WO2025225661A1 - Photosensitive resin composition, and cured relief pattern production method, cured film, and polyimide film production method using photosensitive resin composition - Google Patents

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

This 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.

Conventionally, polyimide resins, polybenzoxazole resins, phenolic resins, and other resins, which combine excellent heat resistance and electrical and mechanical properties, have been used as insulating materials for electronic components, and for passivation films, surface protection films, and interlayer insulating films 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 that involves curing. Such photosensitive resin compositions have the advantage of enabling significant process reductions compared to conventional non-photosensitive materials.

Meanwhile, in recent years, the methods of mounting semiconductor devices to printed wiring boards (packaging structures) have also changed in light of improvements in integration density and computing functionality, as well as the need to reduce chip size. Conventional mounting methods using metal pins and lead-tin eutectic solder have been replaced by structures in which a polyimide coating directly contacts the solder bumps, such as BGA (ball grid array) and CSP (chip size packaging), which enable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, structures have been proposed, such as FO (fan-out), which have multiple redistribution layers on the surface of a semiconductor chip, each with an area larger than the area of the semiconductor chip itself (see Patent Document 1).

Copper is often used for the wiring of semiconductor devices, but in large-area packaging structures, stress caused by differences in the thermal expansion coefficients of different materials can cause peeling between the copper and interlayer insulating material, resulting in a decrease in electrical properties, which can be a particular problem. For this reason, materials used as interlayer insulating films are required to have high adhesion to copper. For example, Patent Document 2 describes the use of purine derivatives to prevent copper discoloration and improve adhesion.

U.S. Pat. No. 1,065,8199 JP 2012-194520 A

In recent years, there has been a demand for finer wiring widths in semiconductor elements and circuits in order to improve the performance, increase functionality, reduce power consumption, and reduce costs of semiconductor devices. As finer wiring advances, higher resolution is also becoming more important for interlayer insulating films. Furthermore, as the wiring width becomes smaller with finer wiring, copper can migrate into the resin layer (interlayer insulating film) (hereinafter referred to as "copper migration" in this disclosure), causing short circuits between wiring.

Furthermore, semiconductor devices are increasingly being used in automobiles and mobile phones, and high reliability is required of semiconductor devices in these fields, so reliability tests are being conducted in high-temperature, high-humidity environments.

Conventional interlayer insulating films may experience the above-mentioned copper migration during reliability tests under high temperature and high humidity (b-HAST: Biased Highly Accelerated Stress Test). Copper migration, particularly in semiconductor devices with fine wiring, can cause short circuits between wiring, 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 wiring and the resin layer. When copper voids occur at the interface between the copper wiring and the resin layer, the adhesion between them may decrease, causing the resin to peel off from the copper, resulting in impaired insulation.
On the other hand, resins are sometimes cured at high temperatures to improve copper migration suppression and film properties, but curing conventional interlayer insulating films at high temperatures can sometimes result in a decrease in copper adhesion.

Therefore, one of the objects of the present disclosure is to provide a photosensitive resin composition that achieves high copper adhesion even when cured at high temperatures, exhibits little copper migration in the b-HAST test, i.e., does not short circuit over long periods 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.

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]
Ingredients:
A photosensitive resin composition comprising: (A) a polyimide precursor and/or a polyimide resin; (B) a heterocyclic compound; and (C) a photopolymerization initiator,
The heterocyclic compound (B) is
(b1) The following general formula (1):
{wherein 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):
{wherein _R3 is an organic group having at least one carbonyl group.}.
[2]
The compound (b1) is represented by the following general formula (3):
{wherein 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):
{wherein _R5 and _R6 each independently represent an organic group having 1 to 10 carbon atoms and having at least one carbonyl group.}
The compound (b2) is represented by the following general formula (5):
{In the formula, _R7 is an organic group having 1 to 6 carbon atoms and at least one carbonyl group.}
The photosensitive resin composition according to [1], wherein the compound is represented by the formula:
[3]
The photosensitive resin composition contains the polyimide precursor, and the polyimide precursor is represented by the following general formula (6):
{In the formula, _X1 is a tetravalent organic group, _Y1 is a divalent organic group, _n1 is an integer from 2 to 150, and _R9 and _R10 are each independently a hydrogen atom or a monovalent organic group.}
and/or the photosensitive resin composition contains the polyimide resin,
The polyimide resin is represented by the following general formula (7):
{In the formula, _X2 is a tetravalent organic group, _Y2 is a divalent organic group, and _n2 is an integer from 2 to 150.}
The photosensitive resin composition according to [1] or [2], having a structural unit represented by the following formula:
[4]
In the above general formula (6), at least one of R ₉ and R ₁₀ is a group represented by the following general formula (8):
{In the formula, L ₁ , L ₂ and L ₃ each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m ₁ represents an integer of 2 to 10.}
The photosensitive resin composition according to [3], having a structural unit represented by the following formula:
[5]
The photosensitive resin composition according to any one of [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 component (B) is 0.01 to 10 parts by mass per 100 parts by mass of the component (A).
[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]
The following steps:
(1) A step of 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;
(4) A method for producing a cured relief pattern, comprising the step of: 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].

This disclosure provides a photosensitive resin composition that achieves high copper adhesion through high-temperature curing, exhibits minimal copper migration in the b-HAST test, and has high resolution. It also provides methods for producing cured relief patterns using this photosensitive resin composition, and methods for producing cured films and polyimide films.

The following describes in detail the embodiments of the present disclosure. The present disclosure is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the disclosure. Note that throughout this disclosure, structures represented by the same symbol in a general formula may be the same or different when multiple structures exist in a molecule. Furthermore, the upper and lower limit values of each numerical range in the present disclosure can be combined in any combination to form any numerical range.

<Photosensitive resin composition>
The photosensitive resin composition of the present disclosure contains (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 invention is characterized in that the heterocyclic compound (B) is
(b1) The following general formula (1):
{wherein 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):
{wherein _R3 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.

(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.

The polyimide precursor (A) is represented by the following general formula (6):
{wherein _X1 is a tetravalent organic group, _Y1 is a divalent organic group, _n1 is an integer of 2 to 150, and _R9 and _R10 are each independently a hydrogen atom or a monovalent organic group.} is preferred.
The polyimide precursor represented by the formula (6) is preferably a polyamide having a structure in which _Y1 does not have an acidic group such as a carboxylic acid group or a phenolic hydroxyl group. Furthermore, in the formula (6), _X1 preferably does not have an acidic group, except for a carboxyl group present when _R9 or _R10 is a hydrogen atom. Since the polyimide precursor (A) does not have an acidic group in its structure, it is easy to obtain a polyimide precursor that is not alkali-soluble.

In the general formula (6), at least one of R ₉ and R ₁₀ preferably contains a photopolymerizable functional group, and is represented by the following general formula (8):
{wherein L ₁ , L ₂ and L ₃ each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m ₁ represents an integer of 2 to 10.}

The proportion of hydrogen atoms in _R9 and _R10 in general formula (6) 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 of R9 and R10. By setting this proportion, it is easy to obtain a polyimide precursor that is not alkali-soluble.
Furthermore, the proportion of _R9 and _R10 in general formula (6) that are monovalent organic groups represented by the above general formula (8) is preferably 70 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more, based on the total number of moles of _R9 and _R10 . It is preferable that the proportion of hydrogen atoms and the proportion of organic groups of general formula (8) are within the above ranges from the viewpoints of photosensitive properties and storage stability.

In the general formula (6), n1 is not limited as long as it is an integer of 2 to 150. From the viewpoint of the photosensitivity and mechanical properties of the photosensitive resin composition, _n1 is preferably an integer of 3 to 100, and more preferably an integer of 5 to 70.

In general formula (6), the tetravalent organic group represented by _X1 is preferably an organic group having 6 to 40 carbon atoms, from the viewpoint of achieving both heat resistance and photosensitive properties, and more preferably an aromatic group in which the _-COOR9 group and the _-COOR10 group are in the ortho position relative to the -CONH- group, or an alicyclic aliphatic group. Specific examples of the tetravalent organic group represented by _X1 include organic groups having 6 to 40 carbon atoms and containing an aromatic ring, such as those represented by the following general formula (9):
{wherein 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 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.
The structure of X ₁ may be one type or a combination of two or more types. The X ₁ group having the structure represented by the above formula (9) is particularly preferred from the viewpoint of achieving both heat resistance and photosensitive properties.

As the _X1 group, among the structures represented by the above formula (9), particularly, those represented by the following formula (10):
A tetravalent organic group represented by the formula: {wherein 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.

In the above general formula (6), the divalent organic group represented by _Y1 is preferably an aromatic group having 6 to 40 carbon atoms, from the viewpoint of achieving both heat resistance and photosensitive properties, and is, for example, a group represented by the following formula (11):
{wherein 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.} However, the examples are not limited to these. The structure of Y ₁ may be one type or a combination of two or more types. A Y ₁ group having a structure represented by the above formula (11) is particularly preferred from the viewpoint of achieving both heat resistance and photosensitive properties.

As the _Y1 group, among the structures represented by the above formula (11), particularly, those represented by the following formula (12):
A divalent group represented by the formula: {wherein 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, 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.

The monovalent organic group having 1 to 3 carbon atoms for _L1 , _L2 , and _L3 in the general formula (8) is, for example, a hydrocarbon group having 1 to 3 carbon atoms, preferably an alkyl group. _L1 is preferably a hydrogen atom or a methyl group, and _L2 and _L3 are preferably hydrogen atoms from the viewpoint of photosensitivity. Furthermore, _m1 is an integer of 2 to 10, preferably an integer of 2 to 4, from the viewpoint of photosensitivity.

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 are the same as R ₉ , R _{10 ,} and n ₁ defined in the above formula (6).}
It is preferable that the polyimide precursor has a structural unit represented by the following formula:

In the general formula (13), at least one of R ₁₂ and R ₁₃ is more preferably a monovalent organic group represented by the above general formula (8).
(A) The polyimide precursor is represented by the following general formula (14):
By including X ₁ represented by the following formula in the structural unit, chemical resistance is particularly enhanced.

In one embodiment, the polyimide precursor (A) is represented by the following general formula (15):
{In the formula, R ₁₄ , R ₁₅ , and n ₁ are the same as R ₉ , R _{10 ,} and n ₁ defined in the above formula (6).}
From the viewpoint of thermal properties, it is preferable that the polyimide precursor has a structural unit represented by the following formula:

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

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

The polyimide precursor (A) is represented by the following general formula (16):
{In the formula, R ₁₆ , R ₁₇ , and n ₁ are the same as R ₉ , R _{10 ,} and n ₁ defined in the above formula (6).}
It is preferable that the polyimide precursor has a structural unit represented by the following formula:

The polyimide precursor (A) is represented by the following general formula (17):
{In the formula, R ₁₈ , R ₁₉ , and n ₁ are the same as R ₉ , R _{10 ,} and n ₁ defined in the above formula (6).}
It is preferable that the polyimide precursor (A) contains a structural unit represented by the general formula (17). When the polyimide precursor (A) contains a structural unit represented by the general formula (17), chemical resistance is particularly improved.

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

(A) Polyimide Precursor Preparation Method The polyimide precursor (A) is obtained by first reacting the above-mentioned tetracarboxylic acid dianhydride containing the tetravalent organic group _X1 with a photopolymerizable alcohol having an unsaturated double bond and, optionally, an alcohol having no unsaturated double bond to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid/ester), and then subjecting the partially esterified tetracarboxylic acid to amide polycondensation with the above-mentioned diamine containing the divalent organic group _Y1 .

(Preparation of Acid/Ester Form)
(A) Examples of tetracarboxylic acid dianhydrides containing a tetravalent organic group _X1 that are suitable for preparing a polyimide precursor include the tetracarboxylic acid 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 acid dianhydride, biphenyl-3,3',4,4'-tetracarboxylic acid dianhydride (BPDA), diphenylsulfone-3,3',4,4'-tetracarboxylic acid dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic acid 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.

(A) Examples of alcohols having a photopolymerizable unsaturated double bond that are suitable for use in preparing a 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, and 2-hydroxy-3-cyclopropyl acrylate. Examples 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.

The above-mentioned photopolymerizable alcohols having an unsaturated double bond can also be partially mixed with alcohols that do not have 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.

Furthermore, as the polyimide precursor (A), a non-photosensitive polyimide precursor prepared solely from the above-mentioned alcohols having no unsaturated double bonds may be used in combination 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 per 100 parts by mass of the photosensitive polyimide precursor. By stirring, dissolving, and mixing the above-mentioned suitable tetracarboxylic acid dianhydride and the above-mentioned alcohols in a solvent described below at a temperature of 20 to 50°C for 4 to 24 hours in the presence of a basic catalyst such as pyridine, the esterification reaction of the acid anhydride proceeds, and the desired acid/ester can be obtained.

(A) Preparation of Polyimide Precursor)
The acid/ester compound (typically a solution in a solvent described below) is mixed with an appropriate dehydration condensation agent, such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, or N,N'-disuccinimidyl carbonate, under ice cooling to convert the acid/ester compound into a polyacid anhydride, to which a diamine containing a divalent organic group _Y1 , dissolved or dispersed in a separate solvent, is added dropwise to carry out amide polycondensation, thereby obtaining the desired polyimide precursor. Alternatively, the acid moiety of the acid/ester compound can be converted into an acid chloride using thionyl chloride or the like, and then the resulting mixture can be reacted with a diamine compound in the presence of a base such as pyridine to obtain the desired polyimide precursor.

The diamines containing the divalent organic group _Y1 include those represented by 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'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4 ... ,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]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis [4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP), 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfonate Examples of diamines include, but are not limited to, 4,4'-oxydianiline (ODA), 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 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 may be used alone or in combination of two or more.

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

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, and 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, and when the (A) polyimide precursor has a weight average molecular weight of 150,000 or less, the dispersibility in a 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 polystyrenes. 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.

(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.

(A) Polyimide resin does not produce resin-derived detached components, which helps prevent the cure shrinkage of the photosensitive resin composition. Therefore, compared to polyimide precursors, it is possible to obtain a photosensitive resin composition with a higher cure residual film rate and improved post-cure flatness.

(A) Polyimide resin may have polymerizable groups in its side chains, but from the viewpoint of the elongation and storage stability of the cured film, it is preferable that it does not have polymerizable groups in its side chains. (A) Polyimide resin preferably does not substantially contain polyamic acid or polyamic acid ester structures. In this disclosure, "substantially does not contain" means, for example, that the imidization rate of the polyimide resin is 90% or more, preferably 95% or more.

(A) The imidization ratio 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 to confirm the presence of absorption peaks of the imide structure (near 1780 cm ^-1 and 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. The peak intensity near 1377 cm ^-1 is compared with the peak intensity before the heat treatment to calculate the imidization ratio of the polyimide resin.

From the viewpoints of solubility in solvents and flatness during coating, the polyimide resin (A) preferably contains a structure represented by general formula (7). This structure is also suitable for solvent-developable photosensitive resin compositions. From the viewpoint of suppressing copper migration, the polyimide resin (A) is preferably a resin that is not alkali-soluble. Furthermore, when the polyimide resin (A) contains a structure represented by general formula (7), it is also preferable that _X2 and / _Y2 do not contain acidic groups such as carboxylic acid groups and phenolic hydroxyl groups.
It is also preferable that the polyimide resin (A) does not contain fluorine atoms, which can further suppress copper migration.
{In the formula, _X2 is a tetravalent organic group, _Y2 is a divalent organic group, and _n2 is an integer from 2 to 150.}

_X2 is a tetravalent organic group, and is not particularly limited as long as it has a structure derived from a known tetracarboxylic dianhydride. However, from the viewpoints of high copper adhesion of the cured film, suppression of copper voids after a high-temperature storage test, suppression of copper migration in a b-HAST test, excellent elongation and chemical resistance of the cured film, and solubility in solvents, it is preferable that X2 have at least one structure represented by the following formulas (19) to (27).

Furthermore, 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, it is preferable that X2 have at least one structure represented by formulas (19) to (26).
Furthermore, from the viewpoint of the heat resistance of a cured film obtained from the photosensitive resin composition of the present disclosure, it is more preferable that _X2 has at least one structure represented by formulas (19) to (21) and (23) to (26).
In addition, it is particularly preferable that _X2 has at least one structure represented by formulas (19) and (24) to (26), since the coating film uniformity and cured film elongation of the photosensitive resin composition of the present disclosure are particularly excellent.

_Y2 in formula (7) is a divalent organic group, and is not particularly limited as long as it is a structure derived from a known diamine. However, from the viewpoints of high copper adhesion of the cured film, inhibition of copper migration in the b-HAST test, excellent elongation and chemical resistance of the cured film, and solubility in solvents, it is preferable that Y2 have at least one structure represented by the following formulas (28) to (36).

Furthermore, _Y2 preferably 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.
Furthermore, 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 _Y2 has at least one structure represented by formulas (28) to (33).
In addition, _Y2 particularly preferably has at least one structure represented by formulas (30) to (33), because this results in particularly excellent coating film uniformity and cured film elongation of the photosensitive resin composition of the present disclosure (in one embodiment, the negative photosensitive resin composition of the present disclosure). 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.

In formula (7), _n2 is an integer of 2 to 150, preferably an integer of 3 to 100, and more preferably an integer of 5 to 70. _n2 is preferably an integer that satisfies the weight average molecular weight of the polyimide resin (A) described below.

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 and 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, k is an integer of 1 or 2, R ₂₃ is a hydrogen atom or an organic group having 1 to 4 carbon atoms, and * indicates a bonding site with an end of the polyimide resin (A).}
(In the formula, R ₂₄ and R ₂₅ each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. Also, * indicates the bonding site with the terminal of the polyimide resin (A).)
{In the formula, R ₂₆ , R ₂₇ , and R ₂₈ each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and j represents an integer of 2 to 10. Additionally, * represents the bonding site with the terminal of the polyimide resin (A).}

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).)

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).)

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).)

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, elongation of the cured film, chemical resistance, and solubility in solvents, it is preferred that _X2 in general formula (7) is any of the structures represented by general formulas (19) to (27), and _Y2 is any of the structures represented by general formulas (28) to (36).

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 of the cured film and copper adhesion, 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.

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.

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

(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.

The method for dehydrating and cyclizing polyamic acid is not limited, but examples include thermal imidization, in which polyamic acid is heated at high temperatures to dehydrate and cyclize, and chemical imidization, in which acetic anhydride and a tertiary amine, which are dehydrating and reducing agents, are added to dehydrate and cyclize polyamic acid.

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, and more preferably 160°C or higher. On the other hand, from the viewpoint of suppressing side reactions, the upper limit is preferably 200°C or lower, and more preferably 180°C or lower.

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).

Diamines are 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'-diphenyl Examples of 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).

When the terminals of the (A) polyimide resin are acid anhydride groups, carboxyl groups, and amino groups, 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 form an imidized polyamic acid. The acid anhydride groups, carboxyl groups, and amino groups at the terminals of the (A) polyimide resin may also be reacted with a specific compound to form the terminals into structures represented by the above general formulas (37) to (39).

(A) Polyimide resins whose terminals have a structure represented by general formula (37) can be obtained, for example, by reacting the amino groups at the polyimide terminals with an isocyanate compound. Specific examples of isocyanate compounds 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 added to a dehydrated, ring-closed polyimide solution and stirred at room temperature to react with the amino groups of the dehydrated, ring-closed polyimide.

(A) Polyimide resin, whose terminals have a structure represented by general formula (38), can be obtained, for example, by reacting the amino groups at the polyimide terminals with a chloride compound. Examples of chloride compounds include acryloyl chloride and methacryloyl chloride. There are no particular restrictions on the method for reacting the chloride compound; however, the dehydrated, ring-closed polyimide solution can be ice-cooled and the chloride compound can be added dropwise to react with the amino groups of the dehydrated, ring-closed polyimide.

(A) Polyimide resins 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 alcohol-based compounds 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.

In the production of the (A) 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 reaction solvents 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.

When a thermal imidization method is used in the production of the (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.

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

(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, _R3 is an organic group having at least one carbonyl group.}

_R1 in general formula (1) is not particularly limited as long as it is an organic group, but it 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). _R1 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, or a xylyl group.
_R2 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). _R2 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, or a xylyl group.
_R3 in general formula (2) 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, and _R3 may also have a functional group, preferably an organic group having 1 to 10 carbon atoms. Examples of the functional group include an acetyl group and an acetoxy group.

When the (B) heterocyclic compound contains the compound (b1) represented by the general formula (1) above or the compound (b2) represented by the general formula (2) above, 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, the copper migration suppression effect and copper void suppression effect can be obtained not only by high-temperature curing but also by low-temperature curing.
The reason for this is unclear, and without being bound by theory, it is believed that when the photosensitive resin composition of this embodiment contains a purine compound represented by 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, and the secondary amine at the 1-position, which is 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.

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-acetylacyclovir, N ² -isobutyryl-2'-deoxyguanosine, 9-ethylguanine, N ² -isobutyrylguanosine, 2-amino-9-phenyl-1H-purin-6(9H)-one, N ² ,9-diacetylguanine, and 9-[(2-acetoxyethoxy)methyl]-N ² -acetylguanine. Among 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, and N ² ,9-diacetylguanine are preferred, and N ² ,9-diacetylguanine is more preferred.

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

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, _R4 is an organic group having 1 to 10 carbon atoms and having at least one hydroxyl group or carbonyl group.}
{In the formula, _R5 and _R6 each independently represent an organic group having 1 to 10 carbon atoms and at least one carbonyl group.}
{In the formula, _R7 is an organic group having 1 to 6 carbon atoms and at least one carbonyl group.}

_R4 in general formula (3) 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.

The carbonyl-containing organic group of 1 to 10 carbon atoms represented by _R5 and _R6 in general formula (4) may be a branched or linear alkyl group or aromatic group having 1 to 10 carbon atoms and having the above-mentioned functional group. 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.

The carbonyl-containing organic group of _R7 in general formula (5) 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 above-mentioned functional group. Examples of the functional group include an acetyl group and an acetoxy group.

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

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, and N ² ,9-diacetylguanine.

Specific examples of the heterocyclic compound (B) represented by general formula (5) include 2-acetamido-6-hydroxypurine, N-(6-oxo-6,7-dihydro-1H-purin-2-yl)isobutyramide, N ² -pivaloylguanine, N-(6-oxo-6,9-dihydro-1H-purin-2-yl)benzamide, 2-acetamido-6-hydroxypurine, and N-(6-oxo-6,7-dihydro-1H-purin-2-yl)isobutyramide. When these compounds are added to the resin composition, they may be in the form of a hydrate.

The content of the (B) heterocyclic compound is preferably 0.001 to 20 parts by mass, more preferably 0.005 to 15 parts by mass, and more preferably 0.01 to 10 parts by mass, per 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 achieve 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, from the viewpoints of copper adhesion, copper migration inhibition, and solubility in the composition. The reason for this is unclear and 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.

(C) Photopolymerization Initiator The photopolymerization initiator (C) will be described. As the photopolymerization initiator (C), 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, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone and other benzophenone derivatives;
acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexyl phenyl ketone;
thioxanthone, thioxanthone derivatives such as 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone;
benzil, benzil dimethyl ketal, benzil-β-methoxyethyl acetal and other benzil derivatives; benzoin, benzoin methyl ether and other benzoin derivatives;
oximes such as 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, and 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime;
Preferred examples include N-arylglycines such as N-phenylglycine, peroxides such as benzoyl perchloride, aromatic biimidazoles, and titanocenes, but are not limited to these.
Among 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.

The content of (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 (A) polyimide precursor and/or polyimide resin. From the viewpoint of photosensitivity or patterning ability, the content is preferably 0.1 parts by mass or more, and from the viewpoint of the physical properties of the photosensitive resin layer after curing of the photosensitive resin composition, the content is preferably 20 parts by mass or less.

(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.

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

The (D) solvent may be one type, or two or more types may be mixed together, but from the viewpoint of appropriately adjusting the stability of the photosensitive resin composition, two or more types are preferred. When the photosensitive resin composition of this embodiment contains two or more (D) solvents, from the viewpoint of in-plane uniformity, 50% by weight or more of the (D) solvents are preferably either gamma-butyrolactone or 3-methoxy-N,N-dimethylpropanamide, and more preferably gamma-butyrolactone.

In the photosensitive resin composition of this embodiment, the content of (D) solvent is preferably 100 to 1,000 parts by mass, more preferably 120 to 700 parts by mass, and even more preferably 125 to 500 parts by mass, per 100 parts by mass of (A) polyimide precursor and/or polyimide resin.

(E) Photopolymerizable Monomer The photosensitive resin composition of the present embodiment may further contain (E) a photopolymerizable monomer. Use of (E) a photopolymerizable monomer promotes crosslinking of the photosensitive resin composition upon exposure, improving resolution, and also reduces the moisture permeability of the cured film, thereby providing an effect of 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 obtain good resolution, the photosensitive resin composition of this embodiment preferably contains 5 parts by mass or more of the (E) photopolymerizable monomer, more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more. On the other hand, if the (E) photopolymerizable monomer is contained in too much amount, copper adhesion may be reduced.
The reason for this is not clear and is not limited to a specific theory, but it is speculated that the high content of (E) photopolymerizable monomer causes a weak layer to form between the copper layer and the photosensitive resin layer, resulting in reduced 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.

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, L ₁₁ , L ₁₂ and L ₁₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and n ₁₁ is an integer of 1 to 10.}

(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:

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 bifunctional or more 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.

(E) The molecular weight (in one embodiment, the weight average molecular weight) of the 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 photopolymerizable monomer (E) within the above range, resolution is improved.

Furthermore, (E) the photopolymerizable monomer may contain a hydroxyl group or a urea group.

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. n ₁₁ is an integer of 1 to 10, and n ₁₂ is an integer of 1 to 10.} In terms of radical reactivity, it is preferable that in the above formula (53), L ₁₁ is a hydrogen atom or a methyl group, and L ₁₂ and L ₁₃ are each a hydrogen atom.
More specifically, the photopolymerizable monomer (E) having a hydroxyl group in the molecule is represented by the following formula (54):
Examples of the compound include, but are not limited to, compounds represented by the following formula:
(E) The photopolymerizable monomer has hydroxyl groups in its molecular structure, which improves copper adhesion. The number of hydroxyl groups in the (E) photopolymerizable monomer molecular structure 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 is improved.

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 X ₂₃ each independently represent 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 at least one of X ₂₀ , X ₂₁ , X ₂₂ and X ₂₃ 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 each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms.} In the above formula (56), it is preferable that L ₁₁ represents a hydrogen atom or a methyl group, and L ₁₂ and L ₁₃ represent hydrogen atoms, from the viewpoint of radical reactivity.

Heteroatoms include oxygen atoms, nitrogen atoms, phosphorus atoms, and sulfur atoms.

When _X20 , _X21 , _X22 and _X23 in formula (55) are monovalent organic groups having 1 to 20 carbon atoms which may contain a heteroatom, they more preferably contain an oxygen atom from the viewpoint of resolution. The number of carbon atoms in _X20 , _X21 , _X22 and _X23 is not limited as long as it is 1 to 20, but from the viewpoint of heat resistance, they preferably have 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms.
In formula (55), _X20 , _X21 , _X22 , and _X23 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. When _X20 , _X21 , _X22 , and _X23 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.
From the viewpoint of forming hydrogen bonds with other molecules, it is preferable that at least one of X ₂₀ , X ₂₁ , X ₂₂ and X ₂₃ is a hydrogen atom, while from the viewpoint of solubility, it is preferable that the number of hydrogen atoms in X ₂₀ , X ₂₁ , X ₂₂ and X ₂₃ is two or less.
Specifically, the following formula (57):
Examples include compounds represented by the following formula:

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 each independently represent 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 at least one of X ₃₀ , X ₃₁ , X ₃₂ and X ₃₃ is a monovalent organic group having a group represented by the following general formula (59), and at least one is a hydroxyl group.}
{In the formula, L ₁₁ , L ₁₂ and L ₁₃ each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms.} In the above formula (59), it is preferable that L ₁₁ represents a hydrogen atom or a methyl group, and L ₁₂ and L ₁₃ represent hydrogen atoms, from the viewpoint of radical reactivity.

In formula (58), when X ₃₀ , X ₃₁ , X ₃₂ and X ₃₃ are monovalent organic groups having 1 to 20 carbon atoms which may contain a heteroatom, they more preferably contain an oxygen atom from the viewpoint of resolution. The number of carbon atoms in X ₃₀ , X ₃₁ , X ₃₂ and X ₃₃ is not limited as long as it is 1 to 20, but from the viewpoint of heat resistance, they preferably have 1 to 10 carbon atoms, more preferably 3 to 10 carbon atoms.
In the formula (58), X ₃₀ , X ₃₁ , X ₃₂ and X ₃₃ may be bonded to each other to form a cyclic structure, but from the viewpoint of chemical resistance, it is preferable that no cyclic structure is formed.
When X ₃₀ , X ₃₁ , X ₃₂ and X ₃₃ 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.
From the viewpoint of forming hydrogen bonds with other molecules, it is preferable that at least one of X ₃₀ , X ₃₁ , X ₃₂ and X ₃₃ is a hydrogen atom. On the other hand, from the viewpoint of solubility, it is preferable that the number of hydrogen atoms in X ₃₀ , X ₃₁ , X ₃₂ and X ₃₃ is two or less.
Specifically, the photopolymerizable monomer (E) having at least one hydroxyl group and at least one urea group in the molecule is represented by the following formula (60):
Examples of the compound are compounds represented by the following formula:

(E) Among the photopolymerizable monomers, the photopolymerizable monomer having a urea group may be produced by any method, but it can be obtained, for example, by reacting an isocyanate compound having a radical polymerizable group with an amine-containing compound. If the amine-containing compound contains a functional group such as a hydroxyl group that can react with isocyanate, part of the isocyanate compound may contain a compound that has reacted with the functional group such as a hydroxyl group.

(E) Photopolymerizable monomers may be used singly or in combination of two or more. When two or more (E) photopolymerizable monomers are used in combination, from the viewpoint of controlling the crosslink density, it is preferable that the number of types be six or less, and more preferably four or less.

When using a mixture of multiple (E) photopolymerizable monomers, it is preferable that at least one of the multiple (E) photopolymerizable monomers has a different number of functional groups. When using three or more (E) photopolymerizable monomers, 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 using multiple (E) photopolymerizable monomers, it is preferable to include at least one monofunctional photopolymerizable monomer from the standpoint of breaking elongation.

(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.

The (F) thermal crosslinking agent 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 (A) polyimide precursor and/or polyimide resin and the (F) thermal crosslinking agent, with each other, or with other components to form a crosslinked product. The reaction temperature is preferably 150°C or higher.

Examples of the (F) thermal crosslinking agent include alkoxymethyl compounds, epoxy compounds, oxetane compounds, bismaleimide compounds, allyl compounds, and blocked isocyanate compounds. From the perspective of suppressing cure shrinkage, it is preferable that the (F) thermal crosslinking agent contain a nitrogen atom.

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

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.).

Examples of epoxy compounds include 4-hydroxybutyl acrylate glycidyl ether, epoxy compounds containing bisphenol A groups, and hydrogenated bisphenol A diglycidyl ether. For example, Epolite 4000 (product name, manufactured by Kyoeisha Chemical Co., Ltd.) is preferably used.

Oxetane compounds include 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, bis[1-ethyl(3-oxetanyl)]methyl ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methyl]biphenyl, 4,4'-bis(3-ethyl-3-oxetanylmethoxy)biphenyl, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, diethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, bis(3 Examples of suitable bis[(3-ethyloxetan-3-yl)methoxy]benzene include 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene, ...

Examples of bismaleimide compounds include 1,2-bis(maleimide)ethane, 1,3-bis(maleimide)propane, 1,4-bis(maleimide)butane, 1,5-bis(maleimide)pentane, 1,6-bis(maleimide)hexane, 2,2,4-trimethyl-1,6-bis(maleimide)hexane, N,N'-1,3-phenylenebis(maleimide), 4-methyl-N,N'-1,3-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.

Allyl compounds 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.

Blocked isocyanate compounds include hexamethylene diisocyanate-based blocked isocyanates (e.g., Asahi Kasei Corporation, trade names: Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B, and WM44-L70G; Mitsui Chemicals, Inc., trade name: Takenate B-882N; Baxenden, Inc., trade names: 7960, 7961, 7982, 7991, and 7992, etc.); tolylene diisocyanate-based blocked isocyanates (e.g., Mitsui Chemicals, Inc., trade name: Takenate B-830, etc.); 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 name: 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).

Among these, alkoxymethyl compounds are preferred from the viewpoint of copper adhesion. (F) Thermal crosslinking agents may be used alone or in combination of two or more types.

The content of the thermal crosslinking agent (F) in the photosensitive resin composition of the present disclosure is preferably 0.2 parts by mass to 40 parts by mass per 100 parts by mass of the polyimide precursor and/or polyimide resin (A).
From the viewpoint of suppressing copper migration, the lower limit of the amount of the thermal crosslinking agent (F) 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.
The upper limit of the amount of the thermal crosslinking agent (F) 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, from the viewpoint of copper adhesion of the photosensitive resin composition of the present disclosure.

(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.

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

In addition, (G) other silane coupling agents include, for example, N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS3610, manufactured by Azmax Co., Ltd.: trade name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Co., Ltd.: trade name SIU9058.0), N-(3-diethoxymethoxysilylpropyl)urea, N-(3-ethoxydimethoxysilylpropyl)urea, N-(propyl)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-tripro N-(3-tripropoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-tripropoxysilylbutyl)urea, 3-(m-aminophenoxy) Examples of such silanes include, but are not limited to, propyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.1), and aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.2).

Furthermore, (G) silane coupling agents include, for example, 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, and tetra-t-butoxysilane. silane, tetrakis(methoxyethoxysilane), tetrakis(methoxy-n-propoxysilane), tetrakis(ethoxyethoxysilane), tetrakis(methoxyethoxyethoxysilane), bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane, bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane, bis(triethoxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide, bis[3-(triethoxysilyl)propyl]tetrasulfide, di-t-butoxydiacetoxysilane silane, di-i-butoxyaluminoxytriethoxysilane, phenyl silanetriol, methyl phenyl silanediol, ethyl phenyl silanediol, n-propyl phenyl silanediol, isopropyl phenyl silanediol, n-butyl phenyl silanediol, isobutyl phenyl silanediol, tert-butyl phenyl silanediol, diphenyl silanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethyl methyl phenyl silanol, n-propyl methyl phenyl silanol, isopropyl methyl phenyl silanol, n-butyl methyl phenyl silane Examples of silanol include, but are not limited to, methylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, and triphenylsilanol.

The (G) silane coupling agents 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 standpoint of copper adhesion.

When (G) a silane coupling agent is used, its 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.

(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.

(H) Examples of acid components 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.

When the (H) acid component is used, its content is preferably 0.001 to 5 parts by mass per 100 parts by mass of the (A) polyimide precursor and/or polyimide resin. From the viewpoint of copper migration suppression in the photosensitive resin composition of the present disclosure, the lower limit of the (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.

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.

(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.

(I) The thermal base generator is not particularly limited in type, but examples include amine compounds protected by a tert-butoxycarbonyl group, or the thermal base generators disclosed in WO 2017/038598. However, it is not limited to these, and other known thermal base generators can also be used.

Amine compounds protected by a tert-butoxycarbonyl group include, for example, 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 amines 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.

The content of (I) the thermal base generator is preferably 0.1 parts 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, per 100 parts by mass of (A) the polyimide precursor and/or polyimide resin. The content is preferably 0.1 parts by mass or more from the viewpoint of the imidization-accelerating effect, and 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.

(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.

(J) Examples of hindered phenol compounds 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, etc.

Furthermore, examples of (J) hindered phenol compounds include 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxybenzyl] 1,3,5-tris[4-t-butyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-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, ,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl )-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, but are not limited to these.

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.

The content of the (J) hindered phenol compound is preferably 0.1 to 20 parts by mass per 100 parts by mass of the (A) polyimide precursor and/or polyimide resin, and more preferably 0.5 to 10 parts by mass from the viewpoint of photosensitivity characteristics. If 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 if the content is 20 parts by mass or less, excellent photosensitivity is achieved.

(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.

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

Specific examples of the (K) organic titanium compound 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 provide good storage stability for the photosensitive resin composition and enable 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), and the like.

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.

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.

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

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

VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate, etc.

VII) Titanate coupling agents: For example, isopropyl tridodecylbenzenesulfonyl titanate, etc.

Among these, from the viewpoint of exhibiting better chemical resistance, 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. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η ⁵ -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

When (K) an organic titanium compound is contained, the content 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 (A) the polyimide precursor and/or polyimide. When the content is 0.05 parts 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.

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

(L) Examples of sensitizers include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylidene indanone, p-Dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 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 isoform 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 combinations of, for example, 2 to 5 types.

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

(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.

(M) Polymerization inhibitors 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.

<Method for producing cured relief pattern and semiconductor device>
The method for producing a cured relief pattern of the present disclosure includes the following steps: (1) applying the above-described photosensitive resin composition of 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.

(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.

(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, mirror projection, or stepper, either directly or through a photomask or reticle having a pattern.

(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.

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.
Preferred good solvents include, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone.
Preferred examples of poor solvents include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When a good solvent and a poor solvent are used in combination, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the photosensitive resin composition. Two or more types of each solvent, for example, several types, can also be used in combination.

The photosensitive resin composition of this embodiment is preferably subjected to solvent development or prepared as a solvent-developable composition. In this disclosure, solvent development refers to development in a developer whose main component is 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.) (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, and more preferably 100% by mass. With 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 suppress copper migration.

(4) Step of Forming Cured Relief Pattern In this step, the relief pattern obtained by the above development is subjected to a heat treatment to dissolve the photosensitive component and also imidize the (A) polyimide precursor, thereby converting it into a cured relief pattern (cured film) made of polyimide.
The heat treatment can be carried out by a variety of methods, such as using a hot plate, an oven, or a temperature-programmable heating oven, etc. The heat treatment can be carried out, for example, at 160°C to 350°C for 30 minutes to 5 hours.
To further improve copper adhesion, the temperature of the heat treatment is preferably 350° C. or lower, more preferably 230° C. or lower, even more preferably 200° C. or lower, and even more preferably 180° C. or lower. To further suppress copper migration, the temperature is preferably 170° C. or higher, more preferably 250° C. or higher.
To achieve both copper adhesion and copper migration suppression, the temperature is preferably 170° C. to 350° C., and more preferably 200° C. to 280° C. As the atmospheric gas during heat curing, air may be used, or an inert gas such as nitrogen or argon may also be used.

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

For the same reason, the preferred X ₁ and Y ₁ in the general formulas (6) and (7) are also preferred in the polyimide having the structure represented by the above general formula (62). In the above general formula, the number of repeating units n ₂ is not particularly limited, but may be an integer of 2 to 150.

<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.

<Display device>
The display device preferably includes a display element and a cured film disposed on the display element, the cured film preferably having the cured relief pattern described above. The cured relief pattern may be laminated in direct contact with the display element, or may be laminated via another layer. 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.

The photosensitive resin composition of the present disclosure is preferably a photosensitive resin composition for forming insulating members or interlayer insulating films. Furthermore, the photosensitive resin composition can be used to form surface protective films, interlayer insulating films, rewiring insulating films, protective films for flip-chip devices, or protective films for semiconductor devices with bump structures. In addition to being applied to semiconductor devices such as those described above, the photosensitive resin composition of the present disclosure is also useful for applications such as interlayer insulating films for multilayer circuits, cover coats for flexible copper-clad boards, solder resist films, and liquid crystal alignment films.

The following describes specific examples of the present disclosure, but the present embodiment is not limited to these examples. 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.

<Measurement and evaluation methods>
(1) Weight-average molecular weight The weight-average molecular weight (Mw) of each resin was measured using gel permeation chromatography (standard polystyrene equivalent) under the following conditions.
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40°C
Column: Showa Denko K.K. Shodex KD-806M, two 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.

(2) Evaluation of Copper Adhesion 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 model, manufactured by ULVAC Corporation). Next, the photosensitive resin composition was spin-coated onto this wafer using a coater developer (D-Spin 60A model, manufactured by SOKUDO Corporation) so that the film thickness after curing would be approximately 8 μm, and the composition was pre-baked on a hot plate at 110° C. for 240 seconds to form a coating film on the copper wafer.
The entire surface was then exposed to 800 mJ/ ^cm2 using a parallel light mask aligner (PLA-501FA, manufactured by Canon Inc.).Then, using a temperature-programmable curing oven (VF-2000, manufactured by Koyo Lindberg Co., Ltd.), the film was heated for 2 hours in a nitrogen atmosphere at the temperatures shown in Tables 1 to 4 to obtain a cured relief pattern (thermocured polyimide coating film).

An Evercel OPP tape (No. 830NEV, manufactured by Sekisui Chemical Co., Ltd.) was applied to this sample, and the tape and polyimide coating were cut into 5 mm widths with a cutter. Then, using a Tensilon universal material testing machine (RTG-1210, manufactured by A&D Co., Ltd.), the tape and polyimide coating were peeled off at an angle of 180 degrees for 60 mm at a speed of 50 mm/min so as to separate the copper and the polyimide. The load applied during this process was calculated as an integrated average, and this value was evaluated as the adhesion strength.
If the evaluation is C or higher, the composition 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 and less than 0.4 N/mm C: Adhesion strength is 0.2 N/mm or more and less than 0.3 N/mm D: Adhesion strength is less than 0.2 N/mm

(3) b-HAST Test: A 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 with SiO _x laminated on the surface. 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. Then, oxygen plasma was applied to the wafer 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 model, manufactured by SOKUDO Corporation) so that the film thickness after curing would be approximately 8 μm, and the coating was pre-baked on a hot plate at 110°C for 240 seconds to form a coating film on the TEG wafer. The wafer was then exposed to 800 mJ/ ^cm2 using a parallel light mask aligner (PLA-501FA model, manufactured by Canon Inc.). At this time, the Cu electrode portion was exposed while masked to prevent light irradiation in order to ensure conductivity during the b-HAST test, and the unexposed portion was removed in the subsequent development.
After 30 minutes or more had elapsed since the exposure, the film was subjected to rotary spray development using cyclopentanone as a developer at 23°C in a coater developer (D-Spin 60A, manufactured by SOKUDO Co., Ltd.) for a time 1.4 times the time required for the unexposed areas to completely dissolve and disappear, followed by rotary spray rinsing with propylene glycol monomethyl ether acetate for 10 seconds. Thereafter, the film was heated for 2 hours in a temperature-rising programmable curing oven (VF-2000, 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.

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

(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 model, manufactured by ULVAC Corporation). Subsequently, the photosensitive resin composition was spin-coated onto this wafer using a coater developer (D-Spin 60A model, manufactured by SOKUDO Corporation) so that the film thickness after curing would be approximately 8 μm, and the composition was pre-baked on a hot plate at 110° C. for 240 seconds to form a coating film on the copper wafer.
The coating was exposed to i-line radiation using a lithography system (Ultratech AP-200, manufactured by Veeco) at a focus of 0 μm, with a dose of 50 mJ/ ^cm² to 300 mJ/ ^cm² in 25 mJ/ ^cm² steps, using a lithography system with a diameter of 9 μm, a diameter of 10 μm, and a diameter of 11 μm. After 30 minutes or more, the coating was subjected to rotary spray development using a coater developer (D-Spin 60A, manufactured by SOKUDO Co., Ltd.) at 23°C using cyclopentanone as the developer for a time period 1.4 times the time required for the unexposed areas to completely dissolve and disappear, followed by a rotary spray rinse with propylene glycol monomethyl ether acetate for 10 seconds. The coating was then heated for 2 hours in a temperature-programmable curing oven (VF-2000, manufactured by Koyo Lindberg Co., Ltd.) under a nitrogen atmosphere at the temperatures listed in Tables 1 to 4, yielding a cured relief pattern.

The circular hole pattern obtained from this sample was observed for its pattern shape and width using a field emission scanning electron microscope S-4800 (Hitachi High-Technologies Corporation). If the circular hole had no hollows at the bottom, a forward tapered opening, and the area of the resulting circular hole opening was at least half the area of the corresponding pattern mask opening, it was considered to have been resolved, and the smallest diameter of the exposure mask among the resolved openings was shown as the evaluation result.

<Production Example>
Preparation 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, followed by the addition of 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone (hereinafter referred to as GBL), and the mixture was stirred at room temperature. 81.5 g of pyridine was added with stirring to obtain a reaction mixture. After the heat generated by the reaction had ceased, the reaction mixture was allowed to cool to room temperature and left to stand for 16 hours.

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 a suspension of 93.0 g of 4,4'-oxydianiline (ODA) in 350 mL of γ-butyrolactone, which was added over 30 minutes with stirring. After further stirring at room temperature for 4 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour, and then 400 mL of γ-butyrolactone was added. The precipitate that formed in the reaction mixture was removed by filtration to obtain the reaction solution.

The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The resulting 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 powdered polymer A1 (polyimide precursor A1). The molecular weight of polyimide precursor A1 was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight average molecular weight (Mw) was found to be 24,000.

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.

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.

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.

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.

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.

Production Example 7: (A) Synthesis of Polyimide Resin A7 (MOI-Modified BCD-PDPE)
A Dean-Stark extractor was attached, and 200 g of GBL and 33.1 g (0.12 mol) of PDPE were added to a nitrogen-purged three-neck flask 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.

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 for 12 hours at room temperature. The resulting reaction solution was added dropwise to 2,000 g of ion-exchanged water to precipitate the 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.

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.

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.

Example 1
Photosensitive resin compositions were prepared using the 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 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 GBL:DMSO solution at a mass ratio of 80:20 to obtain a photosensitive resin composition. The composition was evaluated according to the method described above. The results are shown in Table 1.

<Examples 2 to 51 and 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:

(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.)

(B) Heterocyclic Compound 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 (Tokyo Chemical Industry Co., Ltd.)
B4: Guanosine (Tokyo Chemical Industry Co., Ltd.)
B5: 3'-amino-2',3'-dideoxyguanosine (Fujifilm Wako Pure Chemical Industries, Ltd.)
B6: Penciclovir (Tokyo Chemical Industry Co., Ltd.)
B7: N ² -pivaloylguanine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
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 (Tokyo Chemical Industry Co., Ltd.)
B11: 9-ethylguanine (Sigma-Aldrich)
B12: 2-amino-9-phenyl-1H-purin-6(9H)-one (BLDpharm)
B13: N-(6-oxo-6,9-dihydro-1H-purin-2-yl)benzamide (manufactured by BLDpharm)
B14: N ² ,9-diacetylguanine (Tokyo Chemical Industry Co., Ltd.)
B1': 8-Azaadenine (Tokyo Chemical Industry Co., Ltd.)
B2': 5-amino-1H-tetrazole (manufactured by Chiyoda Chemical Co., Ltd.)
B3': 1,2,3-benzotriazole (Tokyo Chemical Industry Co., Ltd.)
B4': Hypoxanthine (Tokyo Chemical Industry Co., Ltd.)

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

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

(E) Photopolymerizable monomer E1: tetraethylene glycol dimethacrylate (trade 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.)

(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.)

(G) Silane coupling agent 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 (Tokyo Chemical Industry Co., Ltd.)

(H) Acid component H1: (±)-mandelic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
H2: p-toluenesulfonic acid (Tokyo Chemical Industry Co., Ltd.)

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

(L) Sensitizer L1: 2,2'-(phenylimino)diethanol (manufactured by Kanto Chemical Co., Ltd.)

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, show excellent performance in both copper adhesion and copper migration suppression performance.
Comparisons of Comparative Examples 2 to 4 and 6 with Examples 1 to 14, and comparisons of Comparative Example 5 with Example 40 show that use of the heterocyclic compound (B) of the present disclosure improves copper adhesion, and good copper adhesion is exhibited even at a high cure temperature of 250°C.
Furthermore, a comparison of Comparative Example 1 with Examples 18 to 21 shows that the use of the heterocyclic compound (B) of the present disclosure improves copper migration suppression performance and copper adhesion even at a low curing temperature of 200°C.
Furthermore, a comparison between Comparative Example 7 and Example 41 shows 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.

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 more preferable in terms of copper adhesion than those having structures of general formulas (1) or (2). The reason for this is unclear and is not limited by theory, but it is presumed that the hydroxyl groups and carbonyl groups of the (B) heterocyclic compounds strengthen the interaction with copper.
Examples 1 and 15 to 17 have compositions with different contents of the heterocyclic compound (B). Examples 1 and 16, in which the content is in the range of 0.01 to 10 parts by mass, are superior in copper adhesion or copper migration suppression performance.
The reason for this is unclear and is not limited by theory, but it is speculated that by setting the content of the (B) heterocyclic compound to 10 parts by mass or less, the ionic components in the photosensitive resin layer do not increase more than necessary, and the copper migration suppression ability is also improved.

Examples 36 to 39 use polyimide resin, but the (A) polyimide resin used in Examples 36, 37, and 39 does not contain fluorine, and therefore demonstrate better copper migration suppression performance than Example 38, which uses (A) polyimide resin that contains fluorine.

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

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) provides good copper migration suppression performance.

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 minimal 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 that are useful in the manufacture of electrical and electronic materials such as semiconductor devices and multilayer wiring boards. More specifically, it can be used, for example, to form relief patterns for insulating materials for electronic components, as well as passivation films, buffer coating films, and interlayer insulating films in semiconductor devices.

Claims (17)

Ingredients:
A photosensitive resin composition comprising: (A) a polyimide precursor and/or a polyimide resin; (B) a heterocyclic compound; and (C) a photopolymerization initiator,
The heterocyclic compound (B) is
(b1) The following general formula (1):
{wherein 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):
{wherein _R3 is an organic group having at least one carbonyl group.}. The compound (b1) is represented by the following general formula (3):
{wherein 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, _R5 and _R6 each independently represent an organic group having 1 to 10 carbon atoms and at least one carbonyl group.}
is a compound represented by
The compound (b2) is represented by the following general formula (5):
{In the formula, _R7 is an organic group having 1 to 6 carbon atoms and at least one carbonyl group.}
2. The photosensitive resin composition according to claim 1, wherein the compound is represented by the formula: The photosensitive resin composition contains the polyimide precursor, and the polyimide precursor is represented by the following general formula (6):
{In the formula, _X1 is a tetravalent organic group, _Y1 is a divalent organic group, _n1 is an integer from 2 to 150, and _R9 and _R10 are each independently a hydrogen atom or a monovalent organic group.}
and/or the photosensitive resin composition contains the polyimide resin,
The polyimide resin is represented by the following general formula (7):
{In the formula, _X2 is a tetravalent organic group, _Y2 is a divalent organic group, and _n2 is an integer from 2 to 150.}
The photosensitive resin composition according to claim 1 or 2, which has a structural unit represented by the following formula: In the above general formula (6), at least one of R ₉ and R ₁₀ is a group represented by the following general formula (8):
{In the formula, L ₁ , L ₂ and L ₃ each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m ₁ represents an integer of 2 to 10.}
The photosensitive resin composition according to claim 3 , which has a structural unit represented by the following formula: The photosensitive resin composition according to claim 1 or 2, wherein the (C) photopolymerization initiator is a photoradical polymerization initiator. The photosensitive resin composition according to claim 5, wherein the photoradical polymerization initiator is an oxime initiator. The photosensitive resin composition according to claim 1 or 2, wherein the content of component (B) is 0.01 to 10 parts by mass per 100 parts by mass of component (A). The photosensitive resin composition according to claim 1 or 2, further comprising (D) a solvent. The photosensitive resin composition according to claim 1 or 2, further comprising (E) a photopolymerizable monomer. The photosensitive resin composition according to claim 1 or 2, further comprising (F) a thermal crosslinking agent. The photosensitive resin composition according to claim 1 or 2, further comprising (G) a silane coupling agent. The photosensitive resin composition according to claim 1 or 2, which contains (H) an acid component. The photosensitive resin composition according to claim 1 or 2, wherein the photosensitive resin composition 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. 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;
(4) A method for producing a cured relief pattern, comprising the step of: heat-treating the relief pattern to form a cured relief pattern. 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. A cured film comprising a cured product of the photosensitive resin composition described in claim 1 or 2. A method for producing a polyimide film, comprising curing the photosensitive resin composition described in claim 1 or 2.