-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-carboxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl, and piperidine 1-oxyl free radicals. oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-maleimido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, pyrrolidine 1-oxyl free radical compounds, and 3-carboxyproxyl free radical (3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl free radical).

[0079] Examples of phenothiazine compounds include phenothiazine, 10-methylphenothiazine, 2-methylthiophenothiazine, 2-chlorophenothiazine, 2-ethylthiophenothiazine, 2-(trifluoromethyl)phenothiazine, and 2-methoxyphenothiazine.

[0080] 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'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), trimethylolpropane, methylisothiazolinone ... Ethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4- ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4- t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H ,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6 -ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, Examples include azine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0081] From the viewpoints of resolution and the residual film rate after development, the photopolymerization inhibitor is preferably a compound containing an aromatic hydroxyl group or a nitroso compound, more preferably a compound containing an aromatic hydroxyl group, and among these, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 4-methoxyphenol, and 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione are particularly preferred.

[0082] The photopolymerization inhibitor may be used alone, or two or more different compounds may be used in combination. The amount of the photopolymerization inhibitor is preferably 0.005 to 12 parts by mass per 100 parts by mass of component (A). Alternatively, the amount of the photopolymerization inhibitor may be 3.0 to 8.0 parts by mass per 100 parts by mass of component (A).

[0083] (Adhesion Aid) The photosensitive resin composition may optionally contain an adhesion aid in order to improve the adhesion between the film formed using the photosensitive resin composition and the substrate. Examples of the adhesion aid 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]phthalamic acid, benzophenone-3,3′-bis(N-[3-triethoxysilyl]propylamido)-4,4′-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, and 3-(triethoxysilyl)propyl succinic anhydride; Silane coupling agents such as N-phenylaminopropyltrimethoxysilane; and aluminum-based adhesion aids such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0084] Of these adhesion aids, silane coupling agents are preferred from the viewpoint of adhesion strength. The amount of adhesion aid added is preferably 0.5 to 25 parts by mass per 100 parts by mass of component (A).

[0085] (Thermal Crosslinking Agent) The thermal crosslinking agent includes a compound having the function of inducing an addition reaction or a condensation polymerization reaction by heat. These reactions occur between the component (A) and the thermal crosslinking agent; between thermal crosslinking agents; and between the thermal crosslinking agent and other components described below; and the reaction temperature is preferably 150°C or higher.

[0086] Examples of the thermal crosslinking agent include an alkoxymethyl compound, an epoxy compound, an oxetane compound, a bismaleimide compound, an allyl compound, and a blocked isocyanate compound.

[0087] Examples of alkoxymethyl compounds include those of the following formula: Examples of the compound include compounds represented by the following formula:

[0088] Examples of epoxy compounds include epoxy compounds containing a bisphenol A group and hydrogenated bisphenol A diglycidyl ether (for example, Epolite 4000 manufactured by Kyoeisha Chemical Co., Ltd.).

[0089] Examples of the oxetane compound include 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, bis[1-ethyl(3-oxetanyl)]methyl ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methyl]biphenyl, 4,4'-bis(3-ethyl-3-oxetanylmethoxy)biphenyl, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, diethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, bis(3-ethyl-3-oxetanylmethyl) ) 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), and OXT221 (manufactured by Toagosei, trade name).

[0090] Examples of bismaleimide compounds include 1,2-bis(maleimide)ethane, 1,3-bis(maleimide)propane, 1,4-bis(maleimide)butane, 1,5-bis(maleimide)pentane, 1,6-bis(maleimide)hexane, 2,2,4-trimethyl-1,6-bis(maleimide)hexane, N,N'-1,3-phenylenebis(maleimide), 4-methyl-N,N'-1,3- phenylene bis(maleimide), N,N'-1,4-phenylene bis(maleimide), 3-methyl-N,N'-1,4-phenylene bis(maleimide), 4,4'-bis(maleimide)diphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-bis(maleimide)diphenylmethane, and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane.

[0091] Examples of the allyl compound include allyl alcohol, allyl anisole, allyl benzoate, allyl cinnamate, N-allyloxyphthalimide, allylphenol, allylphenylsulfone, allyl urea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl isocyanurate, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallylamine, triallyl 1,3,5-benzenetricarboxylate, triallyl trimellitate, triallyl phosphate, triallyl phosphite, and triallyl citrate.

[0092] Examples of the blocked isocyanate compound include hexamethylene diisocyanate-based blocked isocyanates (e.g., Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B, and WM44-L70G manufactured by Asahi Kasei Corporation, Takenate B-882N manufactured by Mitsui Chemicals, Inc., and 7960, 7961, 7982, 7991, and 7992 manufactured by Baxenden), tolylene diisocyanate-based blocked isocyanates (e.g., Takenate B-830 manufactured by Mitsui Chemicals, Inc.), ), 4,4'-diphenylmethane diisocyanate-based blocked isocyanates (for example, Takenate B-815N manufactured by Mitsui Chemicals, Inc., and Bronate PMD-OA01 and PMD-MA01 manufactured by Daiei Sangyo Co., Ltd.), 1,3-bis(isocyanatomethyl)cyclohexane-based blocked isocyanates (for example, Takenate B-846N manufactured by Mitsui Chemicals, Inc., and Coronate BI-301, 2507, and 2554 manufactured by Tosoh Corporation), and isophorone diisocyanate-based blocked isocyanates (for example, 7950, 7951, and 7990 manufactured by Baxenden).

[0093] From the viewpoint of effectively increasing the glass transition temperature (Tg) of the photosensitive resin composition, the thermal crosslinking agent preferably has at least one group selected from the group consisting of an alkoxymethyl group, a methylol group, and a maleimide group.

[0094] From the viewpoints of heat resistance and relief pattern development characteristics, the content of the thermal crosslinking agent is preferably 0.2 to 40 parts by mass, and more preferably 1 to 20 parts by mass, per 100 parts by mass of the component (A).

[0095] (Plasticizer) The plasticizer is a compound that improves the fluidity of the (A) polyimide precursor or polyimide when the relief pattern formed using the photosensitive resin composition of this embodiment is heat-cured. The plasticizer can impart sufficient solubility to the unexposed areas, so the photosensitive resin composition of this embodiment may optionally contain a plasticizer in order to obtain a sharp cured pattern during development.

[0096] Examples of the plasticizer include polycarboxylic acid ester plasticizers, sulfonamide plasticizers, phosphate ester plasticizers, polyester plasticizers, and polyalkylene glycol plasticizers.

[0097] Specific examples of polycarboxylic acid ester plasticizers include benzoates such as methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, pentyl benzoate, heptyl benzoate, normal octyl benzoate, nonyl benzoate, isononyl benzoate, isodecyl benzoate, 2-ethylhexyl benzoate, isodecyl benzoate, butylbenzyl benzoate, cyclopropyl benzoate, cyclobutyl benzoate, cyclopentyl benzoate, cyclohexyl benzoate, cycloheptyl benzoate, allyl benzoate, butylbenzyl benzoate, and phenyl benzoate. benzoate esters, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dipentyl phthalate, diheptyl phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, bis(2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate, dicyclopropyl phthalate, dicyclobutyl phthalate, dicyclopentyl phthalate, dicyclohexyl phthalate, dicycloheptyl phthalate, diallyl phthalate, bisbutyl benzyl phthalate, diphenyl phthalate Trimethyl trimellitate, triethyl trimellitate, tripropyl trimellitate, tributyl trimellitate, tripentyl trimellitate, triheptyl trimellitate, tri-n-octyl trimellitate, trinonyl trimellitate, triisononyl trimellitate, triisodecyl trimellitate, tris(2-ethylhexyl) trimellitate, triisodecyl trimellitate, trisbutylbenzyl trimellitate, tricyclopropyl trimellitate, tricyclobutyl trimellitate, and trimellitate. trimellitic acid esters such as tricyclopentyl adipate, tricyclohexyl trimellitate, tricycloheptyl trimellitate, triallyl trimellitate, trisbutylbenzyl trimellitate, and triphenyl trimellitate; dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, dipentyl adipate, diheptyl adipate, di-n-octyl adipate, dinonyl adipate, diisononyl adipate, diisodecyl adipate, bis(2-ethylhexyl) adipate, and diisodecyl adipate;Adipic acid esters such as butyl benzyl adipate, dicyclopropyl adipate, dicyclobutyl adipate, dicyclopentyl adipate, dicyclohexyl adipate, dicycloheptyl adipate, diallyl adipate, bisbutyl benzyl adipate, and diphenyl adipate, trimethyl trimellitate, triethyl trimellitate, tripropyl trimellitate, tributyl trimellitate, tripentyl trimellitate, triheptyl trimellitate, tri-n-octyl trimellitate, trinonyl trimellitate, and trimellitate. Trimellitate esters such as triisononyl trimellitate, triisodecyl trimellitate, tris(2-ethylhexyl) trimellitate, triisodecyl trimellitate, trisbutylbenzyl trimellitate, tricyclopropyl trimellitate, tricyclobutyl trimellitate, tricyclopentyl trimellitate, tricyclohexyl trimellitate, tricycloheptyl trimellitate, triallyl trimellitate, trisbutylbenzyl trimellitate, and triphenyl trimellitate; dimethyl sebacate, diethyl sebacate, and sebacate Sebacate esters such as dipropyl, dibutyl sebacate, dipentyl sebacate, diheptyl sebacate, di-n-octyl sebacate, dinonyl sebacate, diisononyl sebacate, diisodecyl sebacate, bis(2-ethylhexyl) sebacate, diisodecyl sebacate, butyl benzyl sebacate, dicyclopropyl sebacate, dicyclobutyl sebacate, dicyclopentyl sebacate, dicyclohexyl sebacate, dicycloheptyl sebacate, diallyl sebacate, bisbutyl benzyl sebacate, and diphenyl sebacate. , dimethyl succinate, diethyl succinate, dipropyl succinate, dibutyl succinate, dipentyl succinate, diheptyl succinate, di-n-octyl succinate, dinonyl succinate, diisononyl succinate, diisodecyl succinate, bis(2-ethylhexyl) succinate, diisodecyl succinate, butylbenzyl succinate, dicyclopropyl succinate, dicyclobutyl succinate, dicyclopentyl succinate, dicyclohexyl succinate, dicycloheptyl succinate, diallyl succinate, bisbutylbenzyl succinate, and diphenyl succinate.

[0098] Examples of sulfonamide plasticizers include aromatic sulfonamide plasticizers, and specific examples thereof include N-butylbenzenesulfonamide, p-toluenesulfonamide, o-toluenesulfonamide, p-toluenesulfonamide, N-ethyl-p-toluenesulfonamide, N-ethyl-o-toluenesulfonamide, N-n-butylbenzenesulfonamide, and N-cyclohexyl-p-toluenesulfonamide.

[0099] Specific examples of the phosphate ester plasticizer include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris(2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, and 2-ethylhexyl diphenyl phosphate.

[0100] Specific examples of polyester-based plasticizers include polyesters composed of an acid component such as adipic acid, terephthalic acid, isophthalic acid, or diphenyldicarboxylic acid and a diol component such as propylene glycol, 1,3-butanediol, 1,4-butanediol, ethylene glycol, or diethylene glycol; and polyesters composed of hydroxycarboxylic acids such as polycaprolactone. These polyesters may be end-capped with a monofunctional carboxylic acid or a monofunctional alcohol, or may be end-capped with an epoxy compound or the like.

[0101] Specific examples of polyalkylene glycol plasticizers include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, ethylene oxide addition polymers of bisphenols, and propylene oxide addition polymers of bisphenols; and terminal-blocking compounds such as the above-mentioned terminal epoxy-modified compounds, terminal ester-modified compounds, and terminal ether-modified compounds.

[0102] Specific examples of other plasticizers include glycerin fatty acid esters such as glycerin monoacetomonolaurate, glycerin diacetomonolaurate, and glycerin monoacetomonostearate; fatty acid amides such as stearic acid amide; aliphatic carboxylic acid esters such as butyl oleate; oxyacid esters such as methyl acetylricinoleate and butyl acetylricinoleate; pentaerythritol; and various sorbitols.

[0103] Among these, polyalkylene glycol plasticizers are preferred, and terminally ether-modified polyethylene glycol or polypropylene glycol is particularly preferred. As the hydrocarbon group for the terminal ether modification, an alkyl group having 1 to 6 carbon atoms is preferred, and a methyl group is particularly preferred.

[0104] From the viewpoint of compatibility and imparting plasticity, the molecular weight of the plasticizer is preferably 100 or more and 2,000 or less, and more preferably 200 or more and 1,500 or less.

[0105] The content of the plasticizer is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and particularly preferably 10 parts by mass or more, relative to 100 parts by mass of the (A) polyimide precursor or polyimide, from the viewpoint of imparting solubility to unexposed areas; and from the viewpoint of improving compatibility and resolution in the photosensitive resin composition, the content is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, and particularly preferably 15 parts by mass or less.

[0106] (Solvent) Examples of the solvent include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and alcohols, such as N-methyl-2-pyrrolidone, 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, and propylene glycol. Examples of solvents that can be used include glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 3-methoxy-N,N-dimethylpropanamide, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, and mesitylene. Among these, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, 3-methoxy-N,N-dimethylpropanamide, benzyl alcohol, phenyl glycol, and tetrahydrofurfuryl alcohol are preferred from the viewpoints of resin solubility, resin composition stability, and substrate adhesion.

[0107] Among these solvents, those which completely dissolve the produced polymer are particularly preferred, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, 3-methoxy-N,N-dimethylpropanamide, tetramethylurea, gamma-butyrolactone, etc. One type of solvent may be used, or two or more types of solvents may be mixed and used.

[0108] In the photosensitive resin composition of the present disclosure, the amount of the solvent used is preferably 100 to 1,000 parts by mass, more preferably 120 to 700 parts by mass, and even more preferably 125 to 500 parts by mass, per 100 parts by mass of component (A).

[0109] [Method for Producing Cured Relief Pattern] One aspect of the present embodiment is a method for producing a cured relief pattern, comprising the following steps: a step (step (1)) of forming a photosensitive resin layer on a substrate by applying a photosensitive resin composition onto the substrate, a step (step (2)) of exposing the photosensitive resin layer to light, a step (step (3)) of developing the exposed photosensitive resin layer to form a relief pattern, and a step (step (4)) of heat-treating the relief pattern to form a cured relief pattern. Some of steps (1) to (4) may be repeated.

[0110] [Step (1)] In one embodiment of this step, a photosensitive resin composition is applied to a substrate, and then dried, if necessary, to form a photosensitive resin layer. From the viewpoint of the effects of the photosensitive resin composition described above, the substrate is preferably formed from copper or a copper alloy. The photosensitive resin composition is preferably one that has a Young's modulus of 4.0 GPa to 10 GPa when a cured film having a film thickness of approximately 7 μm obtained by heating at 230° C. for 2 hours in a nitrogen atmosphere is subjected to a tensile test at a tensile speed of 50 mm / min. Examples of application methods include methods conventionally used for applying photosensitive resin compositions, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printer, etc., and spray application using a spray coater.

[0111] Examples of methods for drying the photosensitive resin composition include air drying, heat drying using an oven or a hot plate, and vacuum drying. Drying of the coating film is desirably carried out under conditions that do not cause imidization of the component (A) in the photosensitive resin composition. Specifically, when air drying or heat drying is carried out, drying can be carried out at a temperature of 20°C to 140°C for 1 minute to 1 hour.

[0112] [Step (2)] In one embodiment of this step, the photosensitive resin layer formed in the above step (1) is exposed to an ultraviolet light source or the like using an exposure device such as a contact aligner, a mirror projection, or a stepper, with or without a photomask or reticle having a pattern.

[0113] Thereafter, for the purpose of improving photosensitivity, etc., post-exposure baking (PEB) and / or pre-development baking may be performed using any combination of temperature and time, as necessary. The baking conditions are preferably a temperature of 40°C to 120°C and a time of 10 seconds to 240 seconds. However, these may be changed as appropriate depending on the properties of the photosensitive resin composition.

[0114] [Step (3)] In one embodiment of this step, unexposed portions of the exposed photosensitive resin layer are developed and removed. Examples of development methods for developing the exposed (irradiated) photosensitive resin layer include conventional photoresist development methods, such as the rotary spray method, the paddle method, and the immersion method accompanied by ultrasonic treatment. Furthermore, after development, post-development baking may be performed at any temperature and time combination, as needed, for purposes such as adjusting the shape of the relief pattern. The developer used for development is preferably, for example, a good solvent for the negative-tone photosensitive resin composition, or a combination of such a good solvent and a poor solvent. Examples of suitable good solvents include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Preferred examples of poor solvents include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When a good solvent and a poor solvent are used in combination, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the photosensitive resin composition. Two or more types of each solvent, for example, several types, can also be used in combination.

[0115] [Step (4)] In one embodiment of this step, the relief pattern obtained by the development is heated to dissolve the photosensitive component and imidize component (A), thereby converting it into a cured relief pattern made of polyimide. Heat-curing methods include, for example, using a hot plate, an oven, or a temperature-programmable heating oven. Heating can be carried out, for example, at a temperature of 200°C to 400°C for 30 minutes to 5 hours. The atmospheric gas during heat-curing may be air or an inert gas such as nitrogen or argon.

[0116] [Semiconductor Device] One aspect of the present embodiment is a semiconductor device including a cured relief pattern obtained from a photosensitive resin composition or a cured relief pattern obtained using a photosensitive resin composition. According to one aspect of the present embodiment, there is provided a semiconductor device having a substrate that is a semiconductor element and a cured relief pattern of polyimide formed on the substrate by the above-described method for producing a cured relief pattern. Furthermore, a further aspect of the present embodiment is a method for producing a semiconductor device using a semiconductor element as the substrate and including the above-described method for producing a cured relief pattern as part of its steps.

[0117] The cured relief pattern formed by the above-described method for producing a cured relief pattern can be formed as: a surface protective film for electronic components, an interlayer insulating film, an insulating film for rewiring, and a protective film for flip-chip devices; a protective film for a semiconductor device having a bump structure; or the like, and then combined with a known method for producing a semiconductor device, thereby manufacturing the semiconductor device of this embodiment.

[0118] In addition to application to semiconductor devices, the photosensitive resin composition is also useful for applications such as interlayer insulation in multilayer circuits, cover coatings for flexible copper-clad boards, solder resist films, and liquid crystal alignment films.

[0119] The present embodiment will be specifically described below using examples. However, the present embodiment is not limited to the examples. In the examples, comparative examples, and production examples, the physical properties of the polymer and photosensitive resin composition were measured and evaluated according to the following methods.

[0120] The weight average molecular weight (Mw) of the polymer was measured by gel permeation chromatography (standard polystyrene equivalent) under the following conditions: the column used for the measurement was a "Shodex 805M / 806M series" manufactured by Showa Denko K.K., standard monodisperse polystyrene was selected, the developing solvent was N-methyl-2-pyrrolidone (NMP), and the detector used was a "Shodex RI-930" manufactured by Showa Denko K.K.

[0121] (1) Patterning Performance of Cured Relief Pattern A photosensitive resin composition prepared by the method described below was sputtered onto a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm) using a sputtering apparatus (L-440S-FHL model, manufactured by Canon Anelva Corporation) to form a 200 nm thick Ti film and a 400 nm thick Cu film, in that order. Subsequently, a photosensitive resin composition prepared by the method described below was spin-coated onto this wafer using a coater developer (D-Spin 60A model, manufactured by SOKUDO Corporation), and then heated and dried on a hot plate at 110°C for 4 minutes to form a photosensitive resin layer with a thickness of approximately 8 μm. This photosensitive resin layer was then subjected to 600 mJ / cm irradiation using a Prisma GHI (manufactured by Ultratech) equipped with an i-line filter, using a test pattern mask. ２The photosensitive resin layer was then spray-developed using cyclopentanone as the developer in a coater developer (D-Spin 60A, manufactured by SOKUDO Corporation) and rinsed with propylene glycol methyl ether acetate to obtain a relief pattern on Cu. The wafer on which the relief pattern was formed on Cu was then heat-treated in a temperature-programmable curing furnace (VF-2000, manufactured by Koyo Lindberg) at 280°C for 2 hours in a nitrogen atmosphere to obtain a cured relief pattern of approximately 5 μm thick made of resin on Cu. The produced relief pattern was observed under an optical microscope to determine the size of the minimum opening pattern. If the area of ​​the opening in the obtained pattern was at least half the area of ​​the corresponding pattern mask opening, it was considered to be resolved, and the resolution was evaluated based on the length of the mask opening side (opening pattern size) corresponding to the smallest area among the resolved openings, using the following evaluation criteria. (Evaluation Criteria) S: The minimum opening pattern size is less than 5 μm. A: The minimum opening pattern size is 5 μm or more and less than 6 μm. B: The minimum opening pattern size is 6 μm or more and less than 7 μm. C: The minimum opening pattern size is 8 μm or more.

[0122] (2) Evaluation of Copper Adhesion A photosensitive resin composition prepared by the method described below was applied to a 6-inch silicon wafer that had been previously sputtered with Ti and Cu, in the same manner as in the preparation of the cured relief pattern described above. The wafer was then pre-baked and subjected to heat treatment for 2 hours at 280°C in a nitrogen atmosphere using a temperature-programmable curing furnace (VF-2000 model, manufactured by Koyo Lindberg Co., Ltd.), thereby obtaining a cured relief pattern of resin approximately 10 µm thick on the Cu. The heat-treated film was evaluated for adhesion properties between the copper substrate and the cured resin coating film according to the cross-cut method of JIS K 5600-5-6 standard, based on the following criteria: (Evaluation Criteria) S: The lattice number of the cured resin coating film adhered to the substrate is 100; A: The lattice number of the cured resin coating film adhered to the substrate is 90 to 99; B: The lattice number of the cured resin coating film adhered to the substrate is 80 to 89; C: The lattice number of the cured resin coating film adhered to the substrate is less than 80.

[0123] (3) Evaluation of Precipitability Photosensitive resin compositions prepared by the method described below were stored for one month in an environment of −20° C., and then coated on a 6-inch silicon wafer on which Ti and Cu had been sputtered in advance, in the same manner as in the preparation of the cured relief pattern described above, and prebaked. The prebaked film was observed with an optical microscope, and the presence or absence of foreign matter was evaluated based on the following criteria. (Evaluation criteria) Good: No foreign matter was found. Poor: Foreign matter was found.

[0124] (4) Evaluation of Young's Modulus of Cured Relief Pattern (Polyimide Coating Film) A photosensitive resin composition was spin-coated, coated, and dried on a 6-inch silicon wafer so that the cured film thickness was approximately 7 μm. The entire surface was then exposed to light and heated at 280°C for 2 hours in a nitrogen atmosphere using a temperature-programmed curing oven (VF-2000 model, manufactured by Koyo Lindberg Co., Ltd.) to obtain a cured relief pattern (thermo-cured polyimide coating film). The resulting polyimide coating film was cut into 3 mm wide strips using a dicing saw (DAD3350 model, manufactured by DISCO Corporation) and then peeled from the silicon wafer using 46% hydrofluoric acid to obtain polyimide tape. The Young's modulus of the resulting polyimide tape was measured using a tensile tester (UTM-II-20 model, manufactured by Orientec Co., Ltd.) in accordance with ASTM D882-09.

[0125] (5) Measurement of absorbance of component (A) and component (B) Component (A) and component (B) were each dissolved in NMP to a concentration of 10 mg / L to prepare a measurement sample. Measurements were performed using a UV-visible spectrophotometer (UV-1800, manufactured by Shimadzu Corporation) and a 1 cm cell. The absorbance of each sample at a wavelength of 365 nm divided by 10 was used as the absorbance.

[0126] [Component (A)] <Production Example 1> (Polymer A-1) 62 g (0.2 mol) of 4,4′-oxydiphthalic dianhydride (ODPA) and 65 g (0.3 mol) of pyromellitic dianhydride (PMDA) were placed in a 2-liter separable flask, and 135 g (1.04 mol) of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added and stirred at room temperature. 79.1 g of pyridine was added with stirring, and the mixture was stirred for 16 hours.

[0127] Next, under ice cooling, a solution of 203 g of dicyclohexylcarbodiimide (DCC) dissolved in 200 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by the addition of 94 g (0.44 mol) of 2,2'-dimethyl-4,4-diaminobiphenyl (m-TB) suspended in 280 ml of γ-butyrolactone over 60 minutes with stirring. The reaction mixture was further stirred at room temperature for 4 hours, after which 40 ml of ethyl alcohol was added and stirred for 1 hour, and then 1 liter of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0128] The resulting reaction solution was added to 4 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered off and dissolved in 2.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 30 liters of water to precipitate the polymer, and the resulting precipitate was filtered off and then vacuum dried to obtain a powdery polymer (Polymer A-1). The molecular weight of Polymer A-1 was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 20,000.

[0129] <Production Example 2> (Polymer A-2) A reaction was carried out in the same manner as in Production Example 1, except that 155 g (0.5 mol) of ODPA was used instead of ODPA and PMDA, and 46 g (0.44 mol) of p-phenylenediamine (pPD) was used instead of m-TB, to obtain Polymer A-2. The molecular weight of Polymer A-2 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 19,000.

[0130] <Production Example 3> (Polymer A-3) Except for using 94 g (0.44 mol) of m-TB instead of pPD, a reaction was carried out in the same manner as in Production Example 2 to obtain Polymer A-3. The molecular weight of Polymer A-3 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 26,000.

[0131] <Production Example 4> (Polymer A-4) A 3 L separable glass flask equipped with a stirrer and a stirring blade was charged with 64.1 g (0.20 mol) of 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB), 97.7 g (0.22 mol) of 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride (6FDA), and 500 g of N,N-dimethylacetamide (DMAc), and the mixture was stirred to dissolve the TFMB and 6FDA in the DMAc. Further, stirring was continued for 12 hours at room temperature under a nitrogen stream to carry out a polymerization reaction, yielding a polyamic acid solution.

[0132] To the resulting polyamic acid solution, 16 g of pyridine was added, and then 82 g of acetic anhydride was added dropwise at room temperature. Thereafter, the liquid temperature was maintained at 20 to 100°C and stirring was continued for 24 hours to carry out the imidization reaction, thereby obtaining a polyimide solution.

[0133] The obtained polyimide solution was poured into 1,000 g of methanol in a 5 L container while stirring, to precipitate a polyimide resin. The solid polyimide resin was then filtered using a suction filter and washed with 1,000 g of methanol. The solid was then dried at 100°C for 24 hours using a vacuum dryer, and then further dried at 200°C for 3 hours. This yielded Polymer (A-4), a polyimide powder having terminal acid anhydride groups. The molecular weight of Polymer A-4 was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight average molecular weight (Mw) was found to be 25,000.

[0134] <Production Example 5> (Polymer A-5) Except for using 89 g (0.44 mol) of diaminodiphenyl ether (DADPE) instead of pPD, a reaction was carried out in the same manner as in Production Example 2 to obtain Polymer A-5. The molecular weight of Polymer A-5 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 20,000.

[0135] Example 1 100 g of (A) polymer A-1, 5.0 g of (B) photopolymerization initiator B-1, 10.0 g of (C) radical polymerizable monomer C-1, 1.0 g of (D) compound D-1, and 0.5 g of Cyanox 1790 as a radical polymerization inhibitor were dissolved in 160 g of (S) solvent S-1 (γ-butyrolactone) and 40 g of solvent S-2 (dimethyl sulfoxide). The viscosity of the resulting solution was adjusted to about 4.0 Pa s by further adding a small amount of the solvent, yielding a photosensitive resin composition.

[0136] Examples 2 to 33 and Comparative Examples 1 to 6 Photosensitive resin compositions were prepared in the same manner as in Example 1, except that the components shown in Table 1 were blended in the blending ratios by mass shown in Table 2, and evaluations were carried out in the same manner as in Example 1. The evaluation results are shown in Table 3.

[0137] It was confirmed that in Examples 2 to 33, including Example 1, semiconductor devices could be fabricated using the cured relief patterns obtained from those photosensitive resin compositions as interlayer insulating films, and that these devices operated without any problems.

[0138] Table 2 shows the compositions of the photosensitive resin compositions of Examples 1 to 33 and Comparative Examples 1 to 6, and Table 3 shows the evaluation results thereof.

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148] The photosensitive resin composition of the present invention is suitable as a photosensitive material used for forming, for example, insulating materials for electronic components, and passivation films, buffer coat films, and interlayer insulating films in semiconductor devices. The photosensitive resin composition of the present invention can also be suitably used in the field of photosensitive materials useful for producing electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

1. A negative-tone photosensitive resin composition comprising: (A) a polyimide precursor or polyimide; (B) a photopolymerization initiator; (C) a radically polymerizable monomer having one photopolymerizable group; and (D) a nitrogen-containing heterocyclic compound; wherein the (C) radically polymerizable monomer is liquid under conditions of a temperature of 25°C and a pressure of 1 atm; the (D) nitrogen-containing heterocyclic compound is at least one selected from the group consisting of tetrazole derivatives, triazole derivatives, triazine derivatives, and purine derivatives; and the purine derivative has an acyl group, an alkoxy group, an alkyl group, a hydroxyalkyl group, or a heteroaryl group.

2. The polyimide precursor (A) is represented by the following general formula (1): {In the formula, X １ is a tetravalent organic group having 6 to 40 carbon atoms, and Y １ is a divalent organic group having 6 to 40 carbon atoms, n is an integer of 2 to 150, and R １ and R ２ are each independently a hydrogen atom, a photopolymerizable group, or a saturated aliphatic group having 1 to 4 carbon atoms. １ and R ２ and both of these cannot be hydrogen atoms at the same time.} and / or the polyimide (A) is a polyamic acid ester represented by the following general formula (3): {In the formula, X ２ is a tetravalent organic group having 6 to 40 carbon atoms, and Y ２ is a divalent organic group having 6 to 40 carbon atoms, and n is an integer of 2 to 50.}. The negative photosensitive resin composition according to claim 1, 3. The photopolymerization initiator (B) is represented by the following general formula (4): {In the formula, R ６ is a hydrogen atom, or an alkyl group, alkoxy group, aryl group, ester group, or acyl group having 3 to 10 carbon atoms, and R ７ and R is a hydrogen atom, or an alkyl group, alkoxy group, aryl group, ester group, or acyl group having 1 to 10 carbon atoms.

4. In the general formula (1) and the general formula (3), Y １ and Y ２ is represented by the following general formula (5): {In the formula, R ８ ~R １５ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aromatic group, or a hydroxyl group, and may be different from each other or the same as each other.} or a group represented by the following general formula (6): {In the formula, R １６ ~R １９ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aromatic group, or a hydroxyl group, and may be different from each other or the same.

5. The photopolymerization initiator (B) is represented by the following general formula (7): {In the formula, R ６ and R is a hydrogen atom, or an alkyl group, alkoxy group, aryl group, ester group, or acyl group having 1 to 10 carbon atoms.

6. The negative photosensitive resin composition according to claim 1 or 2, wherein the absorbance at a wavelength of 365 nm when the photopolymerization initiator (B) is dissolved in N-methyl-2-pyrrolidone at a concentration of 0.1% by volume (vol) is 0.05 or less.

7. The negative photosensitive resin composition according to claim 1 or 2, wherein the photopolymerizable group of the radical polymerizable monomer (C) is a (meth)acrylic group or a (meth)acryloyl group.

8. The negative photosensitive resin composition according to claim 1 or 2, wherein the radical polymerizable monomer (C) has an alkylene oxide structure.

9. The negative photosensitive resin composition according to claim 1 or 2, wherein the radical polymerizable monomer (C) has a linear or cyclic alkyl structure.

10. The negative photosensitive resin composition according to claim 1 or 2, wherein the molecular weight of the radical polymerizable monomer (C) is 500 or less.

11. The negative photosensitive resin composition according to claim 1 or 2, wherein the radical polymerizable monomer (C) does not contain a urethane bond or a urea bond.

12. The negative photosensitive resin composition according to claim 1 or 2, wherein the radical polymerizable monomer (C) does not contain an azole group.

13. The negative photosensitive resin composition according to claim 1 or 2, wherein the nitrogen-containing heterocyclic compound (D) is a purine derivative having an alkyl group having two or more carbon atoms.

14. The negative photosensitive resin composition according to claim 1 or 2, wherein the nitrogen-containing heterocyclic compound (D) is a purine derivative having an acyl group, an alkoxy group, a hydroxyalkyl group, or a heteroaryl group.

15. The negative photosensitive resin composition according to claim 1 or 2, wherein the nitrogen-containing heterocyclic compound (D) is a purine derivative having an acyl group or an alkoxy group.

16. The negative photosensitive resin composition according to claim 15, wherein the acyl group is an aliphatic acyl group.

17. The negative photosensitive resin composition according to claim 1 or 2, wherein the nitrogen-containing heterocyclic compound (D) is a purine derivative and the molecular weight of the nitrogen-containing heterocyclic compound (D) is 300 or less.

18. The negative photosensitive resin composition according to claim 1, further comprising (E) an organic acidic compound.

19. The negative photosensitive resin composition according to claim 18, wherein the organic acidic compound (E) contains a sulfonic acid or a carboxylic acid.

20. The negative photosensitive resin composition according to claim 1 or 2, wherein the composition is heated at 230°C for 2 hours in a nitrogen atmosphere to produce a cured film having a thickness of approximately 7 μm, and when the film is subjected to a tensile test at a tensile speed of 50 mm / min, the Young's modulus is 4.0 GPa to 10 GPa.

21. The negative photosensitive resin composition according to claim 1 or 2, wherein the (A) polyimide precursor or polyimide has an absorbance of 0.8 or more at a wavelength of 365 nm when dissolved in N-methyl-2-pyrrolidone at a concentration of 0.1% by volume (vol).

22. A method for producing a cured relief pattern, comprising the following steps: (1) applying the negative photosensitive resin composition according to claim 1 or 2 onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; and (4) heat-treating the relief pattern to form a cured relief pattern.

23. The method of claim 22, wherein the substrate is formed from copper or a copper alloy.

24. A semiconductor device comprising a cured relief pattern formed using the negative photosensitive resin composition according to claim 1 or 2.

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