Photosensitive resin composition and production method for cured relief pattern, cured film, and production method for polyimide film using same

Abstract

Provided is a photosensitive resin composition that includes (A) a polyimide precursor and / or a polyimide resin, (B) a tetrazole compound that has a pKa of 1.3–4.1, (C) a heterocyclic compound other than (B) the tetrazole compound, and (D) a photopolymerization initiator.

Description

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

[0001] The present disclosure relates to a photosensitive resin composition, a method for producing a cured relief pattern using the same, and a method for producing a cured film and a polyimide film.

[0002] Conventionally, polyimide resins, polybenzoxazole resins, phenolic resins, and the like, which combine excellent heat resistance and electrical and mechanical properties, have been used as insulating materials for electronic components, and passivation films, surface protective films, interlayer insulating films, and the like for semiconductor devices. Among these resins, those provided in the form of photosensitive resin compositions can easily form heat-resistant relief pattern films by applying the composition, exposing it to light, developing it, and subjecting it to a thermal imidization treatment through curing. Such photosensitive resin compositions have the advantage of enabling significant process reduction compared to conventional non-photosensitive materials.

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 Conventional mounting methods using metal pins and lead-tin eutectic solder have been replaced by structures in which a polyimide coating directly contacts the solder bumps, such as BGA (ball grid array) and CSP (chip size packaging), which enable higher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

[0004] Copper is often used for wiring in semiconductor devices, but in large-area packaging structures, the difference in thermal expansion coefficients between different materials causes stress, which can lead to peeling between the copper and the interlayer insulating material, resulting in a deterioration in electrical properties. Therefore, materials used as interlayer insulating films are required to have high adhesion to copper. For example, Patent Document 2 describes the use of a purine derivative to inhibit copper discoloration and improve adhesion.

[0005] US Patent Application Publication No. 2018 / 0061699 JP 2012-194520 A

[0006] In recent years, semiconductor devices have become finer in wiring due to their higher performance, multi-functionality, lower power consumption, and lower costs, which has led to a need for higher resolution in insulating films. Furthermore, as the wiring of semiconductor devices becomes finer, the wiring width and spacing of the semiconductor devices become narrower, which has led to a significant problem of copper migration into resin layers (hereinafter also referred to as "copper migration" in the present disclosure) and short circuits between wirings. Therefore, the ability to inhibit copper migration of a photosensitive resin composition used as an insulating film is one of its important performance characteristics.

[0007] Furthermore, the application of semiconductor devices to automobiles and mobile phones is remarkable, and semiconductor devices in this field are required to have high reliability, and reliability tests are being carried out in high-temperature and high-humidity environments.

[0008] However, conventional interlayer insulating films have insufficient copper migration suppression capabilities, and copper migration sometimes occurs during reliability tests under high temperature and high humidity (b-HAST: Biased Highly Accelerated Stress Test). Furthermore, as copper migration progresses, voids (hereinafter also referred to as "copper voids" in this disclosure) may occur at the interface between the copper wiring and the resin layer. When copper voids occur at the interface between the copper wiring and the resin layer, adhesion between the two decreases, and in severe cases, the resin peels off from the copper, impairing insulation properties. Meanwhile, high-temperature curing is performed to improve copper migration suppression capabilities and film properties, but this tends to result in a decrease in copper adhesion. Therefore, an insulating film that exhibits low copper migration even in b-HAST tests and good copper adhesion even when cured at high temperatures is desired.

[0009] An object of the present disclosure is to provide a photosensitive resin composition that exhibits high copper adhesion even when cured at high temperatures, exhibits minimal copper migration in a b-HAST test, does not short-circuit for a long period of time, and has high resolution. Another object is to provide a method for forming a cured relief pattern using the photosensitive resin composition of the present disclosure, and methods for producing a cured film and a polyimide film.

[0010] Examples of embodiments of the present disclosure are listed in the following items [1] to

[22] .

[0011] [1] A photosensitive resin composition comprising the following components: (A) a polyimide precursor and / or a polyimide resin; (B) a tetrazole compound having a pKa of 1.3 or more and 4.1 or less; (C) a heterocyclic compound other than the (B) tetrazole compound; and (D) a photopolymerization initiator. [2] The photosensitive resin composition according to [1], wherein the (B) tetrazole compound is a compound having a carboxyl group. [3] The photosensitive resin composition according to [1] or [2], wherein the (D) photopolymerization initiator is a photoradical polymerization initiator. [4] The photosensitive resin composition according to [3], wherein the photoradical polymerization initiator is an oxime initiator. [5] The photosensitive resin composition according to any one of [1] to [4], wherein the (C) heterocyclic compound contains a purine derivative. [6] The (B) tetrazole compound is represented by the following general formula (1): {In formula (1), R １ represents a carboxyl group or the following general formula (2): and R ２ is a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with at least one of a halogen atom, a hydroxyl group, an alkoxysilyl group, and an amino group.}. [7] The photosensitive resin composition according to any one of [1] to [5], wherein the heterocyclic compound (C) is a compound represented by the following general formula (3): {In the formula, R ３ is an amino group or an alkoxy group having 1 to 6 carbon atoms, and R ４ is a hydrogen atom or an amino group which may be substituted with a plurality of organic groups having 1 to 10 carbon atoms, and R ５ is a hydrogen atom or an organic group having 1 to 10 carbon atoms.}, a compound represented by the following general formula (4): {In the formula, R ６ is a hydrogen atom or an amino group which may be substituted with a plurality of organic groups having 1 to 10 carbon atoms, and R ７ is a hydrogen atom or an organic group having 1 to 10 carbon atoms.}, a compound represented by the following general formula (5): {In the formula, R ８ is an amino group or an alkoxy group having 1 to 6 carbon atoms, and R ９ is a hydrogen atom or an amino group which may be substituted with a plurality of organic groups having 1 to 10 carbon atoms, and R １０ is a hydrogen atom or an organic group having 1 to 10 carbon atoms.}, or a compound represented by the following general formula (6): {In the formula, R １１ is a hydrogen atom or an amino group which may be substituted with a plurality of organic groups having 1 to 10 carbon atoms, and R １２ is a hydrogen atom or an organic group having 1 to 10 carbon atoms.}. [8] The photosensitive resin composition according to any one of [1] to [6], wherein the heterocyclic compound (C) is a compound represented by the following general formula (7): {In the formula, R １３ is an organic group having 1 to 10 carbon atoms, and R １４ is a hydrogen atom or an organic group having 1 to 10 carbon atoms.}. [9] The photosensitive resin composition according to any one of [1] to [7], wherein the compound is represented by the following general formula (8): {In the formula, X １ is a tetravalent organic group, and Y １ is a divalent organic group, and n １ is an integer from 2 to 150, and R １５ and R １６ are each independently a hydrogen atom or a monovalent organic group.} and / or the polyimide precursor is represented by the following general formula (9): {In the formula, X ２ is a tetravalent organic group, and Y ２ is a divalent organic group, and n ２

[10] The photosensitive resin composition according to any one of [1] to [8], which contains the polyimide resin represented by the general formula (8): １５ and R １６ At least one of the following general formula (10): {In the formula, L １ , L ２ and L ３ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m １is an integer of 2 to 10.}.

[11] The photosensitive resin composition according to any one of [1] to

[10] , wherein the total content of the (B) tetrazole compound and the (C) heterocyclic compound is 0.1 to 10 parts by mass per 100 parts by mass of the (A) component.

[12] The photosensitive resin composition according to any one of [1] to

[11] , wherein the ratio of the content of the (B) tetrazole compound to the content of the (C) heterocyclic compound satisfies the following formula (9): 0.1≦(content of the (B) tetrazole compound (parts by mass) / (content of the (C) heterocyclic compound (parts by mass)≦10 (9).

[13] The photosensitive resin composition according to any one of [1] to

[12] , further containing (E) a solvent.

[14] The photosensitive resin composition according to any one of [1] to

[13] , further containing (F) a photopolymerizable monomer.

[15] The photosensitive resin composition according to any one of [1] to

[14] , further comprising (G) a thermal crosslinking agent.

[16] The photosensitive resin composition according to any one of [1] to

[15] , further comprising (H) a silane coupling agent.

[17] The photosensitive resin composition according to any one of [1] to

[16] , further comprising (I) an acid component other than the (B) tetrazole compound.

[18] The photosensitive resin composition according to any one of [1] to

[17] , which is a photosensitive resin composition for forming a surface protective film, an interlayer insulating film, an insulating film for redistribution wiring, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure.

[19] A method for producing a cured relief pattern, comprising the following steps: (1) applying the photosensitive resin composition according to any one of [1] to

[18] onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer; (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.

[20] A method for producing a cured relief pattern according to

[19] , wherein the heat treatment in step (4) is a heat treatment at 170°C or higher and 350°C or lower.

[21] A cured film comprising a cured product of the photosensitive resin composition according to any one of [1] to

[18] .

[22] A method for producing a polyimide film, comprising curing the photosensitive resin composition according to any one of [1] to

[18] .

[0012] According to the present disclosure, it is possible to provide a photosensitive resin composition that exhibits high copper adhesion even when cured at high temperatures, exhibits little copper migration in the b-HAST test, and has high resolution. It is also possible to provide a method for producing a cured relief pattern using the photosensitive resin composition, and a method for producing a cured film and a polyimide film.

[0013] Hereinafter, embodiments of the present disclosure will be described in detail. The present disclosure is not limited to the following embodiments and can be implemented with various modifications within the scope of the gist thereof. Note that throughout the present disclosure, when a plurality of structures represented by the same symbol in a general formula are present in a molecule, they may be the same or different from each other. Furthermore, the upper and lower limit values ​​in each numerical range of the present disclosure can be arbitrarily combined to form any numerical range.

[0014] <Photosensitive Resin Composition> The photosensitive resin composition of the present disclosure contains the following components (A) to (D): (A) a polyimide precursor and / or a polyimide resin, (B) a tetrazole compound having a pKa of 1.3 or more and 4.1 or less, (C) a heterocyclic compound other than the (B) tetrazole compound, and (D) a photopolymerization initiator.

[0015] (A) Polyimide Precursor (Component A) The (A) polyimide precursor is a resin component contained in the photosensitive resin composition, and is converted to a polyimide by a thermal cyclization treatment. The structure of the (A) polyimide precursor is not limited as long as it is a resin that can be used in the photosensitive resin composition, but it is preferably not an alkali-soluble resin. If the resin used in the (A) polyimide precursor is not alkali-soluble, high chemical resistance and higher copper migration suppression ability can be obtained. In order to obtain a polyimide precursor that is not alkali-soluble, it is preferable that the resin skeleton does not contain acidic groups. It is also preferable that the (A) polyimide precursor does not contain fluorine atoms. This can further suppress copper migration.

[0016] The polyimide precursor (A) is represented by the following general formula (8): {In the formula, X １is a tetravalent organic group, and Y １ is a divalent organic group, and n １ is an integer from 2 to 150, and R １５ and R １６ are each independently a hydrogen atom or a monovalent organic group.} The polyimide precursor represented by the formula (8) is preferably a polyamide containing a structure represented by the formula １ It is also preferred that X is a polyamide having a structure that does not contain acidic groups such as carboxylic acid groups and phenolic hydroxyl groups. １ is R １５ or R １６ is a hydrogen atom, the polyimide precursor (A) preferably does not have an acidic group, except for a carboxy group present in the structure. Since the polyimide precursor (A) does not have an acidic group in the structure, it is easy to obtain a polyimide precursor that is not alkali-soluble.

[0017] In general formula (8), R １５ and R １６ At least one of the above preferably contains a photopolymerizable functional group, and is represented by the following general formula (10): {In the formula, L １ , L ２ and L ３ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m １ is an integer of 2 to 10.}.

[0018] R in general formula (8) １５ and R １６ The proportion of hydrogen atoms in R １５ and R １６ The amount is more preferably 10 mol % or less, more preferably 5 mol % or less, and even more preferably 1 mol % or less, based on the total number of moles. By setting the amount to this range, it is easy to obtain a polyimide precursor that is not alkali-soluble. １５ and R １６ is a monovalent organic group represented by the general formula (10), R １５ and R １６It is preferably 70 mol % or more, more preferably 80 mol % or more, and even more preferably 90 mol % or more, based on the total number of moles. １５ and R １６ is a hydrogen atom, and R in the general formula (8) １５ and R １６ It is preferable that the proportion of the organic group of formula (10) is within the above range from the viewpoint of photosensitive properties and storage stability.

[0019] n in general formula (8) １ is not limited as long as it is an integer of 2 to 150, but is preferably an integer of 3 to 100, more preferably an integer of 5 to 70, from the viewpoint of the photosensitive properties and mechanical properties of the photosensitive resin composition.

[0020] In general formula (8), X １ From the viewpoint of achieving both heat resistance and photosensitive properties, the tetravalent organic group represented by the formula (I) is preferably an organic group having 6 to 40 carbon atoms, and more preferably, -COOR １５ group and -COOR １６ The X group and the —CONH— group are in the ortho position relative to each other, or an alicyclic aliphatic group. １ Specifically, examples of the tetravalent organic group represented by the following general formula (11): {In the formula, R １７ is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a monovalent fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, l is an integer of 0 to 2, m is an integer of 0 to 3, and n is an integer of 0 to 4.}, but is not limited to these. １ The structure of X having the structure represented by the above formula (11) 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.

[0021] X １ As the group, among the structures represented by the above formula (11), the following formula (12): {In the formula, R １８is 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, and m is an integer of 0 to 3.} is preferred from the viewpoints of the imidization rate during low-temperature heating, degassing properties, copper adhesion, chemical resistance, etc.

[0022] In the above general formula (8), Y １ From the viewpoint of achieving both heat resistance and photosensitive properties, the divalent organic group represented by the following general formula (13): {In the formula, R １７ is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a monovalent fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, l is an integer of 0 to 4, m is an integer of 0 to 4, and n is an integer selected from 0 to 4.}, but is not limited to these. １ The structure represented by the formula (13) 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.

[0023] Y １ As the group, among the structures represented by the above formula (13), particularly, the group represented by the following formula (14): {In the formula, R １８ 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, and l is an integer of 0 to 4, and m is an integer of 0 to 4.} is preferred from the viewpoints of the imidization rate during low-temperature heating, degassing properties, copper adhesion, chemical resistance, etc.

[0024] L in the above general formula (10) １ , L ２ and L ３ The monovalent organic group having 1 to 3 carbon atoms is, for example, a hydrocarbon group having 1 to 3 carbon atoms, preferably an alkyl group. １ is preferably a hydrogen atom or a methyl group, and L ２ and L ３is preferably a hydrogen atom from the viewpoint of photosensitive properties. １ is an integer of 2 or more and 10 or less, preferably an integer of 2 or more and 4 or less, from the viewpoint of photosensitivity characteristics.

[0025] In one embodiment, the polyimide precursor (A) is represented by the following general formula (15): {In the formula, R １５ , R １６ , and n １ are each defined in the above general formula (8).}

[0026] In general formula (15), R １５ and R １６ It is more preferable that at least one of the following is a monovalent organic group represented by the general formula (10): X represented by １ Inclusion of these in the structural units results in particularly high chemical resistance.

[0027] In one embodiment, the polyimide precursor (A) is represented by the following general formula (17): {In the formula, R １５ , R １６ , and n １ are defined as in the above general formula (8).} In terms of thermal properties, it is preferable that the polyimide precursor contains a structural unit represented by the following formula:

[0028] In general formula (17), R １５ and R １６ At least one of the groups is more preferably a monovalent organic group represented by the above general formula (10).

[0029] The polyimide precursor (A) tends to have particularly high resolution when it contains both the structural unit represented by general formula (15) and the structural unit represented by general formula (17). For example, the polyimide precursor (A) may contain a copolymer of the structural unit represented by general formula (15) and the structural unit represented by general formula (17), or may be a mixture of a polyimide precursor containing the structural unit represented by general formula (15) and a polyimide precursor containing the structural unit represented by general formula (17).

[0030] The polyimide precursor (A) is represented by the following general formula (18): {In the formula, R １５ , R １６ , and n １ are each defined in the above general formula (8).}

[0031] The polyimide precursor (A) is represented by the following general formula (19): {In the formula, R １５ , R １６ , and n １ are defined as in the general formula (8).} When the (A) polyimide precursor contains a structural unit represented by the general formula (19), chemical resistance is particularly enhanced.

[0032] The polyimide precursor (A) is contained in an amount of preferably 10 to 70% by mass, more preferably 20 to 65% by mass, based on the total mass of the photosensitive resin composition including the solvent.

[0033] (A) Method for Preparing Polyimide Precursor (A) The polyimide precursor is a polyimide precursor having the above-mentioned tetravalent organic group X １ A 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.

[0034] (Preparation of Acid / Ester Form) (A) A tetravalent organic group X suitable for preparing a polyimide precursor １ Examples of tetracarboxylic dianhydrides containing the tetravalent organic group X include pyromellitic dianhydride (PMDA), 4,4'-oxydiphthalic dianhydride (ODPA), benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA), diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane. However, １ The tetracarboxylic dianhydride containing the above is not limited to these. Among these, preferred examples of the tetracarboxylic dianhydride include pyromellitic dianhydride (PMDA), 4,4'-oxydiphthalic dianhydride (ODPA), and biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA). These may be used alone or in combination of two or more.

[0035] (A) Examples of alcohols having a photopolymerizable unsaturated double bond that are preferably used to prepare the polyimide precursor 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.

[0036] The photopolymerizable alcohols having an unsaturated double bond may be partially mixed with alcohols not having an unsaturated double bond, such as methanol, ethanol, 1-propanol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, 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.

[0037] Alternatively, a non-photosensitive polyimide precursor prepared solely from the above-described alcohols having no unsaturated double bonds may be used as the polyimide precursor (A) by mixing it with a photosensitive polyimide precursor. From the viewpoint of resolution, the amount of the non-photosensitive polyimide precursor is preferably 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor. The above-described suitable tetracarboxylic acid dianhydride and the above-described alcohol are stirred, dissolved, and mixed in the presence of a basic catalyst such as pyridine in a solvent described below at a temperature of 20 to 50°C for 4 to 24 hours, whereby an esterification reaction of the acid anhydride proceeds, and the desired acid / ester product can be obtained.

[0038] (A) Preparation of Polyimide Precursor) A suitable dehydration condensation agent, such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate, is added to and mixed with the above acid / ester compound (typically a solution in a solvent described below) under ice cooling to convert the acid / ester compound into a polyacid anhydride, and then a divalent organic group Y １ The target polyimide precursor can be obtained by adding dropwise a solution or dispersion of a diamine containing the compound dissolved or dispersed in a separate solvent and carrying out amide polycondensation. Alternatively, the target polyimide precursor can be obtained by converting the acid moiety of the acid / ester compound into an acid chloride using thionyl chloride or the like, and then reacting the acid / ester compound with a diamine compound in the presence of a base such as pyridine.

[0039] Divalent organic group Y １ Examples of diamines containing the following general formula (20): Examples of the diamines include those having the structure shown in the following formula: p-phenylenediamine (1,4-phenylenediamine (pPD)), m-phenylenediamine, 4,4'-oxydianiline (ODA), 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, Aminobiphenyl, 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 (TPE-Q), 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene (APB), bis[4-(4-aminophenoxy)phenyl]s 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)hexafluoro propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP), 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene (BAFL), and compounds in which some of the hydrogen atoms on the benzene ring have been substituted with a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a halogen, or the like, such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,Examples of the diamine include, but are not limited to, 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, and mixtures thereof. Preferred diamines include 4,4'-oxydianiline (ODA), 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB), and 1,4-phenylenediamine (pPD). These diamines can be used alone or in combination of two or more.

[0040] After the amide polycondensation reaction is completed, the water-absorbing by-product of the dehydrating condensing agent coexisting in the reaction solution is filtered off as needed, and then a poor solvent such as water, an aliphatic lower alcohol, or its reaction solution is added to the resulting polymer component to precipitate the polymer component, and the polymer is purified by repeating redissolution and reprecipitation procedures, followed by vacuum drying to isolate the target polyimide precursor. To improve the degree of purification, the polymer solution may be passed through a column packed with an anion and / or cation exchange resin swollen with an appropriate organic solvent to remove ionic impurities.

[0041] The molecular weight of the (A) polyimide precursor, as measured by gel permeation chromatography in terms of polystyrene equivalent weight average molecular weight, is preferably 8,000 to 150,000, more preferably 9,000 to 50,000. When the (A) polyimide precursor has a weight average molecular weight of 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 recommended as developing solvents for gel permeation chromatography. The weight average molecular weight of the (A) polyimide precursor is determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended that the standard monodisperse polystyrene be selected from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko K.K.

[0042] (A) Polyimide Resin (Component A) The photosensitive resin composition of the present disclosure may contain (A) a polyimide resin in addition to or instead of (A) the polyimide precursor.

[0043] The polyimide resin (A) does not generate resin-derived elimination components, and therefore can suppress the cure shrinkage of the photosensitive resin composition, thereby enabling the production of a photosensitive resin composition having a higher cure residual film rate and improved post-cure flatness compared to polyimide precursors.

[0044] The (A) polyimide resin may have a polymerizable group in a side chain, but preferably does not have a polymerizable group in a side chain from the viewpoint of the elongation and storage stability of the cured film. The (A) polyimide resin preferably does not substantially contain a polyamic acid or polyamic acid ester structure. In the present disclosure, "substantially does not contain a polyamic acid or polyamic acid ester structure" means, for example, that the imidization rate of the polyimide resin is 90% or more, preferably 95% or more.

[0045] (A) The imidization rate of a polyimide resin can be measured by a known method, but in the present disclosure, it is calculated by the following method. First, the infrared absorption spectrum of the polyimide resin before heat treatment is measured, and the absorption peak of the imide structure (1780 cm －１ Near 1377 cm －１ Next, the polyimide resin is heat-treated at 350°C for 1 hour, and the infrared absorption spectrum of the heat-treated polyimide is measured. －１ The imidization rate of the polyimide resin is calculated by comparing the peak intensity in the vicinity with the peak intensity of the polyimide before heat treatment.

[0046] From the viewpoints of solubility in a solvent and flatness during coating, it is preferable that the polyimide resin (A) contains a structure represented by general formula (9). This structure is also suitable for a solvent-developable photosensitive resin composition. From the viewpoint of suppressing copper migration, it is preferable that the polyimide resin (A) is a resin that is not alkali-soluble. Furthermore, when the polyimide resin (A) contains a structure represented by general formula (9), X ２ and / Y２ It is also preferable that the polyimide resin (A) does not have an acidic group such as a carboxylic acid group or a phenolic hydroxyl group. It is also preferable that the polyimide resin (A) does not have a fluorine atom. This can further suppress copper migration. {In the formula, X ２ is a tetravalent organic group, and Y ２ is a divalent organic group, and n ２ is an integer from 2 to 150.

[0047] X ２ is a tetravalent organic group, and is not particularly limited as long as it has a structure derived from a known tetracarboxylic dianhydride. However, from the viewpoints of high copper adhesion of the cured film, suppression of copper voids after a high-temperature storage test, suppression of copper migration in a b-HAST test, excellent elongation and chemical resistance of the cured film, and solubility in solvents, it is preferable that the cured film contains at least one structure represented by the following general formulas (21) to (29):

[0048] Also, X ２ Preferably, X contains one or more structures represented by formulas (21) to (28) from the viewpoints of suppressing copper voids after a high-temperature storage test of a cured film obtained from the photosensitive resin composition of the present disclosure, suppressing copper migration in a b-HAST test, and improving the elongation and chemical resistance of the cured film. ２ From the viewpoint of the heat resistance of the cured film obtained from the photosensitive resin composition of the present disclosure, it is more preferable that X contains one or more structures represented by formulas (21) to (23) and (25) to (28). ２ It is particularly preferred that the photosensitive resin composition of the present disclosure contains one or more structures represented by formulas (21) and (26) to (28), since this results in particularly excellent coating film uniformity and cured film elongation.

[0049] Y in formula (9) ２is a divalent organic group, and is not particularly limited as long as it has a structure derived from a known diamine; however, from the viewpoints of high copper adhesion of the cured film, inhibition of copper migration in the b-HAST test, excellent elongation and chemical resistance of the cured film, and solubility in solvents, it is preferable that the cured film contain one or more structures represented by the following general formulas (30) to (38):

[0050] Also, Y ２ Preferably, Y contains one or more structures represented by formulas (30) to (36) from the viewpoints of suppressing copper voids after a high-temperature storage test of a cured film obtained from the photosensitive resin composition of the present disclosure, suppressing copper migration in a b-HAST test, and improving the elongation and chemical resistance of the cured film. ２ From the viewpoint of the mechanical properties of the cured film obtained from the photosensitive resin composition of the present disclosure, it is more preferable that Y contains one or more structures represented by formulas (30) to (35). ２ It is particularly preferred that the photosensitive resin composition of the present disclosure (in one embodiment, the negative photosensitive resin composition of the present disclosure) contains one or more structures represented by formulas (32) to (35) because the coating film uniformity and cured film elongation are particularly excellent. The structures represented by formulas (32) to (35) have excellent solubility in solvents because these structures contain a pendant phenyl structure.

[0051] n in formula (9) ２ is an integer of 2 to 150, preferably an integer of 3 to 100, and more preferably an integer of 5 to 70. ２ is preferably an integer that satisfies the weight average molecular weight of the polyimide resin (A).

[0052] From the viewpoint of solubility in a solvent, it is preferable that the terminal of the (A) polyimide resin (in one embodiment, the side chain terminal of the (A) polyimide resin or the main chain terminal of the (A) polyimide resin), preferably the main chain terminal of the (A) polyimide resin, contains one or more structures selected from the group consisting of an acid anhydride group, a carboxyl group, an amino group, and the following general formulae (39) to (41): {In the formula, R １９ and R ２０ are each independently selected from a hydrogen atom and a monovalent organic group having 1 to 3 carbon atoms; R ２１ is a divalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and k is an integer of 1 or 2. ２２ represents a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms, and * represents a bonding site with the terminal of the polyimide resin (A). {In the formula, R ２３ and R ２４ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. * indicates the bonding site with the terminal of the (A) polyimide resin. {In the formula, R ２５ , R ２６ and R ２７ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and j is an integer of 2 to 10. In addition, * indicates the bonding site with the end of the polyimide resin (A).

[0053] It is preferred that the acid anhydride group is derived from the raw material tetracarboxylic acid anhydride, the carboxyl group is formed by ring-opening of the aforementioned acid anhydride group, and the amino group is derived from the raw material diamine. More specific examples of the (A) polyimide resin having a terminal structure represented by general formula (39) include structures represented by the following general formulas (42) to (45). {In the formula, * indicates the bonding site with the terminal of the polyimide resin (A).} More specific examples of the structure represented by general formula (40) include structures represented by the following general formulas (46) and (47). (In the formula, * indicates the bonding site with the terminal of the polyimide resin (A).)

[0054] More specific examples of the structure represented by general formula (41) include structures represented by the following general formulae (48) to (51). (In the formula, * indicates the bonding site with the terminal of the polyimide resin (A).)

[0055] From the viewpoints of high copper adhesion of the cured film, suppression of copper voids after high-temperature storage test, suppression of copper migration in b-HAST test, elongation of the cured film, chemical resistance, and solubility in solvents, X in general formula (9) ２ is any one of the structures represented by general formulas (21) to (29), and Y ２ is preferably any one of the structures represented by general formulas (30) to (38).

[0056] The weight-average molecular weight (Mw) of the (A) polyimide resin is not particularly limited as long as it is in a range that allows it to dissolve in a solvent. From the viewpoint of the film properties and copper adhesion of the cured film, the weight-average molecular weight of the (A) polyimide resin is preferably 5,000 or more and 100,000 or less. From the viewpoint of mechanical properties, the lower limit of the weight-average molecular weight of the (A) polyimide resin is more preferably 6,000 or more, and even more preferably 8,000 or more. Furthermore, from the viewpoint of solubility in a solvent and flatness during coating, the upper limit of the weight-average molecular weight of the (A) polyimide resin is more preferably 50,000 or less, and particularly preferably 30,000 or less.

[0057] The molecular weight distribution (Mw / Mn) of the (A) polyimide resin is preferably 1.0 or more and 2.0 or less. From the viewpoint of production efficiency, the lower limit of the molecular weight distribution of the (A) polyimide resin is more preferably 1.15 or more, and even more preferably 1.25 or more. From the viewpoint of resolution, the upper limit of the molecular weight distribution of the (A) polyimide resin is more preferably 1.8 or less, and even more preferably 1.6 or less.

[0058] The content of the polyimide resin (A) is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 65% by mass, based on the total mass of the photosensitive resin composition including the solvent.

[0059] (A) Method for Preparing Polyimide Resin (A) Polyimide resin is obtained by reacting a tetracarboxylic dianhydride with a diamine to obtain a polyamic acid, and then subjecting the polyamic acid to dehydration ring closure to imidization.

[0060] The method for dehydrating and cyclizing the polyamic acid is not limited, but examples thereof include a thermal imidization method in which the polyamic acid is heated at a high temperature to dehydrate and cyclize, and a chemical imidization method in which the polyamic acid is dehydrated and cyclized by adding acetic anhydride and a tertiary amine, which are dehydrating and reducing agents.

[0061] The temperature in the thermal imidization method is not particularly limited, but from the viewpoint of promoting the ring-closing reaction, the lower limit is preferably 150° C. or higher, more preferably 160° C. or higher, while from the viewpoint of suppressing side reactions, the upper limit is preferably 200° C. or lower, more preferably 180° C. or lower.

[0062] The tetracarboxylic dianhydride is not particularly limited, but specific examples include pyromellitic anhydride (PMDA), 4,4'-oxydiphthalic anhydride (ODPA), 3,4'-oxydiphthalic anhydride, 4,4'-biphthalic dianhydride (BPDA), 3,4'-biphthalic dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (BPADA), 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BP AF), norbornane-2-spiro-α-cyclopentanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride (CpODA), bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BCD), 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), and 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride (6FDA). Among these, preferred tetracarboxylic dianhydrides include bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BCD), 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), and 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride (6FDA).

[0063] The diamine is not particularly limited, but specific examples include 4,4'-diaminodiphenyl ether (DADPE), 3,4'-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene (APB), 1,4-bis(4-aminophenoxy)benzene (TPE-Q), 2-phenoxybenzene-1,4-diamine (PND), 9,9-bis(4-aminophenyl)fluorene (BAFL), 6-(4-aminophenoxy)biphenyl-3-amine (PDPE), 3,3'- ... Examples of suitable diamines include 2,2-bis[3-phenyl-4-(4-aminophenoxy)phenyl]propane (DAOPPA), 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)benzidine (TFMB), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP), and 2-(methacryloyloxy)ethyl-3,5-diaminobenzoate (MAEDAB). Among these, preferred diamines include 6-(4-aminophenoxy)biphenyl-3-amine (PDPE) and 9,9'-bis(4-aminophenyl)fluorene (BAFL).

[0064] When the terminals of the (A) polyimide resin are an acid anhydride group, a carboxyl group, and an amino group, the (A) polyimide resin is a polyimide resin obtained by imidizing a polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine through dehydration and ring closure. The terminals of the (A) polyimide resin may be converted to the structures represented by the above general formulas (39) to (41) by reacting the acid anhydride groups, carboxyl groups, and amino groups with a predetermined compound.

[0065] Polyimide resin (A) whose terminal has a structure represented by general formula (39) can be obtained, for example, by reacting the amino group at the polyimide terminal with an isocyanate compound. Specific examples of the isocyanate compound include 2-methacryloyloxyethyl isocyanate (2-isocyanatoethyl methacrylate: MOI), 2-acryloyloxyethyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, and 2-(2-methacryloyloxyethyloxy)ethyl isocyanate. The method for reacting the amino group at the polyimide terminal with the isocyanate compound is not particularly limited. For example, the isocyanate compound can be added to a dehydrated, ring-closed polyimide solution and stirred at room temperature to react with the amino group of the dehydrated, ring-closed polyimide.

[0066] The polyimide resin (A) whose terminal has a structure represented by general formula (40) can be obtained, for example, by reacting the amino group at the polyimide terminal with a chloride compound. Examples of the chloride compound include acryloyl chloride and methacryloyl chloride. The method for reacting the amino group at the polyimide terminal with the chloride compound is not particularly limited. For example, a polyimide solution subjected to dehydration and ring closure can be ice-cooled and the chloride compound can be added dropwise to react with the amino group of the dehydration and ring closure polyimide.

[0067] Polyimide resin (A) whose terminals have a structure represented by general formula (41) can be obtained, for example, by reacting the acid anhydride groups and carboxyl groups at the polyimide terminals with an alcohol-based compound. Examples of the alcohol-based compound include 2-hydroxyethyl methacrylate (2-hydroxyethyl methacrylate: HEMA), 2-hydroxyethyl acrylate, 4-hydroxyethyl methacrylate, and 4-hydroxyethyl acrylate. The method for reacting the acid anhydride groups and carboxyl groups at the polyimide terminals with the alcohol-based compound is not particularly limited, but the acid anhydride groups and carboxyl groups of the dehydrated, ring-closed polyimide can be reacted with the alcohol-based compound using a condensing agent such as N,N'-dicyclohexylcarbodiimide (DCC) or an esterification catalyst such as p-toluenesulfonic acid.

[0068] (A) In the production of polyimide resin, a reaction solvent may be used to efficiently carry out the reaction in a homogeneous system. The reaction solvent is not particularly limited as long as it can uniformly dissolve or suspend the tetracarboxylic dianhydride, diamine, and compound having a terminal polymerizable functional group. Examples of the reaction solvent include γ-butyrolactone (GBL), dimethyl sulfoxide, N,N-dimethylacetoacetamide, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N,N-dimethylacetamide.

[0069] When a thermal imidization method is used in the production of (A) polyimide resin, an azeotropic solvent may be used to promote the imidization reaction. The azeotropic solvent is not particularly limited as long as it is a solvent that forms an azeotrope with water, and examples thereof include toluene, ethyl acetate, N-dicyclohexylpyrrolidone, orthodichlorobenzene, xylene, and benzene.

[0070] The polyimide resin (A) may be purified by a method described in Patent Document 2 (JP 2012-194520 A) or the like. Examples of purification methods include a method in which a solution of the polyimide resin (A) is dropped into water to remove unreacted materials by reprecipitation, a method in which a condensing agent insoluble in the reaction solvent is removed by filtration, and a method in which the catalyst is removed using an ion exchange resin. After these purification steps, the polyimide resin (A) may be dried by a known method and isolated in a powder state.

[0071] (B) Tetrazole Compound (Component B) The (B) tetrazole compound used in this embodiment has an acid dissociation constant (pKa) of 1.3 or more and 4.1 or less. By including such a (B) tetrazole compound, copper adhesion and copper migration suppression effects are obtained, and resolution is also improved. From the viewpoint of copper adhesion and copper migration suppression effects, the pKa is preferably 2.0 or more and 3.6 or less. For pKa, a value calculated using Advanced Chemistry Software V11.02 (1994-2018 ACD / Labs) is used.

[0072] The reason why the use of such a (B) tetrazole compound exhibits the above-mentioned effects is unclear and is not limited by theory, but the present inventors believe as follows. It is believed that the (B) tetrazole compound exerts its effects by coordinating to the copper of the substrate. In this case, it is presumed that if the pKa of the (B) tetrazole compound is 4.1 or less, the interaction with the (A) polyimide resin is strengthened, improving copper adhesion. On the other hand, if the pKa of the (B) tetrazole compound is 1.3 or more, the interaction with the (A) polyimide resin is not too strong, and unnecessary oxidation of the copper surface of the substrate is not caused, thereby suppressing copper migration and improving resolution. Therefore, it is presumed that the moderate acidity of the (B) tetrazole compound allows for both excellent adhesion to copper and the copper migration suppression effect, while also improving resolution.

[0073] Examples of the (B) tetrazole compound having a pKa of 1.3 or more and 4.1 or less include, but are not limited to, 1H-tetrazole-5-carboxylic acid (also known as 1H-tetrazole-5-formic acid), 1H-tetrazole-5-acetic acid, 1H-tetrazole-5-propionic acid, 1H-tetrazole-1-acetic acid, ethyl 1H-tetrazole-5-carboxylate (also known as ethyl 1H-tetrazole-5-formate), methyl 1H-tetrazole-5-acetate, 2-[4-(1H-1,2,3,4-tetrazol-5-yl)phenyl]acetic acid, 2-(2H-tetrazol-5-yl)butanedioic acid, 2,2-bis(2-2H-tetrazol-5-yl)ethyl)propanedioic acid, and 4-(1H-tetrazol-5-yl)benzoic acid. Note that when these compounds are added to the photosensitive resin composition, they may be in the form of a hydrate.

[0074] Furthermore, from the viewpoints of copper adhesion, copper migration suppression effect, and resolution, the (B) tetrazole compound is preferably a compound having a carboxyl group. Examples include, but are not limited to, 1H-tetrazole-5-carboxylic acid (also known as 1H-tetrazole-5-formic acid), 1H-tetrazole-5-acetic acid, 1H-tetrazole-5-propionic acid, 1H-tetrazole-1-acetic acid, 2-[4-(1H-1,2,3,4-tetrazol-5-yl)phenyl]acetic acid, 2-(2H-tetrazol-5-yl)butanedioic acid, 2,2-bis(2-2H-tetrazol-5-yl)ethyl)propanedioic acid, and 4-(1H-tetrazol-5-yl)benzoic acid. When these compounds are added to the resin composition, they may be in the form of hydrates.

[0075] Furthermore, from the viewpoints of copper adhesion, copper migration suppression effect, and resolution, it is preferable that the tetrazole compound (B) is represented by the following general formula (1): {In formula (1), R １ represents a carboxyl group or the following general formula (2): and R ２ is a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with at least one of a halogen atom, a hydroxyl group, an alkoxysilyl group, and an amino group.２ is not particularly limited as long as it is a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with at least one of a halogen atom, a hydroxyl group, an alkoxysilyl group, and an amino group, but examples thereof include a branched or linear alkylene group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, or a structure in which these are linked together. These may have a substituent such as a halogen atom, a hydroxyl group, an alkoxysilyl group, or an amino group. Examples of compounds represented by general formula (1) include, but are not limited to, 1H-tetrazole-5-carboxylic acid (also known as 1H-tetrazole-5-formic acid), 1H-tetrazole-5-acetic acid, 1H-tetrazole-5-propionic acid, 2-[4-(1H-1,2,3,4-tetrazol-5-yl)phenyl]acetic acid, and 4-(1H-tetrazol-5-yl)benzoic acid. More preferred are 1H-tetrazole-5-acetic acid and 4-(1H-tetrazol-5-yl)benzoic acid.

[0076] When the (B) tetrazole compound is a compound represented by the above formula (1), excellent copper adhesion, copper migration suppression effect, and copper void suppression effect can be obtained. The reason for this is unclear and not bound by theory, but it is thought that the unshared electron pair associated with the nitrogen atom in the tetrazole acts on copper and is unevenly distributed at the copper interface, and the constituent atoms of the carboxylic acid in the tetrazole compound form hydrogen bonds with the (A) polyimide precursor, thereby allowing the (A) polyimide resin to interact with copper and improve copper adhesion. The fact that the N at the 1-position of the tetrazole compound is bonded to hydrogen also makes it easier for the (B) tetrazole compound to coordinate to copper. In addition, it is thought that the uneven distribution of the (B) tetrazole compound at the copper interface strongly suppresses oxidation reactions at the copper interface, thereby suppressing copper migration and copper voids. In addition, in general formula (2), R ２ is a hydrocarbon group having 1 to 10 carbon atoms, the boiling point of the molecule is high and the tetrazole compound (B) is unlikely to volatilize during pre-baking when the resin composition is coated on a substrate, so that it can remain in the film, and furthermore, it is likely to move within the film and be unevenly distributed at the interface. Therefore, it is presumed that this is more effective in improving copper adhesion and suppressing copper migration.

[0077] The content of the (B) tetrazole compound is preferably 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, and even more preferably 0.2 parts by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the (A) polyimide precursor and / or polyimide resin. The content is preferably 0.01 parts by mass or more from the viewpoint of copper adhesion, and 20 parts by mass or less from the viewpoint of copper migration suppression and storage stability of the resin composition.

[0078] (C) Heterocyclic Compound (Component C) The photosensitive resin composition of the present disclosure contains a (C) heterocyclic compound other than the (B) component. By including the (C) heterocyclic compound in addition to the (B) component, copper adhesion, copper migration suppression ability, and resolution are improved. Among the (C) heterocyclic compounds, heterocyclic compounds containing oxygen or nitrogen are preferred, and heterocyclic compounds containing nitrogen are particularly preferred. Examples of the (C) heterocyclic compound include azole compounds. Examples of the azole compound include indazole and its derivatives, imidazole and its derivatives, triazole and its derivatives, and tetrazole and its derivatives other than the (B) tetrazole compound.

[0079] Examples of indazole and its derivatives include 1H-indazole, 5-aminoindazole, 6-aminoindazole, 1-benzyl-3-hydroxy-1H-indazole, 5-bromoindazole, 6-bromoindazole, 6-hydroxyindazole, 3-carboxyindazole, and 5-nitroindazole.

[0080] Examples of imidazole compounds and derivatives thereof include imidazole, undecylimidazole, benzimidazole, 5-carboxybenzimidazole, 6-bromobenzimidazole, 5-chlorobenzimidazole, 2-hydroxybenzimidazole, 2-(1-hydroxymethyl)benzimidazole, 2-methylbenzimidazole, 5-nitrobenzimidazole, 2-phenylbenzimidazole, 2-aminobenzimidazole, 5-aminobenzimidazole, and 5-amino-2-mercaptobenzimidazole.

[0081] Examples of triazole and derivatives thereof include 1,2,3-triazole, 1,2,4-triazole, 3-mercaptotriazole, 3-amino-5-mercaptotriazole, benzotriazole, 1H-benzotriazole-1-acetonitrile, 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole, 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole, 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole, 1H-benzotriazole-1-methanol, 5-methyl-1H-benzotriazole, 1-hydroxybenzotriazole, 5-carboxybenzotriazole, 5-aminobenzotriazole, 5-chlorobenzotriazole, and 5-nitrobenzotriazole.

[0082] (B) Examples of tetrazoles and derivatives thereof other than tetrazole compounds include 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 5-benzyl-1H-tetrazole, 5-amino-1-methyltetrazole, 5-(4-methylphenyl)-1H-tetrazole, 1-methyl-5-ethyl-1H-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, and 1-(4-hydroxyphenyl)-5-mercapto-1H-tetrazole.

[0083] Furthermore, among the heterocyclic compounds (C), from the viewpoint of copper adhesion during high-temperature curing and copper migration suppression ability, fused ring compounds are preferred, and in particular, compounds containing nitrogen in each of the fused rings are preferred. Examples of fused ring compounds include, but are not limited to, 7-methyl-2,4-dioxo-1,2,3,4-tetrahydropyrido[2,3-d]pyrimidine-5-carboxylic acid, xanthopterin, allopurinol, 4-[2-(2-amino-4,7-dihydro-4-oxo-3H-pyrrolo[2,3-d]pyrimidin-5-yl)ethyl]benzoic acid, pyrido[2,3-d]pyrimidin-4-ol, 1H,2H,3H,4H-pyrido[2,3-d]pyrimidine-2,4-dione, pteridin-4-ol, lumazine, 7-phenyl-pteridin-4-ol, pterin-6-carboxylic acid, 6-amino-1H-pyrazolo[3,4-d]pyri pyrimidin-4(7H)-one, 1H-pyrazolo[3,4-d]pyrimidine-4,6(2H,5H)-dione, 7-deazahypoxanthine, 7-deazaxanthine, 2-amino-4-oxo-4,7-dihydro-1H-pyrrolo[2,3-d]pyrimidine-5-carboxylic acid, 6-nitro-3H-pyrido[2,3-d]pyrimidine-4-one, 7-chloropyrido[2,3-d]pyrimidine-2,4(1H,3H)-dione, 6-(trifluoromethyl)-1H-pyrazolo[3,4-d]pyrimidin-4-ol, and 5-(4-iodophenyl)-1H-pyrrolo[2,3-d]pyrimidine-2,4(3H,7H)-dione. Purine derivatives are also a type of fused ring compound. The reason for this is unclear, and without being bound by theory, it is thought that, since the heterocyclic compound (C) is a fused ring compound, the heterocyclic compound (C) is less likely to decompose or volatilize even after the high-temperature curing step that is performed when the photosensitive resin composition is made into a cured film, and remains in the cured film, thereby exhibiting copper adhesion and copper migration suppression ability.

[0084] Furthermore, among the heterocyclic compounds (C), it is preferable to contain a purine derivative, particularly from the viewpoint of copper adhesion and copper migration inhibition at high temperatures, and further from the viewpoint of solubility in the photosensitive resin composition. Specific examples of the purine derivative include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 6-methoxypurine, N6-benzoyladenine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, and guanine. Anine oxime, N-(2-hydroxyethyl)adenine, 8-aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine guanosine, 8-azaxanthine, 8-azahypoxanthine, 2-acetamido-6-hydroxypurine, N-(6-oxo-6,9-dihydro-1H-purin-2-yl)benzamide, ganciclovir, guanosine, 3'-amino-2',3'-dideoxyguanosine, penciclovir, N2-pivaloylguanine, 2-[2-isobutyramido-6-oxo-1H-purin-9(6H)-yl]acetic acid, N-acetyl-di-O-acetylganciclovir Examples thereof include clovir, N2-isobutyrylguanosine, 9-ethylguanine, 2-amino-9-phenyl-1H-purin-6(9H)-one, N-(6-oxo-6,7-dihydro-1H-purin-2-yl)isobutyramide, N2,9-diacetylguanine, 9-[(2-acetoxyethoxy)methyl]-N2-acetylguanine, N2-acetylacyclovir, N2-isobutyryl-2'-deoxyguanosine, and derivatives thereof.

[0085] The heterocyclic compound (C) is represented by the following general formula (3): {In the formula, R ３ is an amino group or an alkoxy group having 1 to 6 carbon atoms, and R ４is a hydrogen atom or an amino group which may be substituted with a plurality of organic groups having 1 to 10 carbon atoms, and R ５ is a hydrogen atom or an organic group having 1 to 10 carbon atoms.}, a compound represented by the following general formula (4): {In the formula, R ６ is a hydrogen atom or an amino group which may be substituted with a plurality of organic groups having 1 to 10 carbon atoms, and R ７ is a hydrogen atom or an organic group having 1 to 10 carbon atoms.}, a compound represented by the following general formula (5): {In the formula, R ８ is an amino group or an alkoxy group having 1 to 6 carbon atoms, and R ９ is a hydrogen atom or an amino group which may be substituted with a plurality of organic groups having 1 to 10 carbon atoms, and R １０ is a hydrogen atom or an organic group having 1 to 10 carbon atoms.}, or a compound represented by the following general formula (6): {In the formula, R １１ is a hydrogen atom or an amino group which may be substituted with a plurality of organic groups having 1 to 10 carbon atoms, and R １２ is a hydrogen atom or an organic group having 1 to 10 carbon atoms.} is more preferred from the viewpoints of copper adhesion, copper migration inhibition, and solubility in the photosensitive resin composition.

[0086] R in the formula ３ and R ８ is not particularly limited as long as it is an amino group or an alkoxy group having 1 to 6 carbon atoms, but is more preferably an amino group or an alkoxy group having 1 to 3 carbon atoms from the viewpoints of copper adhesion, copper migration inhibition, and solubility in the photosensitive resin composition.

[0087] Also, R in the formula ４ , R ６ , R ９ and R １１ is not particularly limited as long as it is a hydrogen atom or an amino group which may be substituted with a plurality of organic groups having 1 to 10 carbon atoms. ４ , R ６ , R ９ and R １１The organic group substituting the amino group in the formula may be a branched or linear alkyl group, an aromatic or carboxyl group, or may be substituted with a functional group such as an acetyl group or an acetoxy group. From the viewpoints of copper adhesion, copper migration suppression, and solubility in the photosensitive resin composition, the R ４ , R ６ , R ９ and R １１ is preferably an amino group or an amino group in which one hydrogen atom is substituted with an organic group having 1 to 10 carbon atoms, and more preferably an amino group in which one hydrogen atom is substituted with an organic group having 1 to 6 carbon atoms and a carbonyl group.

[0088] Also, R ５ , R ７ , R １０ and R １２ is not particularly limited as long as it is a hydrogen atom or an organic group having 1 to 10 carbon atoms, but may be a branched or linear alkyl group, an aromatic group, or a carboxyl group, and may be substituted with a functional group such as a hydroxyl group, a carbonyl group, an amino group, an amide group, a nitro group, or a halogen group. From the viewpoints of copper adhesion, copper migration suppression, and solubility in the photosensitive resin composition, R ５ , R ７ , R １０ and R １２ is preferably a hydrogen atom or an organic group having 1 to 10 carbon atoms and having a carbonyl group and / or a hydroxyl group, and more preferably a hydrogen atom or an organic group having 1 to 6 carbon atoms and having a carbonyl group.

[0089] By including a compound represented by the above formula (3), (4), (5), or (6), excellent copper adhesion can be obtained not only by low-temperature curing (curing at 200°C or less in the present disclosure) but also by high-temperature curing. Furthermore, copper migration suppression effects and copper void suppression effects can be obtained not only by high-temperature curing but also by low-temperature curing. In the present disclosure, the high-temperature curing temperature refers to a temperature of 250°C or higher.

[0090] The reason for this is unclear, and without being bound by theory, it is believed that when the photosensitive resin composition of this embodiment contains a purine compound represented by the above formula (3), (4), (5), or (6), the unshared electron pair associated with the nitrogen atom in the purine skeleton acts on copper and is unevenly distributed at the copper interface, and the constituent atoms of the primary or secondary amine form hydrogen bonds with the (A) polyimide precursor or polyimide, thereby allowing the (A) polyimide resin to interact with copper and improve copper adhesion. Furthermore, it is believed that the uneven distribution of the purine compound at the copper interface strongly suppresses oxidation reactions at the copper interface, thereby suppressing copper migration and copper voids. Furthermore, as described above, by having these structures, it is believed that the (C) heterocyclic compound is less likely to decompose or volatilize, even after undergoing a high-temperature curing process when the photosensitive resin composition is formed into a cured film, and remains in the cured film, thereby exhibiting copper adhesion and copper migration suppression capabilities.

[0091] Examples of the compound represented by general formula (3) include adenine, 2,6-diaminopurine, 6-methoxypurine, 9-methyladenine, 9-(2-hydroxyethyl)adenine, and 9-ethyl-N2-methyl-9H-purine-2,6-diamine.

[0092] Examples of the compound represented by general formula (4) include guanine, hypoxanthine, N-methylguanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-acetamido-6-hydroxypurine, N-(6-oxo-6,9-dihydro-1H-purin-2-yl)benzamide, ganciclovir, guanosine, 3'-amino-2',3'-dideoxyguanosine, penciclovir, 9-ethylguanine, N2-pivaloylguanine, 2-[2-isobutylamido-6 -oxo-1H-purin-9(6H)-yl]acetic acid, N-acetyl-di-O-acetylganciclovir, N2-isobutyrylguanosine, 2-amino-9-phenyl-1H-purin-6(9H)-one, N-(6-oxo-6,7-dihydro-1H-purin-2-yl)isobutyramide, N2,9-diacetylguanine, 9-[(2-acetoxyethoxy)methyl]-N2-acetylguanine, N2-acetylacyclovir, and N2-isobutyryl-2'-deoxyguanosine.

[0093] Examples of the compound represented by general formula (5) include 8-azaadenine, 3H-1,2,3-triazolo[4,5-d]pyrimidine-5,7-diamine, 3-ethyl-1,2,3-triazolo[4,5-d]pyrimidine-5,7-diamine, and N5-methyl-3H-1,2,3-triazolo[4,5-d]pyrimidine-5,7-diamine.

[0094] Examples of the compound represented by the general formula (6) include 8-azaguanine and 8-azahypoxanthine.

[0095] Among the compounds represented by general formula (4), the heterocyclic compound (C) is preferably a compound represented by the following general formula (7): {In the formula, R １３ is an organic group having 1 to 10 carbon atoms, and R １４ is a hydrogen atom or an organic group having 1 to 10 carbon atoms.} is more preferred from the viewpoints of copper adhesion and copper migration suppression ability during high-temperature curing, and solubility in the photosensitive resin composition.

[0096] R in the formula １３is not particularly limited as long as it is an organic group having 1 to 10 carbon atoms, but may be a branched or linear alkyl group, an aromatic or carboxyl group, or may be substituted with a functional group such as an acetyl group or an acetoxy group. From the viewpoints of copper adhesion, copper migration suppression, and solubility in the photosensitive resin composition, it is preferably an organic group having 1 to 6 carbon atoms and a carbonyl group. １４ is not particularly limited as long as it is a hydrogen atom or an organic group having 1 to 10 carbon atoms, but may be a branched or linear alkyl group, an aromatic group, or a carboxyl group, and may be substituted with a functional group such as a hydroxyl group, a carbonyl group, an amino group, an amide group, a nitro group, or a halogen group. From the viewpoints of copper adhesion, copper migration suppression, and solubility in the photosensitive resin composition, R １４ is preferably a hydrogen atom or an organic group having 1 to 10 carbon atoms and having a carbonyl group and / or a hydroxyl group, and more preferably a hydrogen atom or an organic group having 1 to 6 carbon atoms and having a carbonyl group.

[0097] Examples of the compound represented by formula (7) include N-methylguanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-acetamido-6-hydroxypurine, N-(6-oxo-6,9-dihydro-1H-purin-2-yl)benzamide, N2-pivaloylguanine, 2-[2-isobutylamido-6-oxo-1H-purin-9(6H)-yl]acetic acid, N-acetyl-di-O-acetylganciclovir, N2-isobutyrylguanosine, and N- Examples include (6-oxo-6,7-dihydro-1H-purin-2-yl)isobutyramide, N2,9-diacetylguanine, 9-[(2-acetoxyethoxy)methyl]-N2-acetylguanine, N2-acetylacyclovir, and N2-isobutyryl-2'-deoxyguanosine. From the viewpoint of copper adhesion, 2-acetamido-6-hydroxypurine, N-(6-oxo-6,7-dihydro-1H-purin-2-yl)isobutyramide, and 9-diacetylguanine are more preferred.

[0098] The content of the heterocyclic compound (C) is preferably 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, and even more preferably 0.2 parts by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the polyimide precursor (A) and / or polyimide resin (B). The content is preferably 0.01 parts by mass or more from the viewpoint of copper adhesion, and is preferably 20 parts by mass or less from the viewpoints of copper migration suppression and storage stability of the photosensitive resin composition.

[0099] The total content of the (B) tetrazole compound and the (C) heterocyclic compound is preferably 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the (A) component. More preferably, the total content of the (B) tetrazole compound and the (C) heterocyclic compound is 0.5 parts by mass or more and 5 parts by mass or less per 100 parts by mass of the (A) component. The total content is preferably 0.1 parts by mass or more to achieve sufficient effects in terms of copper adhesion, copper migration inhibition, and resolution, and is preferably 10 parts by mass or less from the viewpoints of copper adhesion, copper migration inhibition, and solubility in the photosensitive resin composition. The reason for this is unclear and not limited by theory, but it is presumed that with this total content, a brittle layer is less likely to form between the copper of the substrate and the photosensitive resin layer, resulting in good copper adhesion, and the ionic components in the photosensitive resin layer do not increase more than necessary, resulting in good copper migration inhibition. Furthermore, it is believed that the components (B) and (C) are unevenly distributed at the copper interface of the substrate, but the amount of uneven distribution becomes appropriate, and it is believed that the resolution also becomes good.

[0100] Furthermore, in order to improve copper adhesion, copper migration suppression effect, and resolution in a well-balanced manner, it is preferable that the ratio of the content of the (B) tetrazole compound to the content of the (C) heterocyclic compound (the content of the (B) tetrazole compound relative to the content of the (C) heterocyclic compound) satisfies the following formula (9): 0.1≦content (parts by mass) of the (B) tetrazole compound / content (parts by mass) of the (C) heterocyclic compound≦10 (9). From the viewpoint of resolution and copper migration suppression effect, the content (parts by mass) of the (B) tetrazole compound / content (parts by mass) of the (C) heterocyclic compound is preferably 0.1 or more, and from the viewpoint of copper adhesion after high-temperature curing, it is preferably 10 or less. More preferably, the content (parts by mass) of the (B) tetrazole compound / content (parts by mass) of the (C) heterocyclic compound is 1 or more and 5 or less.

[0101] (D) Photopolymerization initiator (Component D) Examples of the (D) photopolymerization initiator include photoacid generators and photoradical polymerization initiators, but from the viewpoint of improving photosensitivity and suppressing copper migration, photoradical polymerization initiators are preferred, and examples thereof include benzophenone derivatives such as benzophenone, o-benzoyl methyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexyl phenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzil derivatives such as benzil, benzil dimethyl ketal, and benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin and benzoin methyl ether; Preferred examples of the photoradical polymerization initiator include, but are not limited to, oximes such as 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, and 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime; N-arylglycines such as N-phenylglycine; peroxides such as benzoyl perchloride; aromatic biimidazoles; and titanocenes. Of the above photoradical polymerization initiators, oximes (oxime initiators) are preferred, particularly in terms of photosensitivity. In one embodiment, from the viewpoint of photosensitivity, the photoradical polymerization initiator is preferably an oxime initiator.Preferred examples of the photoacid generator include, but are not limited to, α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide, diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, and naphthoquinonediazide-4-sulfonic acid esters.

[0102] The content of the (D) photopolymerization initiator is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 8 parts by mass or less, and even more preferably 1 part by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the (A) polyimide precursor and / or polyimide resin. The content is preferably 0.1 parts by mass or more from the viewpoint of photosensitivity or patterning ability, and is preferably 20 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the photosensitive resin composition.

[0103] (E) Solvent (Component E) The photosensitive resin composition of the present embodiment may contain (E) a solvent. Examples of the (E) solvent include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and alcohols. Examples of the (E) solvent include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide (DMSO), tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, Methyl lactate, butyl lactate, γ-butyrolactone (GBL), propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene, and the like can be used. Among these, from the viewpoints of the solubility of the resin, the stability of the photosensitive resin composition, and the adhesion to the substrate, 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, benzyl alcohol, phenyl glycol, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, and tetrahydrofurfuryl alcohol are preferred.

[0104] Among these solvents, those that completely dissolve the polyimide precursor (A) are particularly preferred, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, γ-butyrolactone, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide. In particular, γ-butyrolactone and 3-methoxy-N,N-dimethylpropanamide are preferred from the viewpoint of in-plane uniformity when the photosensitive resin composition is applied onto a substrate.

[0105] The (E) solvent may be used alone or in combination of two or more types, but from the viewpoint of appropriately adjusting the stability of the photosensitive resin composition, two or more types are preferably used. When the photosensitive resin composition of the present embodiment contains two or more (E) solvents, from the viewpoint of in-plane uniformity, it is preferable that 50% by weight or more of the (E) solvents be either γ-butyrolactone or 3-methoxy-N,N-dimethylpropanamide, and it is more preferable that the (E) solvent contains γ-butyrolactone.

[0106] In the photosensitive resin composition of the present embodiment, the content of the (E) solvent is preferably in the range of 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, relative to 100 parts by mass of the (A) polyimide precursor and / or polyimide resin.

[0107] (F) Photopolymerizable Monomer (Component F) The photosensitive resin composition of the present embodiment may further contain (F) a photopolymerizable monomer. Use of (F) a photopolymerizable monomer promotes crosslinking of the photosensitive resin composition upon exposure, improving resolution, and further reducing the moisture permeability of the cured film, thereby providing an effect of inhibiting copper migration.

[0108] The photosensitive resin composition of this embodiment preferably contains 5 to 150 parts by mass of the (F) photopolymerizable monomer per 100 parts by mass of the (A) polyimide precursor and / or polyimide resin. To achieve good resolution, the photosensitive resin composition of this embodiment preferably contains 5 parts by mass or more of the (F) photopolymerizable monomer, more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more. On the other hand, if the (F) photopolymerizable monomer is contained in an excessive amount, copper adhesion may be reduced. While the reason for this is unclear and not limited by theory, it is presumed that a high amount of the (F) photopolymerizable monomer generates a brittle layer between the copper layer and the photosensitive resin layer, thereby reducing copper adhesion. The upper limit, which can be arbitrarily combined with the above lower limit, is preferably 150 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 50 parts by mass or less, from the viewpoint of copper adhesion.

[0109] The photopolymerizable monomer (F) is not particularly limited as long as it is a compound that undergoes a radical polymerization reaction with the photopolymerization initiator (D) and the thermal polymerization initiator (D). However, it is preferably a (meth)acrylic compound, and examples thereof include compounds represented by the following general formula (52): {In formula (52), X ３ is an organic group having 1 to 200 carbon atoms, and L ４ , L ５ and L ６ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. ３ is an integer from 1 to 10.

[0110] (F) Photopolymerizable monomers include, but are not limited to, tris-(2-acryloxyethyl)isocyanurate, mono- or diacrylates and methacrylates of ethylene glycol or polyethylene glycol such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, mono- or diacrylates and methacrylates of propylene glycol or polypropylene glycol, mono-, di-, or triacrylates and methacrylates of glycerol, cyclohexane diacrylate and dimethacrylate, diacrylate and dimethacrylate of 1,4-butanediol, diacrylate and dimethacrylate of 1,6-hexanediol, diacrylate and dimethacrylate of neopentyl glycol, mono- or diacrylate and methacrylate of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and derivatives thereof, methacrylamide and derivatives thereof, Examples include compounds such as trimethylolpropane triacrylate and methacrylate, di-, tri-, or tetraacrylate and methacrylate of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds.

[0111] More specifically, the following general formulas (53) and (54): Examples of the compound include, but are not limited to, compounds represented by the following formula:

[0112] In the present disclosure, when the number of radical polymerizable groups in the (F) photopolymerizable monomer is one, it is referred to as monofunctional; when the number is two or more, it is referred to as x-functional group according to the number x of radical polymerizable groups, but difunctional or higher functional groups may be collectively referred to as polyfunctional. The (F) photopolymerizable monomer may be monofunctional or may be difunctional or higher. From the viewpoint of suppressing copper migration, the (F) photopolymerizable monomer is preferably trifunctional or higher, more preferably tetrafunctional or higher, and even more preferably hexafunctional or higher. On the other hand, from the viewpoint of copper adhesion, the (F) photopolymerizable monomer is preferably decafunctional or lower.

[0113] The lower limit of the weight-average molecular weight of the (F) photopolymerizable monomer is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more. The upper limit of the weight-average molecular weight of the (F) photopolymerizable monomer is preferably 1000 or less, and more preferably 800 or less. By setting the weight-average molecular weight of the (F) photopolymerizable monomer within the above range, resolution is improved.

[0114] The photopolymerizable monomer (F) may contain a hydroxyl group or a urea group in the molecule. Examples of the photopolymerizable monomer (F) having a hydroxyl group in the molecule include those represented by the following general formula (55): {In the formula, X ４ is an organic group having 1 to 200 carbon atoms, and L ７ , L ８ and L ９ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. ４ is an integer from 1 to 10, and n ５ is an integer of 1 to 10. In the above formula (55), L ７ is a hydrogen atom or a methyl group, and L ８ and L ９ is preferably a hydrogen atom from the viewpoint of radical reactivity.

[0115] More specifically, the photopolymerizable monomer (F) having a hydroxyl group in the molecule includes a compound represented by the following general formula (56): Examples include, but are not limited to, compounds represented by the formula: (F) Having a hydroxyl group in the molecular structure of the photopolymerizable monomer (F), improves copper adhesion. The number of hydroxyl groups in the molecular structure of the photopolymerizable monomer (F) is preferably one or more, and more preferably two or more. The upper limit of the number of hydroxyl groups in the molecular structure of the photopolymerizable monomer (F) is preferably 10 or less, more preferably six or less, and even more preferably three or less. By setting the number of hydroxyl groups in the molecular structure of the photopolymerizable monomer (F) within the above range, copper adhesion to the substrate improves.

[0116] The photopolymerizable monomer (F) having a urea group in the molecule is represented by the following general formula (57): {In the formula, X ５, X ６ , X ７ and X ８ are each independently a hydrogen atom, a monovalent organic group containing a group represented by the following general formula (58), or a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and X ５ , X ６ , X ７ and X ８ At least one of the above is a monovalent organic group containing a group represented by the following general formula (58):} Examples of the heteroatom include an oxygen atom, a nitrogen atom, a phosphorus atom, and a sulfur atom. {In the formula, L １０ , L １１ and L １２ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. １０ is a hydrogen atom or a methyl group, and L １１ and L １２ is preferably a hydrogen atom from the viewpoint of radical reactivity.

[0117] In formula (57), X ５ , X ６ , X ７ and X ８ When X is a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, it more preferably contains an oxygen atom from the viewpoint of resolution. ５ , X ６ , X ７ and X ８ The number of carbon atoms in X in formula (57) is not particularly limited as long as it is 1 to 20, but from the viewpoint of heat resistance, the number of carbon atoms is preferably 1 to 10, and more preferably 3 to 10. ５ , X ６ , X ７ and X ８ may be bonded to each other to form a cyclic structure, but from the viewpoint of chemical resistance, it is preferable that they do not have a cyclic structure. ５ , X ６ , X ７ and X ８ When these groups are bonded to each other to form a cyclic structure, the degree of freedom of the bond angle of the urea group is lost, which tends to make it difficult to form a strong hydrogen bond.

[0118] In terms of forming hydrogen bonds with other molecules, X ５ , X ６ , X ７ and X ８ On the other hand, from the viewpoint of solubility, it is preferable that at least one of X is a hydrogen atom. ５ , X ６ , X ７ and X ８ Specifically, the number of hydrogen atoms in the following general formula (59): Examples include compounds represented by the following formula:

[0119] The photopolymerizable monomer (F) having at least one hydroxyl group and at least one urea group in the molecule is, for example, a compound represented by the following general formula (60): {In the formula, X ９ , X １０ , X １１ and X １２ are each independently a hydrogen atom, a monovalent organic group containing a group represented by the following general formula (61), or a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and X ９ , X １０ , X １１ and X １２ at least one of the following is a monovalent organic group containing a group represented by the following general formula (61): ９ , X １０ , X １１ and X １２ At least one of them is a hydroxyl group. {In the formula, L １３ , L １４ and L １５ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. １３ is a hydrogen atom or a methyl group, and L １４ and L １５ is preferably a hydrogen atom from the viewpoint of radical reactivity.

[0120] In formula (60), X ９ , X １０ , X １１ and X １２When X is a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, it is more preferable that X contains an oxygen atom from the viewpoint of resolution. ９ , X １０ , X １１ and X １２ The number of carbon atoms in X in formula (60) is not limited as long as it is 1 to 20, but from the viewpoint of heat resistance, the number of carbon atoms is preferably 1 to 10, and more preferably 3 to 10. ９ , X １０ , X １１ and X １２ may be bonded to each other to form a cyclic structure, but from the viewpoint of chemical resistance, it is preferable that they do not have a cyclic structure. ９ , X １０ , X １１ and X １２ When these groups are bonded to each other to form a cyclic structure, the degree of freedom of the bond angle of the urea group is lost, which tends to make it difficult to form a strong hydrogen bond.

[0121] In terms of forming hydrogen bonds with other molecules, X ９ , X １０ , X １１ and X １２ On the other hand, from the viewpoint of solubility, it is preferable that at least one of X is a hydrogen atom. ９ , X １０ , X １１ and X １２ Preferably, two or less of the above are hydrogen atoms.

[0122] Specifically, the photopolymerizable monomer (F) having at least one hydroxyl group and at least one urea group in the molecule is represented by the following general formula (62): Examples include compounds represented by the following formula:

[0123] The photopolymerizable monomer (F) having a urea group can be produced by, for example, reacting an isocyanate compound having a radical polymerizable group with an amine-containing compound, although the method for producing the photopolymerizable monomer is not particularly limited. When the amine-containing compound contains a functional group such as a hydroxyl group that can react with isocyanate, a part of the isocyanate compound may contain a compound that has reacted with the functional group such as a hydroxyl group.

[0124] The photopolymerizable monomer (F) may be used singly or in a mixture of two or more. When a mixture of two or more photopolymerizable monomers (F) is used, from the viewpoint of controlling the crosslink density, the number of photopolymerizable monomers (F) used is preferably six or less, and more preferably four or less.

[0125] When a mixture of multiple (F) photopolymerizable monomers is used, it is preferable that at least one of the multiple (F) photopolymerizable monomers has a different number of functional groups. When three or more (F) photopolymerizable monomers are used, it is sufficient that at least one of them has a different number of functional groups, but it is preferable that all of the (F) photopolymerizable monomers have different numbers of functional groups. When a plurality of (F) photopolymerizable monomers are used, it is preferable that at least one of them contains a monofunctional photopolymerizable monomer from the viewpoint of breaking elongation.

[0126] (G) Thermal Crosslinking Agent (Component G) In order to suppress copper migration in the cured film, the photosensitive resin composition of this embodiment may optionally contain (G) a thermal crosslinking agent.

[0127] The (G) thermal crosslinking agent is not particularly limited as long as it forms a crosslinked product when the relief pattern formed using the photosensitive resin composition of this embodiment is heat-cured, but is preferably one that can form a crosslinked product by reacting the (A) polyimide precursor and / or polyimide resin with the (G) thermal crosslinking agent, between the (G) thermal crosslinking agents, or between the (G) thermal crosslinking agent and other components. The reaction temperature during crosslinking is preferably 150° C. or higher.

[0128] Examples of the (G) thermal crosslinking agent include an alkoxymethyl compound, an epoxy compound, an oxetane compound, a bismaleimide compound, an allyl compound, and a blocked isocyanate compound. From the viewpoint of suppressing cure shrinkage, the (G) thermal crosslinking agent preferably contains a nitrogen atom.

[0129] Examples of the alkoxymethyl compound include, but are not limited to, compounds represented by the following general formula (63):

[0130] Commercially available alkoxymethyl compounds include alkylated urea resin (product name: MX290, manufactured by Nikalac Co., Ltd.) and 1,3,4,6-tetrakis(methoxymethyl)glycoluril (product name: MX270, manufactured by Nikalac Co., Ltd.).

[0131] Examples of epoxy compounds include 4-hydroxybutyl acrylate glycidyl ether, epoxy compounds containing a bisphenol A group, and hydrogenated bisphenol A diglycidyl ether. For example, Epolite 4000 (product name, manufactured by Kyoeisha Chemical Co., Ltd.) can be suitably used.

[0132] 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 Examples of suitable oxetane derivatives include 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene, ...

[0133] Examples of the bismaleimide compound include 1,2-bis(maleimide)ethane, 1,3-bis(maleimide)propane, 1,4-bis(maleimide)butane, 1,5-bis(maleimide)pentane, 1,6-bis(maleimide)hexane, 2,2,4-trimethyl-1,6-bis(maleimide)hexane, N,N'-1,3-phenylenebis(maleimide), 4-methyl-N,N'-1,3-phenylenebis(maleimide), N,N'-1,4-phenylenebis(maleimide), 3-methyl-N,N'-1,4-phenylenebis(maleimide), 4,4'-bis(maleimide)diphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-bis(maleimide)diphenylmethane, and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane.

[0134] Examples of the allyl compound include allyl alcohol, allyl anisole, allyl benzoate, allyl cinnamate, N-allyloxyphthalimide, allylphenol, allyl phenyl sulfone, allyl urea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl isocyanurate, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallylamine, triallyl 1,3,5-benzenetricarboxylate, triallyl trimellitate, triallyl phosphate, triallyl phosphite, and triallyl citrate.

[0135] Examples of blocked isocyanate compounds include hexamethylene diisocyanate-based blocked isocyanates (for example, Asahi Kasei Corporation, trade names: Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B, and WM44-L70G; Mitsui Chemicals, Inc., trade name: Takenate B-882N; Baxenden, trade names: 7960, 7961, 7982, 7991, and 7992); tolylene diisocyanate-based blocked isocyanates (for example, Mitsui Chemicals, Inc., trade name: Takenate B-830); Examples of such blocked isocyanates include 4,4'-diphenylmethane diisocyanate-based blocked isocyanates (e.g., Mitsui Chemicals, Inc., trade name: Takenate B-815N; Daiei Sangyo Co., Ltd., trade names: Bronate PMD-OA01 and PMD-MA01), 1,3-bis(isocyanatomethyl)cyclohexane-based blocked isocyanates (e.g., Mitsui Chemicals, Inc., trade name: Takenate B-846N; Tosoh Corporation, trade names hereinafter: Coronate BI-301, 2507, and 2554); and isophorone diisocyanate-based blocked isocyanates (e.g., Baxenden, trade names hereinafter: 7950, 7951, and 7990).

[0136] Among these, alkoxymethyl compounds are preferred from the viewpoint of copper adhesion. (G) The thermal crosslinking agent may be used alone or in combination of two or more.

[0137] The content of the (G) thermal crosslinking agent in the photosensitive resin composition of the present disclosure is preferably 0.2 parts by mass or more and 40 parts by mass or less relative to 100 parts by mass of the (A) polyimide precursor and / or polyimide resin. From the viewpoint of suppressing copper migration, the lower limit of the content of the (G) thermal crosslinking agent in the photosensitive resin composition of the present disclosure is more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more. From the viewpoint of copper adhesion of the photosensitive resin composition of the present disclosure, the upper limit of the content of the (G) thermal crosslinking agent in the photosensitive resin composition of the present disclosure is more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less.

[0138] (H) Silane Coupling Agent (Component H) In order to improve the copper adhesion of the cured film, the photosensitive resin composition of this embodiment may optionally contain (H) a silane coupling agent.

[0139] (H) Examples of the silane coupling agent include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM803, manufactured by Chisso Corporation: trade name Sila-Ace S810), N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM573), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Corporation: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS1375, Azmax Corporation), and the like. AZMAX Corporation: trade name SIM6474.0), mercaptomethyltrimethoxysilane (AZMAX Corporation: trade name SIM6473.5C), mercaptomethylmethyldimethoxysilane (AZMAX Corporation: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxy Silane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxy Silane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, (3-triethoxysilylpropyl)-t-butylcarbamate, 4,4-carbonylbis(2-(((3-triethoxysilyl)propyl)amino)carbonyl)benzoic acid, and 2-(3-triethoxysilylpropylcarbamoyl)benzoic acid, but are not limited thereto.

[0140] In addition to the above, examples of the silane coupling agent (H) include N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS3610, manufactured by Azmax Corporation: trade name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Corporation: trade name SIU9058.0), N-(3-diethoxymethoxysilylpropyl)urea, and N-(3-ethoxydimethoxysilylpropyl). N-(3-tripropoxysilylpropyl)urea, N-(3-diethoxypropoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-dimethoxypropoxysilylpropyl)urea, N-(3-methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea, N-(3-ethoxydimethoxysilylethyl)urea, N-(3-tripropoxysilylpropyl)urea, N-(3-diethoxypropoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea,

[0047] Examples of suitable silanes include, but are not limited to, N-(3-trimethoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-tripropoxysilylbutyl)urea, 3-(m-aminophenoxy)propyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.1), and aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.2).

[0141] Further, examples of the silane coupling agent (H) include 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax Corporation: trade name SIT8396.0), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylmethylethyl)pyridine, (3-triethoxysilylpropyl)-t-butylcarbamate, (3-glycidoxypropyl)triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, tetrakis(methoxyethoxysilane), tetrakis(methoxy-n-propoxysilane), tetrakis(ethoxyethoxysilane), tetrakis(methoxyethoxyethoxysilane), bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane, bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane, bis(triethoxysilyl)octadiene, Bis[3-(triethoxysilyl)propyl]disulfide, bis[3-(triethoxysilyl)propyl]tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, di Methoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol,Examples of the silanol include, but are not limited to, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, and triphenylsilanol.

[0142] The silane coupling agents (H) listed above may be used alone or in combination. Among the silane coupling agents (H) listed above, N-phenyl-3-aminopropyltrimethoxysilane, (3-triethoxysilylpropyl)-t-butylcarbamate, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane are preferred from the viewpoint of copper adhesion.

[0143] When (H) silane coupling agent is used, the content is preferably 0.01 to 20 parts by mass per 100 parts by mass of (A) polyimide precursor and / or polyimide resin from the viewpoint of copper adhesion.

[0144] (I) Acid Component Other Than (B) Tetrazole Compound (Component I) In order to improve the copper adhesion of the cured film and to suppress copper migration, the photosensitive resin composition of this embodiment may optionally contain (B) an acid component other than the tetrazole compound (hereinafter referred to as component (I)). By using this acid component in combination with (G) a thermal crosslinking agent, the thermal crosslinking reaction of the (G) thermal crosslinking agent can be promoted, and the copper migration suppression effect can be improved.

[0145] Examples of component (I) include, but are not limited to, (±)mandelic acid, benzoic acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, p-aminobenzoic acid, m-trifluoromethylbenzoic acid, 4-biphenylcarboxylic acid, p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid.

[0146] When component (I) is used, the content is preferably 0.001 to 5 parts by mass per 100 parts by mass of the (A) polyimide precursor and / or polyimide resin. From the viewpoint of copper migration suppression in the photosensitive resin composition of the present disclosure, the lower limit of the content of component (I) is more preferably 0.005 parts by mass or more, and even more preferably 0.01 parts by mass or more. From the viewpoint of copper migration suppression and copper adhesion, the upper limit of the content of component (I) is more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less.

[0147] The photosensitive resin composition of this embodiment may further contain components other than the above components (A) to (I). Examples of components other than components (A) to (I) include, but are not limited to, (J) a thermal base generator, (K) a hindered phenol compound, (L) an organic titanium compound, (M) a sensitizer, and (N) a polymerization inhibitor.

[0148] (J) Thermal Base Generator (Component J) The photosensitive resin composition of this embodiment may contain (J) a thermal base generator. The (J) thermal base generator refers to a compound that generates a base upon heating. By including (J) the thermal base generator, it is possible to further promote imidization of the photosensitive resin composition of this embodiment.

[0149] The type of (J) thermal base generator is not particularly limited, and examples thereof include an amine compound protected by a tert-butoxycarbonyl group, or the thermal base generators disclosed in WO 2017 / 038598. However, the thermal base generator is not limited to these, and other known thermal base generators can also be used.

[0150] Examples of the amine compounds protected by a tert-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, and 2-amino-1,3-propanediol. Diol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanol diamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidyl)-2-propanol, 1,4-butanolbis(3-aminopropyl)ether Examples of such an amine include, but are not limited to, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown-5-ether, diethylene glycol bis(3-aminopropyl)ether, 1,11-diamino-3,6,9-trioxaundecane, and compounds in which the amino group of an amino acid or a derivative thereof is protected with a tert-butoxycarbonyl group.

[0151] The content of the thermal base generator (J) is preferably 0.1 part by mass or more and 30 parts by mass or less, and more preferably 1 part by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the polyimide precursor (A) and / or polyimide resin (B). The content of the thermal base generator (J) is preferably 0.1 part by mass or more from the viewpoint of the imidization-accelerating effect, and is preferably 30 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the photosensitive resin composition.

[0152] (K) Hindered Phenol Compound (Component K) In order to suppress discoloration on copper surfaces, the photosensitive resin composition of this embodiment may optionally contain (K) a hindered phenol compound. (K) Examples of the hindered phenol compound include, but are not limited to, 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), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t -butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-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, and 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene.

[0153] Examples of the hindered phenol compound (K) include 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione. lion, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t- butyl-3-hydroxy-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-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,Examples include, but are not limited to, 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.

[0154] Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione is particularly preferred.

[0155] The content of the (K) hindered phenol compound is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the (A) polyimide precursor and / or polyimide resin, from the viewpoint of photosensitivity characteristics. When the content of the (K) hindered phenol compound is 0.1 part by mass or more, for example, when the photosensitive resin composition is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented, while when the content of the (K) hindered phenol compound is 20 parts by mass or less, excellent photosensitivity is achieved.

[0156] (L) Organotitanium Compound (Component L) The photosensitive resin composition of this embodiment may contain an organotitanium compound (L). By containing the organotitanium compound (L) in the photosensitive resin composition of this embodiment, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at low temperatures. Organotitanium compounds that can be used as the organotitanium compound (L) include those in which an organic chemical substance is bonded to a titanium atom via a covalent bond or an ionic bond.

[0157] Specific examples of the (L) organic titanium compound are shown below in I) to VII): I) Titanium chelate compound: A titanium chelate having two or more alkoxy groups is more preferred because it improves the storage stability of the photosensitive resin composition and allows for the formation of good patterns. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), and titanium diisopropoxide bis(ethylacetoacetate).

[0158] II) Tetraalkoxytitanium compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, and titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}].

[0159] III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η ５ -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium and bis(η ５ -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.

[0160] IV) Monoalkoxytitanium compounds: for example, titanium tris(dioctylphosphate) isopropoxide and titanium tris(dodecylbenzenesulfonate) isopropoxide.

[0161] V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, and the like.

[0162] VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate.

[0163] VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate.

[0164] From the viewpoint of exhibiting better chemical resistance, the (L) organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η ５ 3-(1H-pyrrol-1-yl)phenyl)titanium is preferred.

[0165] The content of the (L) organotitanium compound is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the (A) polyimide precursor and / or polyimide resin. When the content of the (L) organotitanium compound is 0.05 part by mass or more, good heat resistance and chemical resistance are exhibited, and when the content of the (L) organotitanium compound is 10 parts by mass or less, excellent storage stability is achieved.

[0166] (M) Sensitizer (Component M) The photosensitive resin composition of this embodiment may optionally contain (M) a sensitizer in order to improve photosensitivity.

[0167] Examples of the (M) sensitizer 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, p-dimethylaminocinnamylideneindanone, p -dimethylaminobenzylideneindanone, 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-7-dimethylazoline ...1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylazoline, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-di coumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, dimethylaminobenzoic acid isoa Examples of suitable mercaptobenzoates include 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, and 2,2'-(phenylimino)diethanol. These may be used alone or in combination of, for example, 2 to 5 types.

[0168] The content of the sensitizer (M) in the photosensitive resin composition of this embodiment is preferably 0.1 to 25 parts by mass per 100 parts by mass of the polyimide precursor and / or polyimide resin (A).

[0169] (N) Polymerization Inhibitor (Component N) The photosensitive resin composition of the present embodiment may optionally contain (N) a polymerization inhibitor in order to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition of the present embodiment, particularly during storage in the form of a solution containing a solvent.

[0170] Examples of the (N) polymerization inhibitor that can be used include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

[0171] <Method for Producing Cured Relief Pattern and Semiconductor Device> The method for producing a cured relief pattern according to the present disclosure includes the following steps: (1) applying the above-described photosensitive resin composition according to the present disclosure 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.

[0172] (1) Photosensitive Resin Layer Formation Step In this step, the photosensitive resin composition of the present embodiment is applied to a substrate, and then dried as necessary to form a photosensitive resin layer. As the application method, a method conventionally used for applying a photosensitive resin composition, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., or spray application using a spray coater, etc., can be used.

[0173] (2) Exposure Step In this step, the photosensitive resin layer formed above 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, either directly or through a photomask or reticle having a pattern.

[0174] (3) Relief Pattern Forming Step In this step, the unexposed portions of the exposed photosensitive resin layer are developed and removed. The developing method for developing the exposed (irradiated) photosensitive resin layer can be any method selected from conventionally known photoresist developing methods, such as the rotary spray method, the paddle method, and the immersion method accompanied by ultrasonic treatment. After development, post-development baking may be performed at any combination of temperature and time, as needed, for the purpose of adjusting the shape of the relief pattern, etc.

[0175] The developer used for development is preferably, for example, a good solvent for the photosensitive resin composition of this embodiment, or a combination of a good solvent and a poor solvent. Examples of good solvents include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Examples of poor solvents include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When a mixture of a good solvent and a poor solvent is used, 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 of this embodiment. Furthermore, two or more of each solvent can also be used in combination.

[0176] The photosensitive resin composition of this embodiment is preferably subjected to solvent development or prepared as a solvent-developable composition. In the present disclosure, solvent development refers to development in a developer containing an organic solvent (e.g., N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc.) as the main component (the developer contains the organic solvent at a concentration of 50% by mass or more). The concentration of the organic solvent in the developer is preferably 90% by mass or more, more preferably 100% by mass. In solvent development, the developer contains fewer ionic components, making it less likely for the ionic components to be mixed into the cured film, and thus more likely to exhibit the effect of suppressing copper migration.

[0177] (4) Cured Relief Pattern Formation Step In this step, the relief pattern obtained by the development described above is heat-treated to dissolve the photosensitive component and to cure the (A) polyimide precursor through imidization, thereby converting it into a cured relief pattern (cured film) made of polyimide. Heat treatment can be performed using a variety of methods, including a hot plate, an oven, or a temperature-programmable heating oven. Heat treatment can be performed, for example, at 160°C to 350°C for 30 minutes to 5 hours. To further improve copper adhesion, the heat treatment temperature is preferably 350°C or less, more preferably 230°C or less, even more preferably 200°C or less, and even more preferably 180°C or less. To further suppress copper migration, the heat treatment temperature is preferably 170°C or more, more preferably 250°C or more. To achieve both copper adhesion and copper migration suppression, heat treatment is preferably performed at a temperature of 170°C to 350°C, more preferably 200°C to 280°C. The atmospheric gas during heat curing may be air, or an inert gas such as nitrogen or argon.

[0178] <Polyimide Film> The polyimide film (cured film) of the present disclosure can be produced by curing the photosensitive resin composition of the present disclosure, and the present disclosure also provides a cured film formed from a cured product of the photosensitive resin composition of the present disclosure. For example, a polyimide film can be produced from a photosensitive resin composition containing the polyimide resin (A) of the present disclosure based on the method for producing a cured relief pattern described above. Alternatively, a polyimide film can be produced by imidizing a photosensitive resin composition containing the polyimide precursor (A) of the present disclosure to form a cured product with an imidization rate of 80 to 100%. In this case, too, a polyimide film can be produced based on the method for producing a cured relief pattern described above.

[0179] The polyimide contained in the cured relief pattern formed from the polyimide precursor composition is represented by the following general formula (64): {In the formula, X ３ , Y ３ , and n ３ are the same as X in the above general formulas (8) and (9), respectively. １ and X ２ , Y １ and Y ２ and n １ and n ２ It is preferable that the compound contains a structural unit represented by the following formula:

[0180] Preferred X in formula (8) １ and Y １ and preferred X in formula (9) ２ and Y ２ For the same reason as above, X in the general formula (64) ３ and Y ３ In the above general formula (64), the number of repeating units n ３ is not particularly limited, but may be an integer from 2 to 150.

[0181] <Semiconductor Device> The semiconductor device preferably has a cured relief pattern obtained by the above-described method for producing a cured relief pattern. The semiconductor device preferably has 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. The semiconductor device can be manufactured using a semiconductor element as the substrate and using the method for producing a cured relief pattern of the present disclosure as part of its manufacturing process. More specifically, the semiconductor device of the present disclosure can be manufactured by a method for producing a semiconductor device that includes forming the cured relief pattern formed by the method for producing a cured relief pattern of the present disclosure as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure.

[0182] <Display Device> The display device is a display device including a display element and a cured film provided on the display element, and the cured film preferably has the cured relief pattern described above. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer sandwiched therebetween. Examples of the cured film include surface protection films, insulating films, and planarizing films for TFT liquid crystal display elements and color filter elements, protrusions for MVA-type liquid crystal display devices, and partition walls for cathodes of organic EL elements.

[0183] The photosensitive resin composition of the present disclosure is preferably a photosensitive resin composition for forming an insulating member or an interlayer insulating film. The photosensitive resin composition of the present disclosure can also be used to form a surface protective film, an interlayer insulating film, a rewiring insulating film, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure. In addition to being applied to the semiconductor device described above, the photosensitive resin composition of the present disclosure is also useful for applications such as an interlayer insulating film for a multilayer circuit, a cover coat for a flexible copper-clad board, a solder resist film, and a liquid crystal alignment film.

[0184] Examples of the present disclosure will be specifically described below, but the present embodiment is not limited thereto. In the examples, comparative examples, and production examples, the physical properties of the polyimide precursor / polyimide resin or photosensitive resin composition were measured and evaluated according to the following methods.

[0185] <Measurement and Evaluation Methods> (1) Weight-Average Molecular Weight The weight-average molecular weight (Mw) of each resin was measured using gel permeation chromatography (standard polystyrene equivalent) under the following conditions: Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40°C Column: Showa Denko K.K. Shodex KD-806M (two columns in series), or Showa Denko K.K. Shodex 805M / 806M (two columns in series) Standard monodisperse polystyrene: Showa Denko K.K. Shodex STANDARD SM-105 Mobile phase: 0.1 mol / L LiBr / N-methyl-2-pyrrolidone (NMP) Flow rate: 1 mL / min

[0186] (2) Copper Adhesion Evaluation A 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputtered with a 200 nm thick titanium (Ti) and a 400 nm thick copper (Cu) in that order using a sputtering device (SME-200E model, manufactured by ULVAC). Subsequently, the photosensitive resin composition prepared in the Examples and the like was spin-coated on this wafer using a coater developer (D-Spin 60A model, manufactured by SOKUDO Co., Ltd.) so that the film thickness after curing would be approximately 8 μm, and the wafer was pre-baked on a hot plate at 110°C for 240 seconds to form a coating film on the copper wafer. Subsequently, a parallel light mask aligner (PLA-501FA model, manufactured by Canon Inc.) was used to apply 800 mJ / cm ２ The entire surface of the film was then exposed to light. Thereafter, the film was heated for 2 hours in a temperature-programmable curing oven (VF-2000 model, manufactured by Koyo Lindberg) under a nitrogen atmosphere at the temperatures shown in Table 1 to obtain a sample with a cured relief pattern (a heat-cured polyimide coating film).

[0187] An Evercel OPP tape (No. 830NEV, manufactured by Sekisui Chemical Co., Ltd.) was applied to this sample, and the OPP tape and polyimide coating film were cut to a width of 5 mm using a cutter. Thereafter, using a Tensilon universal material testing machine (RTG-1210, manufactured by A&D Co., Ltd.), the polyimide coating film was peeled off so that it peeled off between the copper substrate and the polyimide. Specifically, the polyimide coating film with the OPP tape attached was peeled off from the copper substrate by 60 mm at a rate of 50 mm / min using a Tensilon universal material testing machine (RTG-1210, manufactured by A&D Co., Ltd.) so that the peeling direction was 180 degrees relative to the adhesive surface with the copper substrate. The load at this time was calculated as an integrated average, and this value was used as the adhesion strength to evaluate copper adhesion. A rating of C or higher can be suitably used as the cured relief pattern of this embodiment. A: Adhesion strength is 0.4 N / mm or more B: Adhesion strength is 0.3 N / mm or more and less than 0.4 N / mm C: Adhesion strength is 0.2 N / mm or more and less than 0.3 N / mm D: Adhesion strength is less than 0.2 N / mm

[0188] (3) b-HAST test SiO on the surface ｘ A TEG wafer was prepared by forming comb-shaped copper wiring with a line / space of 10 μm / 10 μm and a height of 5 μm on a silicon wafer laminated with the above. The TEG wafer was immersed in a 1% by mass aqueous acetic acid solution and ion-exchanged water for 1 minute each, in that order, then rinsed with running ion-exchanged water and dried with an air gun. Then, oxygen plasma was applied using an ashing device (NA-8000, manufactured by ULVAC) at an oxygen flow rate of 1500 mL / min, 50 Pa, MW 1500 W, RF 200 W, and 25°C for 120 seconds. The photosensitive resin composition prepared in the examples was then spin-coated using a coater developer (D-Spin 60A, manufactured by SOKUDO) to a film thickness of approximately 8 μm after curing, and pre-baked on a hot plate at 110°C for 240 seconds to form a coating film on the TEG wafer. Then, a parallel light mask aligner (PLA-501FA type, manufactured by Canon Inc.) was used to irradiate the laser beam at 800 mJ / cm ２The sample was exposed to light. To ensure electrical continuity during the b-HAST test, the copper electrode portions were masked to avoid exposure to light, and the unexposed portions were subsequently removed by development. After 30 minutes or more had elapsed since exposure, the sample was subjected to rotary spray development using a coater developer (D-Spin 60A, manufactured by SOKUDO Co., Ltd.) at 23°C and cyclopentanone as the developer for a time 1.4 times the time required for the unexposed portions to completely dissolve and disappear, followed by rotary spray rinsing with propylene glycol monomethyl ether acetate for 10 seconds. The sample was then heated for 2 hours in a nitrogen atmosphere at the temperatures listed in Table 1 using a temperature-programmable curing oven (VF-2000, manufactured by Koyo Lindberg Co., Ltd.) to obtain a cured relief pattern sample.

[0189] This sample was subjected to a b-HAST test using an ion migration evaluation system (AMI-025-U-5, manufactured by Espec Corporation) and a highly accelerated life tester HAST chamber (EHS-222M, manufactured by Espec Corporation) at an applied voltage of 50 V under an environment of 130°C and 85% RH. The insulation resistance between the copper wirings was measured at 30-minute intervals, and the resistance was 1 × 10 ４ When the resistance dropped to Ω or less, it was deemed to have undergone dielectric breakdown. The time from the start of the test to dielectric breakdown was calculated and evaluated based on the following criteria. If the evaluation was C or higher, the pattern can be suitably used as the cured relief pattern of this embodiment. A: 500 hours or more have elapsed until dielectric breakdown B: 300 hours or more but less than 500 hours have elapsed until dielectric breakdown C: 100 hours or more but less than 300 hours have elapsed until dielectric breakdown D: Less than 100 hours have elapsed until dielectric breakdown

[0190] (4) Resolution Evaluation A 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputtered with a 200 nm thick titanium (Ti) and a 400 nm thick copper (Cu) in that order using a sputtering device (SME-200E type, manufactured by ULVAC). Subsequently, the photosensitive resin composition was spin-coated on this wafer using a coater developer (D-Spin 60A type, manufactured by SOKUDO) so that the film thickness after curing would be approximately 8 μm, and the wafer was pre-baked on a hot plate at 110° C. for 240 seconds to form a coating film on the copper wafer. This coating film was then irradiated with 50 mJ / cm using a lithography system (Ultratech AP-200, manufactured by Veeco) through circular masks of φ9 μm and φ10 μm. ２ to 300 mJ / cm ２ up to 25 mJ / cm ２ The film was exposed to i-line irradiation at a focus of 0 μm in a stepwise fashion. After 30 minutes or more had elapsed, the film was subjected to rotary spray development using a coater developer (D-Spin 60A model, manufactured by SOKUDO Corporation) at 23°C using cyclopentanone as a developer for a time 1.4 times the time required for the unexposed areas to completely dissolve and disappear, followed by rotary spray rinsing with propylene glycol monomethyl ether acetate for 10 seconds. Thereafter, the film was heated for 2 hours in a temperature-rising programmable curing oven (VF-2000 model, manufactured by Koyo Lindberg Co., Ltd.) under a nitrogen atmosphere at the temperature listed in Table 1 to obtain a cured relief pattern sample.

[0191] The circular hole pattern obtained from this sample was observed for its pattern shape and width using a field emission scanning electron microscope S-4800 (manufactured by Hitachi High-Technologies Corporation). If there were no hollows at the bottom of the circular holes, the holes were tapered forward, and the area of ​​the resulting circular hole opening was at least half the area of ​​the corresponding opening in the pattern mask, the pattern was considered to be resolved, and was evaluated as follows: If the evaluation rank was C or higher, the pattern can be suitably used as the cured relief pattern of this embodiment. A: When the opening or pattern-removed area (unexposed area) does not discolor, and the circular hole formed with the φ9 μm circular mask is open. B: When the opening or pattern-removed area (unexposed area) does not discolor, and the circular hole formed with the φ10 μm circular mask is open. C: When the opening or pattern-removed area (unexposed area) discolors, but the circular hole formed with the φ10 μm circular mask is open. D: When there is residue of the photosensitive resin composition in the opening or pattern-removed area (unexposed area), and the circular hole formed with the φ10 μm circular mask is not open.

[0192] <Production Examples> - Production Example 1: (A) Synthesis of Polyimide Precursor A1 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was placed in a 2 L separable flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone (hereinafter referred to as GBL) were added, and 81.5 g of pyridine was added with stirring at room temperature to obtain a reaction mixture. After the heat generation due to the reaction had ceased, the reaction mixture was allowed to cool to room temperature and left to stand for 16 hours.

[0193] Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 200 mL of γ-butyrolactone was added to the reaction mixture over 20 minutes with stirring, followed by the addition of a suspension of 93.0 g of 4,4'-oxydianiline (ODA) in 350 mL of γ-butyrolactone over 30 minutes with stirring. After further stirring at room temperature for 4 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour, and then 400 mL of γ-butyrolactone was added. The precipitate that formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0194] The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered off and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 28 L of water to precipitate the polymer, and the resulting precipitate was filtered and then vacuum dried to obtain a powdered polymer A1 (polyimide precursor A1). The molecular weight of polyimide precursor A1 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 24,000.

[0195] Production Example 2: (A) Synthesis of Polyimide Precursor A2

[0063] Except for using 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) instead of 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), a reaction was carried out in the same manner as in the above Production Example 1 to obtain a polymer A2 (polyimide precursor A2). The molecular weight of the polyimide precursor A2 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 21,000.

[0196] Production Example 3: (A) Synthesis of Polyimide Precursor A3

[0063] Except for using 124.0 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 29.4 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) instead of 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), a reaction was carried out in the same manner as in the above Production Example 1 to obtain Polymer A3 (Polyimide Precursor A3). The molecular weight of Polyimide Precursor A3 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 24,000.

[0197] Production Example 4: (A) Synthesis of Polyimide Precursor A4

[0063] Except for using 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) instead of 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 49.2 g of 1,4-phenylenediamine (pPD) instead of 93.0 g of 4,4'-oxydianiline (ODA), a reaction was carried out in the same manner as in the above Production Example 1 to obtain Polymer A4 (Polyimide Precursor A4). The molecular weight of Polyimide Precursor A4 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 21,000.

[0198] Production Example 5: (A) Synthesis of Polyimide Precursor A5

[0066] Except for using 62 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 88.3 g of pyromellitic dianhydride (PMDA) instead of 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), and using 98.6 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) instead of 93.0 g of 4,4'-oxydianiline (ODA), a reaction was carried out in the same manner as in the above Production Example 1 to obtain Polymer A5. The molecular weight of Polymer A5 (Polyimide Precursor A5) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 28,000.

[0199] Production Example 6: (A) Synthesis of Polyimide Resin A6 In a nitrogen-purged three-necked flask equipped with a Dean-Stark extractor, 200 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 33.1 g (0.012 mol) of 6-(4-aminophenoxy)biphenyl-3-amine (PDPE) were dissolved, and 24.8 g (0.1 mol) of bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BCD) and 50.0 g of toluene were added and heated to 180 °C. After confirming that the theoretical amount of water and the added toluene had been extracted into the Dean-Stark extractor, heating was stopped and the mixture was cooled to room temperature to prepare a reaction solution. The resulting reaction solution was added dropwise to 2000 g of ion-exchanged water to precipitate a polymer, which was then filtered and vacuum-dried at 40 °C to obtain powdered polymer A6 (polyimide resin A6). The weight average molecular weight of Polyimide Resin A6 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be Mw=14,300.

[0200] Production Example 7: (A) Synthesis of Polyimide Resin A7 (MOI-Modified BCD-PDPE) 200 g of GBL and 33.1 g (0.12 mol) of PDPE were added to a nitrogen-substituted three-necked flask equipped with a Dean-Stark extractor and dissolved therein, to which 24.8 g (0.1 mol) of BCD and 50.0 g of toluene were added and heated to 180° C. After confirming that the theoretical amount of water and the added toluene had been extracted into the Dean-Stark extractor, heating was stopped and the mixture was cooled to room temperature.

[0201] Next, 6.2 g of 2-isocyanatoethyl methacrylate (hereinafter referred to as MOI) was added at room temperature, and the mixture was allowed to react at room temperature for 12 hours. The resulting reaction solution was added dropwise to 2,000 g of ion-exchanged water to precipitate a polymer, which was then filtered and vacuum-dried at 40°C to obtain powdered polymer A7 (polyimide resin A7). The weight-average molecular weight of polyimide resin A7 was measured by gel permeation chromatography (standard polystyrene equivalent) to find Mw = 15,200.

[0202] Production Example 8: (A) Synthesis of Polyimide Resin A8 Polymer A8 (polyimide resin A8) was obtained in the same manner as in Production Example 6, except that NMP in Production Example 6 was changed to GBL, the amount of PDPE added was changed to 23.0 g (0.083 mol), and BCD was changed to 44.4 g (0.1 mol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA). The weight average molecular weight of polyimide resin A8 was measured by gel permeation chromatography (standard polystyrene equivalent) to find that Mw was 14,000.

[0203] Production Example 9: (A) Synthesis of Polyimide Resin A9 Polymer A9 (polyimide resin A9) was obtained in the same manner as in Production Example 6, except that NMP in Production Example 6 was changed to GBL, PDPE was changed to 30.1 g (0.088 mol) of 9,9'-bis(4-aminophenyl)fluorene (BAFL), and BCD was changed to 19.6 g (0.1 mol) of 1,2,3,4-cyclobutanetetracarboxylic anhydride (CBDA). The weight average molecular weight of polyimide resin A9 was measured by gel permeation chromatography (standard polystyrene equivalent) to find that Mw was 29,000.

[0204] Example 1 Photosensitive resin compositions were prepared using polyimide precursors A1 and A2 by the following method, and the prepared photosensitive resin compositions were evaluated. (A) Polyimide precursors A1 and A2: 40 g of the polyimide precursor A1 described in Production Example 1 and 60 g of the polyimide precursor A2 described in Production Example 2, (B) tetrazole compound B1: 1 g of 1H-tetrazole-5-acetic acid, (C) heterocyclic compound C1: 0.5 g of N-(6-oxo-6,7-dihydro-1H-purin-2-yl)isobutyramide, (D) photopolymerization initiator D1: 5 g of 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, (F) photopolymerizable monomer F1: 10 g of tetraethylene glycol dimethacrylate, (G) thermal 1 g of alkylated urea resin (G1) as a crosslinking agent, 1 g of N-phenyl-3-aminopropyltrimethoxysilane (H1) as a silane coupling agent, 0.5 g of diisopropoxytitanium bis(ethyl acetate) (L1) as an organic titanium compound, and 5 g of 2,2'-(phenylimino)diethanol (M1) as a sensitizer were dissolved in a mixed solvent of 80 g of γ-butyrolactone (E1) (hereinafter referred to as GBL, manufactured by Mitsubishi Chemical Corporation) and 20 g of dimethyl sulfoxide (E2) (hereinafter referred to as DMSO, manufactured by Toray Fine Chemicals Co., Ltd.). The viscosity of the resulting solution was adjusted to approximately 40 poise by adding the required amount of a solution of GBL:DMSO = 80:20 (mass ratio), to prepare a photosensitive resin composition (Example 1). This composition was evaluated according to the method described above. The results are shown in Table 1.

[0205] Examples 2 to 43, Comparative Examples 1 to 8 Photosensitive resin compositions of Examples 2 to 43 and Comparative Examples 1 to 8 were prepared and evaluated by adjusting the viscosity of the components other than the (E) solvent in the same manner as in Example 1, except that the components were adjusted in the blending ratios shown in Table 1. The compounds listed in Table 1 are as follows:

[0206] (A) Polyimide precursor / polyimide resin or comparative polymer A1: Polyimide precursor described in Production Example 1 A2: Polyimide precursor described in Production Example 2 A3: Polyimide precursor described in Production Example 3 A4: Polyimide precursor described in Production Example 4 A5: Polyimide precursor described in Production Example 5 A6: Polyimide resin described in Production Example 6 A7: Polyimide resin described in Production Example 7 A8: Polyimide resin described in Production Example 8 A9: Polyimide resin described in Production Example 9 A'1: ZCR-1797H (acid-modified epoxy acrylate having a biphenyl skeleton, manufactured by Nippon Kayaku Co., Ltd.)

[0207] (B) Tetrazole Compounds B1: 1H-tetrazole-5-acetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) B2: 1H-tetrazole-5-carboxylic acid (manufactured by Advanced ChemBlocks) B3: 1H-tetrazole-5-propionic acid (manufactured by Enamine Building Blocks) B4: 4-(1H-tetrazol-5-yl)benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) B5: 1H-tetrazole-1-acetic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) B6: 2,2-bis(2-2H-tetrazol-5-yl)ethyl)propanedioic acid B7: 1H-tetrazole-5-ethyl carboxylate (manufactured by Tokyo Chemical Industry Co., Ltd.) The pKa values ​​of B1 to B7 listed in Table 1 and C13 to C15 described below are those of Advanced ChemBlocks The values ​​were calculated using Chemistry Software V11.02 (1994-2018 ACD / Labs).

[0208] (C) Heterocyclic Compounds C1: N-(6-oxo-6,7-dihydro-1H-purin-2-yl)isobutyramide (manufactured by Tokyo Chemical Industry Co., Ltd.) C2: 2-acetamido-6-hydroxypurine (manufactured by Tokyo Chemical Industry Co., Ltd.) C3: N2,9-diacetylguanine (manufactured by Tokyo Chemical Industry Co., Ltd.) C4: 6-methoxypurine (manufactured by Tokyo Chemical Industry Co., Ltd.) C5: Adenine (manufactured by Tokyo Chemical Industry Co., Ltd.) C6: Guanosine (manufactured by Tokyo Chemical Industry Co., Ltd.) C7: Hypoxanthine (manufactured by Tokyo Chemical Industry Co., Ltd.) C8: 8-azaadenine (manufactured by Tokyo Chemical Industry Co., Ltd.) C9: 8-azahypoxanthine (manufactured by Tokyo Chemical Industry Co., Ltd.) C10: N6-benzoyladenine (manufactured by Tokyo Chemical Industry Co., Ltd.) C11: Xanthopterin (manufactured by Tokyo Chemical Industry Co., Ltd.) C12: 4-[2-(2-amino-4,7-dihydro-4-oxo-3H-pyrrolo[2,3-d]pyrimidin-5-yl)ethyl]benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) C13: 5-amino-1H-tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.) C14: 1-methyl-1H-tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.) C15: 5-carboxybenzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0209] (D) Photopolymerization initiator D1: 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime (manufactured by Changzhou New Power Electronic Materials Co., Ltd.) D2: TR-PBG3057 (manufactured by Changzhou New Power Electronic Materials Co., Ltd.)

[0210] (E) Solvent E1: GBL (manufactured by Mitsubishi Chemical Corporation) E2: DMSO (manufactured by Toray Fine Chemicals Co., Ltd.)

[0211] (F) Photopolymerizable Monomers F1: Tetraethylene glycol dimethacrylate (product name: NK Ester 4G, manufactured by Shin-Nakamura Chemical Co., Ltd.) F2: Tris-(2-acryloxyethyl) isocyanurate (product name: NK Ester A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.) F3: Methoxypolyethylene glycol monomethacrylate (product name: PME-400, manufactured by NOF Corporation)

[0212] (G) Thermal crosslinking agent G1: Alkylated urea resin (product name: Nikalac MX-290, manufactured by Sanwa Chemical Co., Ltd.) G2: 1,3,4,6-tetrakis(methoxymethyl)glycoluril (product name: Nikalac MX-270, manufactured by Sanwa Chemical Co., Ltd.)

[0213] (H) Silane Coupling Agents H1: N-phenyl-3-aminopropyltrimethoxysilane (product name: KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.) H2: (3-triethoxysilylpropyl)-t-butylcarbamate (manufactured by Gelest) H3: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0214] (I) (B) Acid components other than tetrazole compounds I1: (±) mandelic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) I2: p-toluenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0215] (L) Organic titanium compound L1: diisopropoxytitanium bis(ethyl acetate) (product name Orgatix TC-750, manufactured by Matsumoto Fine Chemical Co., Ltd.) (M) Sensitizer M1: 2,2'-(phenylimino)diethanol (manufactured by Kanto Chemical Co., Ltd.)

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[0220]

[0221] Looking at the results in Table 1, Comparative Examples 1 to 8, which do not satisfy the requirements of the present disclosure, are unable to improve all of the copper adhesion, copper migration suppression performance (corresponding to the b-HAST test results), and resolution. On the other hand, Examples 1 to 43, which satisfy the requirements of the present disclosure, were excellent in all of the copper adhesion, copper migration suppression performance, and resolution.

[0222] A comparison of Comparative Example 1 with Example 1 shows that the use of the (A) polyimide precursor and / or polyimide resin of the present disclosure improves both copper adhesion and copper migration inhibition performance. Furthermore, a comparison of Comparative Example 2 and Comparative Example 3 with Example 1 shows that the inclusion of the (B) tetrazole compound of the present disclosure, which has a pKa of 1.3 or more and 4.1 or less, among tetrazole compounds, improves all of copper adhesion, copper migration inhibition performance, and resolution. Furthermore, a comparison of Comparative Example 4 with Example 1 shows that the inclusion of the (B) component of the present disclosure, which is a tetrazole compound among compounds having a pKa of 1.3 or more and 4.1 or less, improves all of copper adhesion, copper migration inhibition performance, and resolution. Furthermore, a comparison of Comparative Example 5 with Example 7 and Comparative Example 8 with Example 8 shows that the inclusion of the (B) tetrazole compound of the present disclosure improves copper migration inhibition performance. Subsequently, a comparison of Comparative Example 6 with Example 17 shows that the inclusion of the (C) heterocyclic compound of the present disclosure improves copper adhesion. Furthermore, up to this point, the comparison was made at a high cure temperature of 250°C. However, by comparing Comparative Example 7 with Example 34, it can be seen that the inclusion of the tetrazole compound (B) results in good copper migration suppression performance even at a low cure temperature of 200°C.

[0223] Comparing Examples 13 and 14 with Example 12, Example 12, which contains a fused ring compound as the (C) heterocyclic compound, exhibits superior copper adhesion. Comparing Example 10 with Example 11, a comparison of Example 10 with Example 11 reveals that a (C) heterocyclic compound containing a purine derivative provides a well-balanced and superior copper adhesion, copper migration suppression, and resolution. Furthermore, comparing Example 10 with Examples 4 to 9, and comparing Examples 4 to 9 with Examples 1 to 3, it is clear that a (C) heterocyclic compound containing a purine derivative represented by any of formulas (3) to (6), or even a compound represented by formula (7), improves copper adhesion. Furthermore, comparing Example 20 with Examples 19 and 18 reveals that the presence of a carboxyl group in the (B) tetrazole compound improves copper adhesion and copper migration suppression. Furthermore, comparing Examples 18 and 19 with Examples 15 to 17 reveals that the presence of a (B) tetrazole compound represented by formula (1) improves copper adhesion.

[0224] Next, comparing Example 21 with Example 1, it is found that the inclusion of the (F) photopolymerizable monomer improves resolution. Furthermore, comparing Examples 21 to 24, it is found that a good balance of copper adhesion, copper migration suppression performance, and resolution is achieved when the total content of the (B) tetrazole compound and the (C) heterocyclic compound is 0.1 to 10 parts by mass. Furthermore, comparing Example 21 with Examples 25 to 28, it is found that a good balance of performance is achieved when the ratio of the content of the (B) tetrazole compound to the content of the (C) heterocyclic compound is 0.1 ≦ (B) tetrazole compound content (parts by mass) / (C) heterocyclic compound content (parts by mass) ≦ 10.

[0225] A comparison of Example 30 with Example 31 shows that the inclusion of (G) a thermal crosslinking agent improves copper migration suppression performance. Furthermore, a comparison of Example 32 with Examples 29 and 30 shows that the inclusion of (I) an acid component other than the tetrazole compound (B) improves copper migration suppression performance. A comparison of Example 33 with Example 30 shows that the inclusion of (H) a silane coupling agent improves copper adhesion. Furthermore, a comparison of Example 21 with Examples 34 to 36 shows that all performances are excellent at all cure temperatures of 200°C, 250°C, 280°C, and 350°C.

[0226] By using the photosensitive resin composition according to the present disclosure, it is possible to obtain a cured relief pattern with excellent copper adhesion even when cured at high temperatures, with little copper migration in the b-HAST test, and with high resolution. The photosensitive resin composition according to the present disclosure can be suitably used in the field of photosensitive materials useful for manufacturing electrical and electronic materials such as semiconductor devices and multilayer wiring boards. More specifically, it can be used, for example, in forming relief patterns of insulating materials for electronic components, and passivation films, buffer coat films, interlayer insulating films, and the like in semiconductor devices.

Claims

1. A photosensitive resin composition comprising the following components: (A) a polyimide precursor and / or a polyimide resin; (B) a tetrazole compound having a pKa of 1.3 or more and 4.1 or less; (C) a heterocyclic compound other than the (B) tetrazole compound; and (D) a photopolymerization initiator.

2. The photosensitive resin composition according to claim 1, wherein the tetrazole compound (B) is a compound having a carboxyl group.

3. The photosensitive resin composition according to claim 1 or 2, wherein the (D) photopolymerization initiator is a photoradical polymerization initiator.

4. The photosensitive resin composition according to claim 3, wherein the photoradical polymerization initiator is an oxime initiator.

5. The photosensitive resin composition according to claim 1 or 2, wherein the heterocyclic compound (C) is a purine derivative.

6. The tetrazole compound (B) is represented by the following general formula (1): {In formula (1), R １ represents a carboxyl group or the following general formula (2): and R ２ is a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with at least one of a halogen atom, a hydroxyl group, an alkoxysilyl group, and an amino group.

7. The heterocyclic compound (C) is represented by the following general formula (3): {In the formula, R ３ is an amino group or an alkoxy group having 1 to 6 carbon atoms, and R ４ is a hydrogen atom or an amino group which may be substituted with a plurality of organic groups having 1 to 10 carbon atoms, and R ５ is a hydrogen atom or an organic group having 1 to 10 carbon atoms.}, a compound represented by the following general formula (4): {In the formula, R ６ is a hydrogen atom or an amino group which may be substituted with a plurality of organic groups having 1 to 10 carbon atoms, and R ７ is a hydrogen atom or an organic group having 1 to 10 carbon atoms.}, a compound represented by the following general formula (5): {In the formula, R ８ is an amino group or an alkoxy group having 1 to 6 carbon atoms, and R ９ is a hydrogen atom or an amino group which may be substituted with a plurality of organic groups having 1 to 10 carbon atoms, and R １０ is a hydrogen atom or an organic group having 1 to 10 carbon atoms.}, or a compound represented by the following general formula (6): {In the formula, R １１ is a hydrogen atom or an amino group which may be substituted with a plurality of organic groups having 1 to 10 carbon atoms, and R １２ is a hydrogen atom or an organic group having 1 to 10 carbon atoms.}. The photosensitive resin composition according to claim 1 or 2, 8. The heterocyclic compound (C) is represented by the following general formula (7): {In the formula, R １３ is an organic group having 1 to 10 carbon atoms, and R １４ is a hydrogen atom or an organic group having 1 to 10 carbon atoms.

9. The following general formula (8): {In the formula, X １ is a tetravalent organic group, and Y １ is a divalent organic group, and n １ is an integer from 2 to 150, and R １５ and R １６ are each independently a hydrogen atom or a monovalent organic group.} and / or the polyimide precursor is represented by the following general formula (9): {In the formula, X ２ is a tetravalent organic group, and Y ２ is a divalent organic group, and n ２ and n is an integer of 2 to 150.}. The photosensitive resin composition according to claim 1 or 2, comprising the polyimide resin represented by the formula:

10. In the above general formula (8), R １５ and R １６ At least one of the following general formula (10): {In the formula, L １ , L ２ and L ３ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m １ and n is an integer of 2 to 10.}. The photosensitive resin composition according to claim 9, 11. The photosensitive resin composition according to claim 1 or 2, wherein the total content of the tetrazole compound (B) and the heterocyclic compound (C) is 0.1 to 10 parts by mass per 100 parts by mass of the component (A).

12. The photosensitive resin composition according to claim 1 or 2, wherein the ratio of the content of the (B) tetrazole compound to the content of the (C) heterocyclic compound satisfies the following formula (9): 0.1≦Content of the (B) tetrazole compound (parts by mass) / Content of the (C) heterocyclic compound (parts by mass)≦10 (9).

13. The photosensitive resin composition according to claim 1 or 2, further comprising (E) a solvent.

14. The photosensitive resin composition according to claim 1 or 2, further comprising (F) a photopolymerizable monomer.

15. The photosensitive resin composition according to claim 1 or 2, further comprising (G) a thermal crosslinking agent.

16. The photosensitive resin composition according to claim 1 or 2, further comprising (H) a silane coupling agent.

17. The photosensitive resin composition according to claim 1 or 2, which contains (I) an acid component other than the (B) tetrazole compound.

18. The photosensitive resin composition according to claim 1 or 2, which is a photosensitive resin composition for forming a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure.

19. A method for producing a cured relief pattern, comprising the following steps: (1) applying the 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.

20. The method for producing a cured relief pattern according to claim 19, wherein the heat treatment in step (4) is a heat treatment at 170°C or higher and 350°C or lower.

21. A cured film comprising a cured product of the photosensitive resin composition according to claim 1 or 2.

22. A method for producing a polyimide film, comprising curing the photosensitive resin composition according to claim 1 or 2.

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