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

Abstract

Provided is a photosensitive resin composition which comprises (A) a polyimide precursor and / or a polyimide resin, (B) a heterocyclic compound, and (C) a photoinitiator, and in which (B) the heterocyclic compound includes a compound represented by (b1) general formula (1) or (b2) general formula (2). (1) {In formula, R1 represents an organic group and R2 represents a hydrogen atom or an organic group.} (2) {In formula, R3 represents an organic group at least having one or more carbonyl groups.}

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 Conventional mounting methods using metal pins and lead-tin eutectic solder have been replaced by structures in which a polyimide coating directly contacts the solder bumps, such as BGA (ball grid array) and CSP (chip size packaging), which enable higher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 No. 10,658,199 JP 2012-194520 A

[0006] In recent years, miniaturization of wiring widths in semiconductor elements and circuits has been required to improve the performance, increase functionality, reduce power consumption, and reduce costs of semiconductor devices. As finer wiring advances, higher resolution is also important for interlayer insulating films. Furthermore, as the wiring width becomes smaller due to finer wiring, copper may migrate into the resin layer (interlayer insulating film) (hereinafter also referred to as "copper migration" in this disclosure), causing short circuits between wirings.

[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, high-humidity environments.

[0008] Conventional interlayer insulating films may experience the above-mentioned copper migration during reliability tests (b-HAST: Biased Highly Accelerated Stress Test) under high temperature and high humidity. Copper migration can cause short circuits between interconnects, particularly in semiconductor devices with finer interconnects, preventing the film from fully performing as an insulating film. As copper migration progresses, voids (hereinafter also referred to as "copper voids" in this disclosure) may occur at the interface between the copper interconnect and the resin layer. The occurrence of copper voids at the interface between the copper interconnect and the resin layer can reduce adhesion between the two, causing the resin to peel off from the copper, resulting in impaired insulation. Meanwhile, resins are sometimes cured at high temperatures to improve copper migration suppression capabilities and film properties, but curing conventional interlayer insulating films at high temperatures can sometimes result in reduced copper adhesion.

[0009] Therefore, 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 little copper migration in a b-HAST test, i.e., does not short circuit over 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 a method for producing a cured film and a polyimide film.

[0010] The present inventors have found that the above-mentioned problems can be solved by adding a specific heterocyclic compound to a photosensitive resin composition. Examples of embodiments of the present disclosure are listed in the following items [1] to

[17] . [1] A photosensitive resin composition comprising the following components: (A) a polyimide precursor and / or polyimide resin, (B) a heterocyclic compound, and (C) a photopolymerization initiator, wherein the heterocyclic compound (B) is represented by the following general formula (1): (b1) {In the formula, R １ is an organic group, and R ２ is a hydrogen atom or an organic group.}, or (b2) a compound represented by the following general formula (2): {In the formula, R ３ is an organic group having at least one carbonyl group.}. [2] A photosensitive resin composition comprising a compound represented by the following general formula (3): {In the formula, R ４ is an organic group having 1 to 10 carbon atoms and having at least one hydroxyl group or carbonyl group.}, or a compound represented by the following general formula (4): {In the formula, R ５ and R ６ are each independently an organic group having 1 to 10 carbon atoms and having at least one carbonyl group.}, and the compound (b2) is a compound represented by the following general formula (5): {In the formula, R ７ is an organic group having 1 to 6 carbon atoms and having at least one carbonyl group.}. [3] The photosensitive resin composition according to [1], wherein the compound is a compound represented by the following general formula (6): {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 ９ and R １０ are each independently a hydrogen atom or a monovalent organic group.}, and / or the photosensitive resin composition contains the polyimide resin, and the polyimide resin is represented by the following general formula (7): {In the formula, X２ is a tetravalent organic group, and Y ２ is a divalent organic group, and n ２ is an integer of 2 to 150.}. [4] The photosensitive resin composition according to [1] or [2], having a structural unit represented by the following general formula (6): ９ and R １０ At least one of the following general formula (8): {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.}. [5] The photosensitive resin composition according to [1] to [4], wherein the (C) photopolymerization initiator is a photoradical polymerization initiator. [6] The photosensitive resin composition according to [5], wherein the photoradical polymerization initiator is an oxime initiator. [7] The photosensitive resin composition according to any one of [1] to [6], wherein the content of the (B) component is 0.01 to 10 parts by mass per 100 parts by mass of the (A) component. [8] The photosensitive resin composition according to any one of [1] to [7], further comprising (D) a solvent. [9] The photosensitive resin composition according to any one of [1] to [8], further comprising (E) a photopolymerizable monomer.

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

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

[10] , further comprising (G) a silane coupling agent.

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

[11] , further comprising (H) an acid component.

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

[12] , 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.

[14] 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

[13] 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.

[15] The method for producing a cured relief pattern according to

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

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

[13] .

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

[13] .

[0011] According to the present disclosure, it is possible to provide a photosensitive resin composition that can achieve high copper adhesion 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.

[0012] 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.

[0013] <Photosensitive Resin Composition> The photosensitive resin composition of the present disclosure includes (A) a polyimide precursor and / or a polyimide resin, (B) a heterocyclic compound, and (C) a photopolymerization initiator. The photosensitive resin composition of the present disclosure further includes (B) a heterocyclic compound represented by the following general formula (1): {In the formula, R １ is an organic group, and R ２ is a hydrogen atom or an organic group.}, or (b2) a compound represented by the following general formula (2): {In the formula, R ３ is an organic group having at least one carbonyl group.}. This makes it possible to provide a photosensitive resin composition that exhibits high copper adhesion when cured at high temperatures, exhibits little copper migration in the b-HAST test, and has high resolution. Each component will be described in detail below.

[0014] (A) Polyimide Precursor 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. The resin used in the (A) polyimide precursor is preferably not alkali-soluble, since this allows for high chemical resistance and a higher copper migration suppression capability to be obtained. To obtain a polyimide precursor that is not alkali-soluble, it is preferable that the resin skeleton does not contain an acidic group. It is also preferable that the (A) polyimide precursor does not contain a fluorine atom. This allows for better suppression of copper migration.

[0015] The polyimide precursor (A) is represented by the following general formula (6): {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 ９ and R １０ are each independently a hydrogen atom or a monovalent organic group.} The polyimide precursor represented by the above formula (6) is preferably a polyamide having a structure represented by the above formula (6). １ In the above formula (6), X is preferably a polyamide having a structure that does not have an acidic group such as a carboxylic acid group or a phenolic hydroxyl group. １ is R ９ or R １０ is a hydrogen atom, the polyimide precursor (A) preferably does not have an acidic group, except for a carboxyl 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.

[0016] In general formula (6), R ９ and R １０ At least one of the above preferably contains a photopolymerizable functional group, and is represented by the following general formula (8): {In the formula, L １ , L ２ and L ３are 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.}.

[0017] R in general formula (6) ９ and R １０ The proportion of hydrogen atoms in R ９ and R １０ 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. ９ and R １０ is a monovalent organic group represented by the general formula (8), R ９ and R １０ It is preferable that the proportion of hydrogen atoms and the proportion of the organic group of general formula (8) are within the above ranges, based on the total number of moles, of 70 mol % or more, more preferably 80 mol % or more, and even more preferably 90 mol % or more. It is preferable that the proportion of hydrogen atoms and the proportion of the organic group of general formula (8) are within the above ranges, from the viewpoint of photosensitive properties and storage stability.

[0018] n in general formula (6) 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.

[0019] In general formula (6), 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 ９ group and -COOR １０ The X group and the —CONH— group are in the ortho position relative to each other, or an alicyclic aliphatic group. １ Specific examples of the tetravalent organic group represented by the formula (9) include an organic group having 6 to 40 carbon atoms containing an aromatic ring, such as a group represented by the formula (9) below: {In the formula, R １１is 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 selected from 0 to 2, m is an integer selected from 0 to 3, and n is an integer selected from 0 to 4.}, but is not limited to these. １ The structure of X having the structure represented by the above formula (9) 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.

[0020] X １ As the group, among the structures represented by the above formula (9), particularly, the group represented by the following formula (10): {In the formula, R １２ 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 m is an integer selected from 0 to 3.} is preferred from the viewpoints of the imidization rate during low-temperature heating, degassing properties, copper adhesion, chemical resistance, etc.

[0021] In the above general formula (6), Y １ From the viewpoint of achieving both heat resistance and photosensitive properties, the divalent organic group represented by the formula (11) below is preferably an aromatic group having 6 to 40 carbon atoms, for example. {In the formula, R １１ 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 (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.

[0022] Y １ As the group, among the structures represented by the above formula (11), particularly, the group represented by the following formula (12): {In the formula, R １１ 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 selected from 0 to 4.} is preferred from the viewpoints of the imidization rate during low-temperature heating, degassing properties, copper adhesion, chemical resistance, etc.

[0023] L in the above general formula (8) 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 ３ is 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.

[0024] In one embodiment, the polyimide precursor (A) is represented by the following general formula (13): {In the formula, R １２ , R １３ , and n １ is R defined in the above formula (6). ９ , R １０ and n １ The same applies to the polyimide precursor having a structural unit represented by the following formula:

[0025] In general formula (13), R １２ and R １３ It is more preferable that at least one of the groups represented by the general formula (8) is a monovalent organic group represented by the following general formula (14): X represented by １ Inclusion of these in the structural units results in particularly high chemical resistance.

[0026] In one embodiment, the polyimide precursor (A) is represented by the following general formula (15): {In the formula, R １４ , R １５ , and n１ is R defined in the above formula (6). ９ , R １０ and n １ In view of thermal properties, a polyimide precursor having a structural unit represented by the following formula (I) is preferred.

[0027] In general formula (15), R １４ and R １５ At least one of the groups is more preferably a monovalent organic group represented by the above general formula (8).

[0028] The polyimide precursor (A) tends to have particularly high resolution when it contains both the structural unit represented by general formula (13) and the structural unit represented by general formula (15). For example, the polyimide precursor (A) may contain a copolymer of the structural unit represented by general formula (13) and the structural unit represented by general formula (15), or may be a mixture of the polyimide precursor represented by general formula (13) and the polyimide precursor represented by general formula (15).

[0029] The polyimide precursor (A) is represented by the following general formula (16): {In the formula, R １６ , R １７ , and n １ is R defined in the above formula (6). ９ , R １０ and n １ The same applies to the polyimide precursor having a structural unit represented by the following formula:

[0030] The polyimide precursor (A) is represented by the following general formula (17): {In the formula, R １８ , R １９ , and n １ is R defined in the above formula (6). ９ , R １０ and n １ The polyimide precursor (A) preferably has a structural unit represented by the following formula (17): When the polyimide precursor (A) contains a structural unit represented by the following formula (17), the chemical resistance is particularly enhanced.

[0031] 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.

[0032] (A) Method for Preparing Polyimide Precursor (A) The polyimide precursor is prepared by first reacting 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.

[0033] (Preparation of Acid / Ester Form) (A) A tetravalent organic group X suitable for preparing a polyimide precursor １ Examples of the tetracarboxylic dianhydride containing the formula (9) include the tetracarboxylic dianhydride represented by the general formula (9) above, as well as, for example, 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, but are not limited thereto. Among these, preferred tetracarboxylic dianhydrides 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.

[0034] (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 cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

[0035] 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.

[0036] 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.

[0037] (A) Preparation of Polyimide Precursor) A suitable dehydration condensation agent, for example, dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, or the like 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.

[0038] Divalent organic group Y １ Examples of diamines containing the following general formula (18): 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.

[0039] 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 a mixture thereof 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 desired 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.

[0040] 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 the (A) polyimide precursor has a weight average molecular weight of 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.

[0041] (A) Polyimide Resin The photosensitive resin composition of the present disclosure may contain (A) a polyimide resin in addition to or instead of (A) the polyimide precursor.

[0042] The polyimide resin (A) does not generate any 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.

[0043] The (A) polyimide resin may have a polymerizable group in the side chain, but preferably does not have a polymerizable group in the 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" means, for example, that the imidization rate of the polyimide resin is 90% or more, preferably 95% or more.

[0044] (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 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 after the heat treatment is measured. －１ The imidization rate of the polyimide resin is calculated by comparing the peak intensity in the vicinity with the peak intensity before the heat treatment.

[0045] 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 (7). 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 (7), X ２ and / Y ２It 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.

[0046] 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 for the cured film to have at least one structure represented by the following formulas (19) to (27).

[0047] Also, X ２ Preferably, X has at least one structure represented by formulas (19) to (26) 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 has at least one structure represented by formulas (19) to (21) and (23) to (26). ２ It is particularly preferred that the photosensitive resin composition of the present disclosure has at least one structure represented by formulas (19) and (24) to (26), since this results in particularly excellent coating film uniformity and cured film elongation.

[0048] Y in formula (7) 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 for it to have at least one structure represented by the following formulas (28) to (36):

[0049] Also, Y ２ Preferably, Y has at least one structure represented by formulas (28) to (34) 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 has at least one structure represented by formulas (28) to (33). 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) have at least one structure represented by formulas (30) to (33) because the coating film uniformity and cured film elongation are particularly excellent. The excellent solubility in solvents of the structures represented by formulas (30) to (33) is due to the fact that these structures have a pendant phenyl structure.

[0050] n in formula (7) 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) described below.

[0051] 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, has at least one structure selected from the group consisting of an acid anhydride group, a carboxyl group, an amino group, and the following general formulae (37) to (39): {In the formula, R ２０ , R ２１ are each independently selected from a hydrogen atom and a monovalent organic group having 1 to 3 carbon atoms; R ２２ is an organic group having 1 to 20 carbon atoms which may contain a heteroatom, and k is an integer of 1 or 2. ２３ represents a hydrogen atom or an organic group having 1 to 4 carbon atoms, and * represents the bonding site with the terminal of the (A) polyimide resin.} {In the formula, R ２４ , R ２５ 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 ２６ , R ２７ , R ２８ 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).

[0052] 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 (37) include structures represented by the following formulas (40) to (43). (In the formula, * indicates the bonding site with the terminal of the polyimide resin (A).)

[0053] More specific examples of the structure represented by general formula (38) include structures represented by the following formulae (44) and (45). (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 (39) include structures represented by the following formulae (46) to (49). (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 (7) ２ is any one of the structures represented by general formulas (19) to (27), and Y ２ is preferably any one of the structures represented by general formulas (28) to (36).

[0056] The weight-average molecular weight (Mw) of the (A) polyimide resin is not particularly limited as long as it is within the range in which it can be dissolved 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 reacting a tetracarboxylic dianhydride with a diamine to obtain a polyamic acid, which is then subjected to dehydration ring closure to be imidized. The acid anhydride group, carboxyl group, and amino group at the terminals of the (A) polyimide resin may be reacted with a predetermined compound to give the terminals a structure represented by the above general formulas (37) to (39).

[0065] Polyimide resin (A) whose terminal has a structure represented by general formula (37) 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 isocyanate compound is not particularly limited; however, the isocyanate compound can be reacted with the amino group of the dehydrated, ring-closed polyimide by adding the isocyanate compound to a dehydrated, ring-closed polyimide solution and stirring at room temperature.

[0066] The polyimide resin (A) whose terminal has a structure represented by general formula (38) 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 chloride compound is not particularly limited, but the chloride compound can be reacted with the amino group of the dehydrated, ring-closed polyimide by ice-cooling the polyimide solution and adding the chloride compound dropwise.

[0067] Polyimide resin (A) whose terminals have a structure represented by general formula (39) 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 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 polymerizable functional group at its terminal. 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) Heterocyclic Compound The (B) heterocyclic compound includes a compound (b1) represented by the following general formula (1) or a compound (b2) represented by the following general formula (2). {In the formula, R １ is an organic group, and R ２ is a hydrogen atom or an organic group. {In the formula, R ３ is an organic group having at least one carbonyl group.

[0072] R in general formula (1)１ is not particularly limited as long as it is an organic group, but may be a branched or linear alkyl group, an aromatic group, or a carboxyl group, and may also have a functional group (e.g., an acetyl group or an acetoxy group). １ is preferably an organic group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a phenyl group, a tolyl group, and a xylyl group. ２ is not particularly limited as long as it is a hydrogen atom or an organic group, but may be a branched or linear alkyl group, an aromatic group, or a carboxyl group, and may also have a functional group (for example, an acetyl group or an acetoxy group). ２ is preferably an organic group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a phenyl group, a tolyl group, and a xylyl group. ３ is not particularly limited as long as it is an organic group having one or more carbonyl groups, but may be a branched or linear alkyl group, an aromatic group, or a carboxyl group. ３ may have a functional group, and is preferably an organic group having 1 to 10 carbon atoms. For example, the functional group may be an acetyl group or an acetoxy group.

[0073] When the (B) heterocyclic compound contains the compound (b1) represented by the general formula (1) or the compound (b2) represented by the general formula (2), 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 (curing at 250°C or more in the present disclosure). Furthermore, copper migration suppression and copper void suppression effects can be obtained not only by high-temperature curing but also by low-temperature curing. The reason for this is unclear and we are not bound by theory; however, it is believed that when the photosensitive resin composition of this embodiment contains the purine compound represented by the formula (1) or (2), the unshared electron pair associated with the nitrogen atom in the purine skeleton acts on copper and is unevenly distributed at the copper interface. Furthermore, the secondary amine at the 1-position, formed by the ketone at the 6-position, forms a hydrogen bond with the polyimide precursor or polyimide, thereby allowing the polyimide resin to interact with copper and improve copper adhesion. Furthermore, the uneven distribution of the purine compound at the copper interface is thought to strongly suppress oxidation reactions at the copper interface, thereby suppressing copper migration and copper voids.

[0074] Specific examples of the heterocyclic compound (b1) (B) represented by general formula (1) include ganciclovir, guanosine, 3'-amino-2',3'-dideoxyguanosine, penciclovir, 2-[2-isobutylamido-6-oxo-1H-purin-9(6H)-yl]acetic acid, 2-{2-[(tert-butoxycarbonyl)amino]-6-oxo-1H-purin-9(6H)-yl}acetic acid, N-acetyl-di-O-acetylganciclovir, N-acetylacyclo ... ２ -isobutyryl-2'-deoxyguanosine, 9-ethylguanine, N ２ -isobutyrylguanosine, 2-amino-9-phenyl-1H-purin-6(9H)-one, N ２ , 9-diacetylguanine, 9-[(2-acetoxyethoxy)methyl]-N ２Among these, from the viewpoint of copper adhesion and copper migration inhibition, ganciclovir, guanosine, 3'-amino-2',3'-dideoxyguanosine, penciclovir, 2-[2-isobutylamido-6-oxo-1H-purin-9(6H)-yl]acetic acid, N-acetyl-di-O-acetylganciclovir, N ２ ,9-diacetylguanine is preferred, and N ２ , 9-diacetylguanine.

[0075] Specific examples of the heterocyclic compound (b2) (B) represented by the general formula (2) include 2-acetamido-6-hydroxypurine, N-(6-oxo-6,7-dihydro-1H-purin-2-yl)isobutyramide, N ２ Among these, from the viewpoint of copper adhesion and copper migration suppression, 2-acetamido-6-hydroxypurine, N-(6-oxo-6,7-dihydro-1H-purin-2-yl)isobutylamide, N-(6-oxo-6,9 ... ２ 2-acetamido-6-hydroxypurine and N-(6-oxo-6,7-dihydro-1H-purin-2-yl)isobutyramide are more preferred. When these are added to the resin composition, they may be in the form of a hydrate.

[0076] In particular, from the viewpoint of copper adhesion during high-temperature curing, the heterocyclic compound (B) is preferably a compound represented by the following general formula (3), (4) or (5). {In the formula, R ４ is an organic group having 1 to 10 carbon atoms and having at least one hydroxyl group or carbonyl group. {In the formula, R ５ and R ６ are each independently an organic group having 1 to 10 carbon atoms and having at least one carbonyl group. {In the formula, R ７ is an organic group having 1 to 6 carbon atoms and having at least one carbonyl group.

[0077] R in general formula (3) ４ is not particularly limited as long as it is an organic group having 1 to 10 carbon atoms and having a hydroxyl group or a carbonyl group, but may also be a branched or linear alkyl group or aromatic group having 1 to 10 carbon atoms and having the above-mentioned functional group. Examples of the functional group include a hydroxymethyl group, a hydroxyethyl group, an acetyl group, and an acetoxy group.

[0078] R in general formula (4) ５ and R ６ The carbonyl group-containing organic group having 1 to 10 carbon atoms may be a branched or linear alkyl group or aromatic group having 1 to 10 carbon atoms and having the functional group described above. Preferred examples of the functional group include alkyl groups having 1 to 5 carbon atoms and having a carbonyl group, such as an acetyl group or an acetoxy group.

[0079] R in general formula (5) ７ The carbonyl-containing organic group having 1 to 6 carbon atoms may be a branched or linear alkyl group or aromatic group having 1 to 6 carbon atoms and having the functional group described above. Examples of the functional group include an acetyl group and an acetoxy group.

[0080] Specific examples of the heterocyclic compound (B) represented by the general formula (3) include ganciclovir, guanosine, 3'-amino-2',3'-dideoxyguanosine, and penciclovir.

[0081] Specific examples of the heterocyclic compound (B) represented by general formula (4) include 2-[2-isobutylamido-6-oxo-1H-purin-9(6H)-yl]acetic acid, 2-{2-[(tert-butoxycarbonyl)amino]-6-oxo-1H-purin-9(6H)-yl}acetic acid, N-acetyl-di-O-acetylganciclovir, N ２ , 9-diacetylguanine.

[0082] Specific examples of the heterocyclic compound (B) represented by the general formula (5) include 2-acetamido-6-hydroxypurine, N-(6-oxo-6,7-dihydro-1H-purin-2-yl)isobutyramide, N ２2-acetamido-6-hydroxypurine, and N-(6-oxo-6,7-dihydro-1H-purin-2-yl)isobutyramide. When these are added to the resin composition, they may be in the form of a hydrate.

[0083] The content of the (B) heterocyclic compound is preferably 0.001 parts by mass or more and 20 parts by mass or less, more preferably 0.005 parts by mass or more and 15 parts by mass or less, and more preferably 0.01 parts by mass or more and 10 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 to exhibit sufficient effects in terms of copper adhesion and copper migration inhibition, and is preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less, in terms of copper adhesion, copper migration inhibition, and solubility in the composition. The reason for this is unclear and is not limited by theory, but it is presumed that by setting the upper limit of the content to 10 parts by mass or less, a brittle layer is less likely to form between the copper layer and the polyimide resin layer, resulting in good copper adhesion, and the ionic components in the resin layer do not increase more than necessary, thereby providing good copper migration inhibition.

[0084] (C) Photopolymerization Initiator The (C) photopolymerization initiator will be described. As the (C) photopolymerization initiator, a photoacid generator or a photoradical polymerization initiator can be used, but from the viewpoint of improving photosensitivity and suppressing copper migration, a photoradical polymerization initiator is preferred. Examples of the photoradical polymerization initiator 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; benzyl 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.

[0085] The content of the (C) 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.

[0086] (D) Solvent The photosensitive resin composition of this embodiment may contain a solvent (D), which will be described below. Examples of the solvent include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and alcohols. Examples of the solvent include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, and γ-butyronitrile. Lactone, 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, etc. Among these, from the viewpoints of resin solubility, resin composition stability, and substrate adhesion, 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.

[0087] 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, 3-butoxy-N,N-dimethylpropanamide, etc. 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.

[0088] The (D) solvent may be one type, or two or more types may be mixed and used, 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 this embodiment contains two or more types of (D) solvent, from the viewpoint of in-plane uniformity, 50 wt % or more of the (D) solvent is preferably either γ-butyrolactone or 3-methoxy-N,N-dimethylpropanamide, and more preferably γ-butyrolactone.

[0089] In the photosensitive resin composition of the present embodiment, the content of the (D) 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.

[0090] (E) Photopolymerizable Monomer The photosensitive resin composition of this embodiment may further contain (E) a photopolymerizable monomer. The use of (E) a photopolymerizable monomer promotes crosslinking of the photosensitive resin composition upon exposure, improving resolution, and also reducing the moisture permeability of the cured film, thereby suppressing copper migration. The photosensitive resin composition of this embodiment preferably contains 5 to 150 parts by mass of the 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 or more parts by mass of the (E) photopolymerizable monomer, more preferably 10 or more parts by mass, and even more preferably 20 or more parts by mass. On the other hand, if the (E) 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 speculated that a high content of (E) a photopolymerizable monomer may create 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.

[0091] The photopolymerizable monomer (E) is not particularly limited as long as it is a compound that undergoes a radical polymerization reaction with a photopolymerization initiator and a thermal polymerization initiator, but is preferably a (meth)acrylic compound, for example, a compound represented by the following general formula (50): {In the formula, X １１ is an organic group, and L １１ , L １２ and L １３ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. １１ is an integer from 1 to 10.

[0092] (E) Photopolymerizable monomers include, but are not limited to, 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; and diacrylate and dimethacrylate of 1,6-hexanediol. acrylate, diacrylate and dimethacrylate of neopentyl glycol, mono- or diacrylate and methacrylate of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, di- or triacrylate and methacrylate of glycerol, di-, tri-, or tetraacrylate and methacrylate of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds. More specifically, compounds represented by the following formulas (51) and (52): Examples of the compound include, but are not limited to, compounds represented by the following formula:

[0093] In the present disclosure, when the number of radical polymerizable groups in the (E) photopolymerizable monomer is one, it is referred to as a monofunctional group, and when the number is two or more, it is referred to as an x-functional group according to the number x of radical polymerizable groups, but difunctional or higher functional groups may also be collectively referred to as polyfunctional. The (E) photopolymerizable monomer may be monofunctional or may be difunctional or higher. From the viewpoint of suppressing copper migration, the (E) photopolymerizable monomer (e.g., a radical polymerizable compound) 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 (E) photopolymerizable monomer is preferably decafunctional or lower.

[0094] The molecular weight (in one embodiment, the weight average molecular weight) of the (E) photopolymerizable monomer is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more. The upper limit is preferably 1000 or less, and even more preferably 800 or less. By setting the weight average molecular weight of the (E) photopolymerizable monomer within the above range, resolution is improved.

[0095] The photopolymerizable monomer (E) may contain a hydroxyl group or a urea group.

[0096] The photopolymerizable monomer (E) having a hydroxyl group in the molecule includes a monomer represented by the following general formula (53): {In the formula, X １１ is an organic group having 1 to 200 carbon atoms, and L １１ , L １２ and L １３ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. １１ is an integer from 1 to 10, and n １２ is an integer of 1 to 10. In the above formula (53), L １１ is a hydrogen atom or a methyl group, and L １２ , L １３ is preferably a hydrogen atom from the viewpoint of radical reactivity. More specifically, the photopolymerizable monomer (E) having a hydroxyl group in the molecule is represented by the following formula (54): Examples include, but are not limited to, compounds represented by the formula: (E) Having a hydroxyl group in the molecular structure of the photopolymerizable monomer improves copper adhesion. The number of hydroxyl groups in the molecular structure of the photopolymerizable monomer (E) is preferably one or more, and more preferably two or more. The upper limit of the number of hydroxyl groups in the molecular structure 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 (E) photopolymerizable monomer within the above range, copper adhesion to the substrate improves.

[0097] The photopolymerizable monomer (E) having a urea group in the molecule is represented by the following general formula (55): {In the formula, X ２０ , X ２１ , X ２２ and X２３ are each independently a hydrogen atom, a monovalent organic group having a group represented by the following general formula (56), or a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and X ２０ , X ２１ , X ２２ and X ２３ At least one of the groups is a monovalent organic group having a group represented by the following general formula (56): {In the formula, L １１ , L １２ and L １３ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. １１ is a hydrogen atom or a methyl group, and L １２ , L １３ is preferably a hydrogen atom from the viewpoint of radical reactivity.

[0098] Examples of the heteroatom include an oxygen atom, a nitrogen atom, a phosphorus atom, and a sulfur atom.

[0099] X in formula (55) ２０ , X ２１ , X ２２ and X ２３ When 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. ２０ , X ２１ , X ２２ and X ２３ The number of carbon atoms in X in formula (55) 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. ２０ , X ２１ , X ２２ and X ２３ 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. ２０ , X ２１ , X ２２ and X ２３ When X are bonded to each other to form a cyclic structure, the degree of freedom of the bond angle of the urea group is lost, making it difficult to form a strong hydrogen bond. ２０ , X２１ , X ２２ and X ２３ On the other hand, from the viewpoint of solubility, it is preferable that at least one of X is a hydrogen atom. ２０ , X ２１ , X ２２ and X ２３ It is preferable that the number of hydrogen atoms in the formula (57) is two or less. Examples include compounds represented by the following formula:

[0100] The photopolymerizable monomer (radical polymerizable compound) (E) 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 (58): {In the formula, X ３０ , X ３１ , X ３２ and X ３３ are each independently a hydrogen atom, a monovalent organic group having a group represented by the following general formula (59), or a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and X ３０ , X ３１ , X ３２ , X ３３ At least one of the groups is a monovalent organic group having a group represented by the following general formula (59), and at least one of the groups is a hydroxyl group.} {In the formula, L １１ , L １２ and L １３ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. １１ is a hydrogen atom or a methyl group, and L １２ , L １３ is preferably a hydrogen atom from the viewpoint of radical reactivity.

[0101] In formula (58), X ３０ , X ３１ , X ３２ and X ３３ When 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. ３０ , X ３１ , X ３２ and X ３３The number of carbon atoms in X in formula (58) 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. ３０ , X ３１ , X ３２ , X ３３ 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. ３０ , X ３１ , X ３２ and X ３３ When X are bonded to each other to form a cyclic structure, the degree of freedom of the bond angle of the urea group is lost, making it difficult to form a strong hydrogen bond. ３０ , X ３１ , X ３２ and X ３３ On the other hand, from the viewpoint of solubility, it is preferable that at least one of X is a hydrogen atom. ３０ , X ３１ , X ３２ and X ３３ The number of hydrogen atoms in the photopolymerizable monomer (E) having at least one hydroxyl group and at least one urea group in the molecule is preferably two or less. Specifically, the photopolymerizable monomer (E) is represented by the following formula (60): Examples of the compound include compounds represented by the following formula:

[0102] The photopolymerizable monomer (E) 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 same 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.

[0103] The photopolymerizable monomer (E) may be used singly or in a mixture of two or more. When two or more photopolymerizable monomers (E) are used in a mixture, the number of types is preferably six or less, and more preferably four or less, from the viewpoint of controlling the crosslink density.

[0104] When a mixture of multiple (E) photopolymerizable monomers is used, it is preferable that at least one of the multiple (E) photopolymerizable monomers has a different number of functional groups. When three or more (E) 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 (E) photopolymerizable monomers have different numbers of functional groups. When a mixture of multiple (E) photopolymerizable monomers is used, it is preferable that at least one monofunctional photopolymerizable monomer is included from the viewpoint of elongation at break.

[0105] (F) Thermal Crosslinking Agent In order to suppress copper migration in the cured film, the photosensitive resin composition of this embodiment may optionally contain (F) a thermal crosslinking agent.

[0106] The thermal crosslinking agent (F) is not particularly limited as long as it forms crosslinks when the relief pattern formed using the photosensitive resin composition of this embodiment is heat-cured, but it can react with the polyimide precursor (A) and / or the polyimide resin (F), with the thermal crosslinking agent (F), with each other, or with other components to form a crosslinked product. The reaction temperature is preferably 150° C. or higher.

[0107] Examples of the (F) 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 (F) thermal crosslinking agent preferably contains a nitrogen atom.

[0108] Examples of the alkoxymethyl compound include, but are not limited to, compounds represented by the following formula (61):

[0109] Commercially available alkoxymethyl compounds include alkylated urea resin (product name: Nikalac MX290, manufactured by Sanwa Chemical Co., Ltd.) and 1,3,4,6-tetrakis(methoxymethyl)glycoluril (product name: Nikalac MX270, manufactured by Sanwa Chemical Co., Ltd.).

[0110] 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.

[0111] 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, ...

[0112] 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.

[0113] 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.

[0114] Examples of the blocked isocyanate compound include hexamethylene diisocyanate-based blocked isocyanates (for example, manufactured by Asahi Kasei Corporation under the trade names Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B, and WM44-L70G; manufactured by Mitsui Chemicals, Inc. under the trade name Takenate B-882N; and manufactured by Baxenden under the trade names 7960, 7961, 7982, 7991, and 7992); tolylene diisocyanate-based blocked isocyanates (for example, manufactured by Mitsui Chemicals, Inc. under the trade name Takenate B-830); 4,4'- Examples of such blocked isocyanates include 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).

[0115] Among these, alkoxymethyl compounds are preferred from the viewpoint of copper adhesion. (F) The thermal crosslinking agent may be used alone or in combination of two or more kinds.

[0116] The content of the (F) thermal crosslinking agent in the photosensitive resin composition of the present disclosure is preferably 0.2 parts by mass to 40 parts by mass 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 (F) 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 (F) 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.

[0117] (G) Silane Coupling Agent In order to improve the copper adhesion of the cured film, the photosensitive resin composition of this embodiment may optionally contain (G) a silane coupling agent.

[0118] Examples of the silane coupling agent (G) 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, manufactured by Azmax Corporation: trade name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Corporation: trade name SIM6473.5C), and mercaptomethylmethyldimethoxysilane (manufactured by Azmax Corporation: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltrippropoxysilane, 2-mercaptoethyltripropoxysilane Examples of the mercaptosilane include, but are not limited to, mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 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.

[0119] Other examples of the silane coupling agent (G) include N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd. under the trade name LS3610, and Azmax Co., Ltd. under the trade name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Co., Ltd. under the trade name SIU9058.0), N-(3-diethoxymethoxysilylpropyl)urea, N-(3-ethoxydimethoxysilylpropyl)urea, N-(3-tripropoxysilylpropyl)urea, N-(3-diethoxypropoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-dimethoxypropoxysilylpropyl)urea, N-(3-methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea, N-(3-ethoxydimethoxysilylethyl ) urea, N-(3-trippropoxysilylethyl) urea, N-(3-trippropoxysilylethyl) urea, N-(3-ethoxydipropoxysilylethyl) urea, N-(3-dimethoxypropoxysilylethyl) urea, N-(3-methoxydipropoxysilylethyl) urea, N-(3-trimethoxysilylbutyl) urea, N-(3-triethoxysilylbutyl) urea, N-(3-trippropoxysilylbutyl) urea, 3-(m-aminophenoxy)propyltrimethoxysilane (trade name, manufactured by Azmax Corporation) Examples of the silane include, but are not limited to, 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).

[0120] Further, examples of the silane coupling agent (G) 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(methacryloylsilane), bis(triethoxysilane), 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, phenyl silanetriol, methyl phenyl silanediol, ethyl phenyl silanediol, n-propyl phenyl silanediol, isopropyl phenyl silanediol, n-butyldiphenyl silanediol, isobutylphenyl silanediol, tert-butylphenyl silanediol, diphenyl silanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethyl methyl phenyl silanol, n-propyl methyl phenyl silanol, isopropyl methyl phenyl silanol, n-butylmethyl phenyl silanol, isobutylmethyl phenyl silanol, tert-butylmethyl phenyl silanol, ethyl n-propyl phenyl silanol, ethyl isopropyl phenyl silanol, n-butylethyl phenyl silanol, isobutylethyl phenyl silanol, tert-butylethyl phenyl silanol,Examples of the silanol include, but are not limited to, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, and triphenylsilanol.

[0121] The silane coupling agents (G) listed above may be used alone or in combination. Among the silane coupling agents listed above, N-phenyl-3-aminopropyltrimethoxysilane, (3-triethoxysilylpropyl)-t-butylcarbamate, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane are preferred from the viewpoint of copper adhesion.

[0122] When (G) the silane coupling agent is used, the content is preferably 0.01 to 20 parts by mass per 100 parts by mass of (A) the polyimide precursor and / or polyimide resin from the viewpoint of copper adhesion.

[0123] (H) Acid Component 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 an (H) acid component. By using the acid component in combination with the (F) thermal crosslinking agent, the thermal crosslinking reaction of the (F) thermal crosslinking agent can be promoted, and the copper migration suppression effect can be improved.

[0124] Examples of the (H) acid component 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.

[0125] When the (H) acid component is used, the content thereof is preferably 0.001 to 5 parts by mass relative to 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 (H) acid component 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 adhesion, the upper limit of the (H) acid component is more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less.

[0126] The photosensitive resin composition of this embodiment may further contain components other than the above components (A) to (H). Examples of components other than components (A) to (H) include, but are not limited to, (I) a thermal base generator, (J) a hindered phenol compound, (K) an organic titanium compound, (L) a sensitizer, and (M) a polymerization inhibitor.

[0127] (I) Thermal Base Generator The photosensitive resin composition of this embodiment may contain (I) a thermal base generator. The (I) thermal base generator refers to a compound that generates a base upon heating. By containing the (I) thermal base generator, it is possible to further promote imidization of the photosensitive resin composition.

[0128] (I) The thermal base generator is not particularly limited in type, 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.

[0129] 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.

[0130] The content of the (I) thermal base generator 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 (A) polyimide precursor and / or polyimide resin. The content 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.

[0131] (J) Hindered Phenol Compound In order to suppress discoloration on the copper surface, the photosensitive resin composition of this embodiment may optionally contain (J) a hindered phenol compound.

[0132] (J) 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, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, and the like.

[0133] Examples of the hindered phenol compound (J) 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.

[0134] 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.

[0135] The content of the (J) 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. When the content 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 is 20 parts by mass or less, excellent photosensitivity is achieved.

[0136] (K) Organotitanium Compound The photosensitive resin composition of this embodiment may contain (K) an organotitanium compound. By containing (K) the photosensitive resin composition of this embodiment, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at low temperature.

[0137] Usable organic titanium compounds (K) include those in which an organic chemical substance is bonded to a titanium atom via a covalent bond or an ionic bond.

[0138] Specific examples of (K) organic titanium compounds are shown below in I) to VII): I) Titanium chelate compounds: Among these, titanium chelates having two or more alkoxy groups are more preferred because they improve the storage stability of the photosensitive resin composition and allow 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), titanium diisopropoxide bis(ethylacetoacetate), etc.

[0139] 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, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], etc.

[0140] III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η ５ -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η ５ -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.

[0141] IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.

[0142] V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.

[0143] VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate.

[0144] VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate.

[0145] Among these, it is preferable that the (K) organic titanium compound is at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of exhibiting better chemical resistance. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η ５ 3-(1H-pyrrol-1-yl)phenyl)titanium is preferred.

[0146] When the (K) organotitanium compound is contained, the content thereof 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. When the content is 0.05 part by mass or more, good heat resistance and chemical resistance are exhibited, while when the content is 10 parts by mass or less, excellent storage stability is achieved.

[0147] (L) Sensitizer The photosensitive resin composition of the present embodiment may optionally contain (L) a sensitizer in order to improve photosensitivity.

[0148] Examples of the (L) 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 iso amyl, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, 2,2′-(phenylimino)diethanol, etc. These can be used alone or in combination of, for example, 2 to 5 types.

[0149] When the photosensitive resin composition of the present embodiment contains the sensitizer (L), the content thereof is preferably 0.1 to 25 parts by mass per 100 parts by mass of the polyimide precursor and / or polyimide resin (A).

[0150] (M) Polymerization Inhibitor The photosensitive resin composition of the present embodiment may optionally contain (M) a polymerization inhibitor in order to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition, particularly during storage in the form of a solution containing a solvent.

[0151] Examples of the (M) 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.

[0152] <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.

[0153] (1) Photosensitive Resin Layer Formation Step In this step, a photosensitive resin composition 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.

[0154] (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.

[0155] (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.

[0156] The developer used for development is preferably, for example, a good solvent for the photosensitive resin composition, or a combination of the 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. Furthermore, two or more types of each solvent, for example, several types, can be used in combination.

[0157] 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.

[0158] (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 imidize the (A) polyimide precursor, 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 higher, more preferably 250°C or higher. To achieve both copper adhesion and copper migration suppression, the heat treatment temperature is preferably 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.

[0159] <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 above-described method for producing a cured relief pattern. 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 polyimide product with an imidization rate of 80 to 100%. In this case, too, a polyimide film can be produced based on the above-described method for producing a cured relief pattern. The structure of the polyimide contained in the cured relief pattern formed from the polyimide precursor composition is represented by the following general formula (62):

[0160] Preferred X in formulas (6) and (7) １ , Y １ For the same reason, is also preferred in the polyimide having the structure represented by the general formula (62). ２ is not particularly limited, but may be an integer from 2 to 150.

[0161] <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.

[0162] <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.

[0163] 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 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.

[0164] 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.

[0165] <Measurement and Evaluation Methods> (1) Weight-Average Molecular Weight The weight-average molecular weight (Mw) of each resin was measured by 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 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.

[0166] (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 type, manufactured by ULVAC Corporation). Subsequently, the photosensitive resin composition was spin-coated on this wafer using a coater developer (D-Spin 60A type, 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 type, 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 Co., Ltd.) under a nitrogen atmosphere at the temperatures shown in Tables 1 to 4 to obtain a cured relief pattern (thermo-cured polyimide coating film).

[0167] An Evercel OPP tape (No. 830NEV, manufactured by Sekisui Chemical Co., Ltd.) was applied to this sample, and the 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 tape and polyimide coating film were peeled off at an angle of 180 degrees at a speed of 50 mm / min for 60 mm so as to separate the copper and the polyimide, and the load at this time was calculated as an integrated average, and this value was evaluated as the adhesion strength. If the evaluation was C or higher, the sample can be suitably used as a cured relief pattern for semiconductors. A: Adhesion strength is 0.4 N / mm or more B: Adhesion strength is 0.3 N / mm or more but less than 0.4 N / mm C: Adhesion strength is 0.2 N / mm or more but less than 0.3 N / mm D: Adhesion strength is less than 0.2 N / mm

[0168] (3) b-HAST test SiO on the surface ｘA TEG wafer was prepared by forming comb-shaped Cu 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, then rinsed with running ion-exchanged water and dried with an air gun. An oxygen plasma treatment was then performed using an ashing device (NA-8000, manufactured by ULVAC) at an oxygen flow rate of 1500 mL / min, 50 Pa, MW 1500 W, and RF 200 W at 25°C for 120 seconds. The photosensitive resin composition was then spin-coated using a coater developer (D-Spin 60A, manufactured by SOKUDO Corporation) 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 . ２ The film was exposed to light. To ensure electrical continuity during the b-HAST test, the Cu electrode portion was masked to prevent exposure to light, and the unexposed portion was removed by subsequent development. After 30 minutes or more had elapsed since the exposure, the film was subjected to rotary spray development using a coater developer (D-Spin 60A model, manufactured by SOKUDO Co., Ltd.) at 23°C using cyclopentanone as the developer for a time 1.4 times the time required for the unexposed portion to completely dissolve and disappear, followed by rotary spray rinsing with propylene glycol monomethyl ether acetate for 10 seconds. The film was then heated for 2 hours in a temperature-programmable curing oven (VF-2000 model, manufactured by Koyo Lindberg Co., Ltd.) under a nitrogen atmosphere at the temperatures listed in Tables 1 to 4, yielding a cured relief pattern.

[0169] This sample was subjected to a b-HAST test using an ion migration evaluation system (AMI-025-U-5, manufactured by Espec Corp.) and a highly accelerated life tester HAST chamber (EHS-222M, manufactured by Espec Corp.) 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 value was 1 × 10 ４When the resistance dropped to Ω or less, it was deemed to have been a dielectric breakdown. The time from the start of the test to the 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 a cured relief pattern for semiconductors. A: 500 hours or more have passed until the dielectric breakdown. B: 300 hours or more but less than 500 hours have passed until the dielectric breakdown. C: 100 hours or more but less than 300 hours have passed until the dielectric breakdown. D: Less than 100 hours have passed until the dielectric breakdown.

[0170] (4) Resolution Evaluation A 200 nm thick titanium (Ti) and a 400 nm thick copper (Cu) were sputtered in this order onto a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm) using a sputtering device (SME-200E type, manufactured by ULVAC Corporation). Subsequently, the photosensitive resin composition was spin-coated onto this wafer using a coater developer (D-Spin 60A type, 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. This coating film was then irradiated with 50 mJ / cm using a lithography system (Ultratech AP-200, manufactured by Veeco) through circular masks with diameters of 9 μm, 10 μm, and 11 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 Co., Ltd.) at 23°C using cyclopentanone as a developer for a time period 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-programmable curing oven (VF-2000 model, manufactured by Koyo Lindberg Co., Ltd.) under a nitrogen atmosphere at the temperatures listed in Tables 1 to 4, to obtain a cured relief pattern.

[0171] The circular hole pattern obtained for 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 the circular hole had no hollow at the bottom, a forward tapered opening, and the area of ​​the obtained circular hole opening was at least half the area of ​​the corresponding pattern mask opening, the pattern was deemed to have been resolved, and the smallest diameter of the exposure mask among the resolved openings was shown as the evaluation result.

[0172] <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 the mixture was stirred at room temperature, and 81.5 g of pyridine was added while stirring 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.

[0173] 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 formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0174] 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.

[0175] Production Example 2: (A) Synthesis of Polyimide Precursor A2

[0047] 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.

[0176] 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.

[0177] 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.

[0178] Production Example 5: (A) Synthesis of Polyimide Precursor A5

[0077] 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.

[0179] Production Example 6: (A) Synthesis of Polyimide Resin A6

[0049] 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. 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.

[0180] 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-neck 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.

[0181] 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.

[0182] 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.

[0183] 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.

[0184] Example 1 Photosensitive resin compositions were prepared using polyimide precursors A1 and A2 by the following method, and the prepared compositions were evaluated. (A) As polyimide precursors, polymers A1 and A2: 40 g of the polyimide precursor described in Production Example 1 and 60 g of the polyimide precursor described in Production Example 2; (B) as heterocyclic compounds, B1: 0.5 g of 2-acetamido-6-hydroxypurine (manufactured by Tokyo Chemical Industry Co., Ltd.); (C) as photopolymerization initiator, C1: 5 g of 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.); (E) as photopolymerizable monomer, E1: 5 g of NK Ester 4G (manufactured by Shin-Nakamura Chemical Co., Ltd.); (F) as thermal crosslinking agent, F1: 1 g of Nikalac MX-290 (manufactured by Sanwa Chemical Co., Ltd.); (G) as silane coupling agent, G1: 1 g of KBM573 (manufactured by Shin-Etsu Chemical Co., Ltd.); (K) as organic titanium compound, K1: Orgatix 0.5 g of TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.), 10 g of L1: 2,2'-(phenylimino)diethanol (manufactured by Kanto Chemical Co., Ltd.) as a sensitizer (L), and 80 g of D1: γ-butyrolactone (hereinafter referred to as GBL, manufactured by Mitsubishi Chemical Corporation) as a solvent (D) and 20 g of solvent D2: dimethyl sulfoxide (hereinafter referred to as DMSO, manufactured by Toray Fine Chemicals Co., Ltd.) were dissolved in a mixed solvent. 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. The composition was evaluated according to the method described above. The results are shown in Table 1.

[0185] Examples 2 to 51, Comparative Examples 1 to 7 Photosensitive resin compositions were prepared by dissolving the components other than the (D) solvent in the (D) solvent in the blending ratios shown in Tables 1 to 4, and adjusting the viscosity in the same manner as in Example 1. The photosensitive resin compositions shown in Tables 1 to 3 were evaluated for copper adhesion and copper migration inhibition performance. The photosensitive resin compositions shown in Table 4 were evaluated for copper adhesion and copper migration inhibition performance, as well as for resolution. The results of the examples are shown in Tables 1 to 4. The compounds (components (A) to (L)) listed in Tables 1 to 4 are as follows:

[0186] (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 A1': ZCR-1797H (acid-modified epoxy acrylate having a biphenyl skeleton, manufactured by Nippon Kayaku Co., Ltd.)

[0187] (B) Heterocyclic Compounds B1: 2-acetamido-6-hydroxypurine (manufactured by Tokyo Chemical Industry Co., Ltd.) B2: N-(6-oxo-6,7-dihydro-1H-purin-2-yl)isobutyramide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) B3: Ganciclovir (manufactured by Tokyo Chemical Industry Co., Ltd.) B4: Guanosine (manufactured by Tokyo Chemical Industry Co., Ltd.) B5: 3'-amino-2',3'-dideoxyguanosine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) B6: Penciclovir (manufactured by Tokyo Chemical Industry Co., Ltd.) B7: N ２ B8: 2-(2-isobutylamido-6-oxo-1H-purin-9(6H)-yl)acetic acid (Sigma-Aldrich) B9: N-acetyl-di-O-acetylganciclovir (Tokyo Chemical Industry Co., Ltd.) B10: N ２ -isobutyrylguanosine (manufactured by Tokyo Chemical Industry Co., Ltd.) B11: 9-ethylguanine (manufactured by Sigma-Aldrich) B12: 2-amino-9-phenyl-1H-purin-6(9H)-one (manufactured by BLDpharm) B13: N-(6-oxo-6,9-dihydro-1H-purin-2-yl)benzamide (manufactured by BLDpharm) B14: N ２ B1': 8-azaadenine (manufactured by Tokyo Chemical Industry Co., Ltd.) B2': 5-amino-1H-tetrazole (manufactured by Chiyoda Chemical Co., Ltd.) B3': 1,2,3-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.) B4': hypoxanthine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0188] (C) Photopolymerization initiator C1: 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.)

[0189] (D) Solvent D1: GBL (manufactured by Mitsubishi Chemical Corporation) D2: DMSO (manufactured by Toray Fine Chemicals Co., Ltd.)

[0190] (E) Photopolymerizable Monomers E1: Tetraethylene glycol dimethacrylate (product name NK Ester 4G, manufactured by Shin-Nakamura Chemical Co., Ltd.) E2: Tris-(2-acryloxyethyl) isocyanurate (product name NK Ester A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.) E3: Pentaerythritol tetraacrylate (product name NK Ester A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.) E4: Tricyclodecane dimethanol dimethacrylate (product name NK Ester DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0191] (F) Thermal crosslinking agent F1: Alkylated urea resin (product name: Nikalac MX-290, manufactured by Sanwa Chemical Co., Ltd.) F2: 1,3,4,6-tetrakis(methoxymethyl)glycoluril (product name: Nikalac MX-270, manufactured by Sanwa Chemical Co., Ltd.)

[0192] (G) Silane coupling agents G1: N-phenyl-3-aminopropyltrimethoxysilane (product name: KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.) G2: (3-triethoxysilylpropyl)-t-butylcarbamate (manufactured by Gelest) G3: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0193] (H) Acid Components H1: (±)-Mandelic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) H2: p-Toluenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0194] (K) Organic titanium compound K1: diisopropoxytitanium bis(ethyl acetate) (product name: Orgatix TC-750, manufactured by Matsumoto Fine Chemical Co., Ltd.)

[0195] (L) Sensitizer L1: 2,2'-(phenylimino)diethanol (Kanto Chemical Co., Ltd.)

[0196]

[0197]

[0198]

[0199]

[0200] Looking at the results in Tables 1 to 3, Comparative Examples 1 to 7, which do not satisfy the requirements of the present disclosure, are unable to improve both copper adhesion and copper migration performance (b-HAST test results). On the other hand, Examples 1 to 51, which satisfy claim 1 of the present disclosure, demonstrate excellent performance in both copper adhesion and copper migration suppression performance. Comparisons of Comparative Examples 2 to 4 and Comparative Example 6 with Examples 1 to 14, and a comparison of Comparative Example 5 with Example 40, reveal that the use of the (B) heterocyclic compound of the present disclosure improves copper adhesion, demonstrating good copper adhesion even at a high cure temperature of 250°C. Furthermore, a comparison of Comparative Example 1 with Examples 18 to 21 reveals that the use of the (B) heterocyclic compound of the present disclosure improves copper migration suppression performance and copper adhesion, even at a low cure temperature of 200°C. Furthermore, a comparison of Comparative Example 7 with Example 41 reveals that the use of the (A) polyimide precursor and / or polyimide resin of the present disclosure improves both copper adhesion and copper migration suppression performance.

[0201] Next, looking at the Examples, a comparison of Examples 1 to 9 and 14 with Examples 10 to 13 reveals that (B) heterocyclic compounds of the present disclosure having structures of general formulas (3) to (5) are preferable in terms of copper adhesion compared to those having structures of general formulas (1) or (2). While the reason for this is unclear and not limited by theory, it is speculated that the hydroxyl groups and carbonyl groups of the (B) heterocyclic compounds strengthen their interaction with copper. Examples 1 and 15 to 17 have compositions with different (B) heterocyclic compound contents, but Examples 1 and 16, in which the content is in the range of 0.01 to 10 parts by mass, exhibit superior copper adhesion or copper migration suppression performance. While the reason for this is unclear and not limited by theory, it is speculated that by setting the (B) heterocyclic compound content to 10 parts by mass or less, the ionic components in the photosensitive resin layer do not increase more than necessary, resulting in improved copper migration suppression performance.

[0202] Examples 36 to 39 are examples in which polyimide resins were used, but the polyimide resin (A) used in Examples 36, 37, and 39 did not contain fluorine, and therefore it was found that the copper migration suppression performance was better than that of Example 38, which used a polyimide resin (A) containing fluorine.

[0203] Comparing Example 50 and Example 51 in Table 4, the inclusion of the photopolymerizable monomer (E) reduces the minimum opening size and improves the resolution. It is presumed that the use of the photopolymerizable monomer (E) promotes crosslinking of the photosensitive resin composition, thereby improving the resolution.

[0204] A comparison of Example 1 with Example 49 shows that the inclusion of the thermal crosslinking agent (F) improves copper adhesion and copper migration suppression performance. Furthermore, a comparison of Example 1 with Examples 43 to 45 shows that the inclusion of the silane coupling agent (G) improves copper adhesion. Furthermore, a comparison of Examples 46 to 48 shows that the inclusion of the acid component (H) improves copper migration suppression performance.

[0205] By using the photosensitive resin composition according to the present disclosure, it is possible to obtain a cured relief pattern that exhibits excellent copper adhesion even when cured at high temperatures and exhibits little copper migration in the b-HAST test. 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, as well as passivation films, buffer coat films, and interlayer insulating films in semiconductor devices.

Claims

1. A photosensitive resin composition comprising the following components: (A) a polyimide precursor and / or polyimide resin; (B) a heterocyclic compound; and (C) a photopolymerization initiator, wherein the heterocyclic compound (B) is a compound represented by the following general formula (1): {In the formula, R １ is an organic group, and R ２ is a hydrogen atom or an organic group.}, or (b2) a compound represented by the following general formula (2): {In the formula, R ３ is an organic group having at least one carbonyl group.

2. The compound (b1) is represented by the following general formula (3): {In the formula, R ４ is an organic group having 1 to 10 carbon atoms and having at least one hydroxyl group or carbonyl group.}, or a compound represented by the following general formula (4): {In the formula, R ５ and R ６ are each independently an organic group having 1 to 10 carbon atoms and having at least one carbonyl group.}, and the compound (b2) is a compound represented by the following general formula (5): {In the formula, R ７ is an organic group having 1 to 6 carbon atoms and having at least one carbonyl group.}.

3. The photosensitive resin composition contains the polyimide precursor, and the polyimide precursor is represented by the following general formula (6): {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 ９ and R １０ are each independently a hydrogen atom or a monovalent organic group.}, and / or the photosensitive resin composition contains the polyimide resin, and the polyimide resin is represented by the following general formula (7): {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, wherein n is an integer of 2 to 150.

4. In the above general formula (6), R ９ and R １０ At least one of the following general formula (8): {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 3, wherein n is an integer of 2 to 10.

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

6. The photosensitive resin composition according to claim 5, wherein the photoradical polymerization initiator is an oxime initiator.

7. The photosensitive resin composition according to claim 1 or 2, wherein the content of said component (B) is 0.01 to 10 parts by mass per 100 parts by mass of said component (A).

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

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

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

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

12. The photosensitive resin composition according to claim 1 or 2, which contains an acid component (H).

13. 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.

14. 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.

15. The method for producing a cured relief pattern according to claim 14, wherein the heat treatment in step (4) is a heat treatment at 170°C or higher and 350°C or lower.

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

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

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