Photosensitive resin composition, and methods for using the same to produce cured relief pattern and produce cured film and polyimide film

Abstract

To provide: a photosensitive resin composition that exhibits high adhesion to copper during high-temperature curing, has low copper migration in the b-HAST test, i.e., does not cause short-circuiting over a long period, and has high resolution; and methods for using the photosensitive resin composition to form a cured relief pattern and produce a cured film and a polyimide film.SOLUTION: A photosensitive resin composition is provided which comprises a polyimide precursor and / or a polyimide resin, a compound having a specific heterocyclic structure, and a photopolymerization initiator. Also provided are methods for using the photosensitive resin composition to form a cured relief pattern and produce a cured film and a polyimide film.SELECTED DRAWING: None

Description

[Technical Field]

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

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

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 Conventional mounting methods using metal pins and lead-tin eutectic solder have been replaced by structures in which a polyimide coating directly contacts the solder bumps, such as BGA (ball grid array) and CSP (chip size packaging), which enable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

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

[0005] [Patent Document 1] U.S. Patent No. 10,658,199 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-194520 Summary of the Invention [Problem to be solved by the invention]

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

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

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

[0009] In view of the above problems, an object of the present disclosure is to provide a photosensitive resin composition that exhibits high copper adhesion even when cured at high temperatures, exhibits little copper migration in a b-HAST test, i.e., does not short circuit over a long period of time, and has high resolution. Another object is to provide a method for forming a cured relief pattern using the photosensitive resin composition of the present disclosure, and a method for producing a cured film and a polyimide film. [Means for solving the problem]

[0010] The present inventors have found that the above-mentioned problems can be solved by adding a specific heterocyclic compound to a photosensitive resin composition. <1> ~ <14> are listed below. <1> Ingredients: (A) a polyimide precursor and / or a polyimide resin, (B) a heterocyclic compound; (C) a photopolymerization initiator; A photosensitive resin composition comprising: The heterocyclic compound (B) is represented by the following general formula (1): [ka] In the formula, X1 is a nitrogen atom or a carbon atom substituted with R4, and R1, R2, R3, and R4 are each independently a hydrogen atom or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, a nitro group, a halogen group, and an organic group. A compound represented by the following general formula (2): [ka] {In the formula, R5, R6, and R7 each independently represent a hydrogen atom or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, a nitro group, a halogen group, and an organic group.} A compound represented by the following general formula (3): [ka] {In the formula, R8 and R9 each independently represent a hydrogen atom or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, a nitro group, a halogen group, and an organic group.} A compound represented by the following general formula (4): [ka] wherein X3 is a nitrogen atom or R 11 is a carbon atom substituted with R 10 , R 11 and R 12 are each independently a hydrogen atom or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, a nitro group, a halogen group, and an organic group. or a compound represented by the following general formula (5): [ka] wherein X4 is a nitrogen atom or R 13 is a carbon atom substituted with R 13 and R 14 are each independently a hydrogen atom or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, a nitro group, a halogen group, and an organic group. A photosensitive resin composition comprising a compound represented by the formula: <2> The heterocyclic compound (B) is represented by the following general formula (6): [ka] wherein X5 is a nitrogen atom or R 18 is a carbon atom substituted with R 15 , R 16 , R 17 and R 18 are each independently a hydrogen atom, or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, and an organic group having 1 to 10 carbon atoms which may have at least one of a hydroxyl group, an amino group, an amide group, a carbonyl group, and a carboxyl group.} A compound represented by the following general formula (7): [ka] {where, R 19 , R 20 and R 21 are each independently a hydrogen atom, or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, and an organic group having 1 to 10 carbon atoms which may have at least one of a hydroxyl group, an amino group, an amide group, a carbonyl group, and a carboxyl group.} A compound represented by the following general formula (8): [ka] {where, R 22 and R 23 are each independently a hydrogen atom, or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, and an organic group having 1 to 10 carbon atoms which may have at least one of a hydroxyl group, an amino group, an amide group, a carbonyl group, and a carboxyl group.} A compound represented by the following general formula (9): [ka] wherein X7 is a nitrogen atom or R 25 is a carbon atom substituted with R 24 , R 25 and R 26are each independently a hydrogen atom, or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, and an organic group having 1 to 10 carbon atoms which may have at least one of a hydroxyl group, an amino group, an amide group, a carbonyl group, and a carboxyl group.} or a compound represented by the following general formula (10): [ka] wherein X8 is a nitrogen atom or R 27 is a carbon atom substituted with R 27 and R 28 are each independently a hydrogen atom, or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, and an organic group having 1 to 10 carbon atoms which may have at least one of a hydroxyl group, an amino group, an amide group, a carbonyl group, and a carboxyl group.} Item 2. The photosensitive resin composition according to item 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 (11): [ka] wherein X9 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer of 2 to 150, and R 29 and R 30 are each independently a hydrogen atom or a monovalent organic group. and / or the photosensitive resin composition contains the polyimide resin, and the polyimide resin has a structural unit represented by the following general formula (12): [ka] {where, X 10 is a tetravalent organic group, Y2 is a divalent organic group, and n2 is an integer of 2 to 150.} 3. The photosensitive resin composition according to item 1 or 2, having a structural unit represented by the following formula: <4> In the above general formula (11), R 29 and R 30At least one of the following general formula (13): [ka] {In the formula, L1, L2, and L3 each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 represents an integer of 2 to 10.} Item 4. The photosensitive resin composition according to item 3, having a structural unit represented by the following formula: <5> 5. The photosensitive resin composition according to any one of items 1 to 4, wherein the content of the component (B) is 0.01 to 10 parts by mass relative to 100 parts by mass of the component (A). <6> 6. The photosensitive resin composition according to any one of items 1 to 5, further comprising (D) a solvent. <7> 7. The photosensitive resin composition according to any one of items 1 to 6, further comprising (E) a photopolymerizable monomer. <8> 8. The photosensitive resin composition according to any one of items 1 to 7, further comprising: (F) a thermal crosslinking agent. <9> 9. The photosensitive resin composition according to any one of items 1 to 8, further comprising (G) a silane coupling agent. <10> (H) The photosensitive resin composition according to any one of items 1 to 9, further comprising an acid component. <11> 11. The photosensitive resin composition according to any one of items 1 to 10, wherein the photosensitive resin composition 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. <12> The following steps: (1) A step of applying the photosensitive resin composition according to any one of items 1 to 11 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) heat-treating the relief pattern to form a hardened relief pattern; 1. A method for producing a cured relief pattern, comprising: <13> Item 13. The method for producing a cured relief pattern according to Item 12, wherein the temperature in the heat treatment in step (4) is 170°C or higher and 350°C or lower. <14> 12. A cured film comprising a cured product of the photosensitive resin composition according to any one of items 1 to 11. <15> 12. A method for producing a polyimide film, comprising curing a photosensitive resin composition according to any one of items 1 to 11. [Effects of the Invention]

[0011] According to the present disclosure, it is possible to provide a photosensitive resin composition that can achieve high copper adhesion through high-temperature curing, exhibits little copper migration in the b-HAST test, and has high resolution. Furthermore, according to the present disclosure, it is possible to provide a method for producing a cured relief pattern using the photosensitive resin composition, and a method for producing a cured film and a polyimide film. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, embodiments of the present disclosure will be described in detail. The present disclosure is not limited to the following embodiments and can be implemented with various modifications within the scope of the gist. Note that throughout the present disclosure, when a plurality of structures represented by the same symbol in a general formula are present in a molecule, they may be the same or different from each other. Furthermore, the upper and lower limit values ​​in each numerical range of the present disclosure can be arbitrarily combined to form any numerical range.

[0013] <Photosensitive resin composition> The photosensitive resin composition of the present disclosure contains (A) a polyimide precursor and / or a polyimide resin, (B) a heterocyclic compound, and (C) a photopolymerization initiator.

[0014] (A) Polyimide precursor The (A) polyimide precursor is a resin component contained in the photosensitive resin composition, and is converted into 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 preferable that it is not alkali-soluble. If the polyimide precursor is not alkali-soluble, high chemical resistance can be obtained. It is also preferable that the (A) polyimide precursor does not contain a fluorine atom. This can further suppress copper migration of the polyimide.

[0015] The polyimide precursor is represented by the following general formula (11): [ka] wherein X9 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer of 2 to 150, and R 29 and R 30 are each independently a hydrogen atom or a monovalent organic group.} is preferred. It is also preferred that the polyimide precursor does not have an acidic group such as a carboxylic acid group or a phenolic hydroxyl group in the above Y1.

[0016] In general formula (11), R 29 and R 30 At least one of the following general formula (13): [ka] It is preferable that the compound has a structural unit represented by the following formula: {wherein L1, L2, and L3 each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 represents an integer of 2 to 10.}

[0017] R in general formula (11) 29 and R 30 The proportion of hydrogen atoms is R 29 and R 30 It is more preferably 10% or less, more preferably 5% or less, and even more preferably 1% or less, based on the total number of moles.29 and R 30 The proportion of monovalent organic groups represented by the general formula (13) is 29 and R 30 The proportion of hydrogen atoms and the proportion of the organic group of general formula (13) are preferably within the above ranges, based on the total number of moles, more preferably 70% or more, and even more preferably 80% or more, and most preferably 90% or more, from the viewpoints of photosensitive properties and storage stability.

[0018] In general formula (11), n1 is not limited as long as it is an integer of 2 to 150, but is preferably an integer of 3 to 100, more preferably an integer of 5 to 70, from the viewpoint of the photosensitivity and mechanical properties of the photosensitive resin composition.

[0019] In the general formula (11), the tetravalent organic group represented by X9 is preferably an organic group having 6 to 40 carbon atoms, more preferably -COOR 29 Group and -COOR 30 The tetravalent organic group represented by X9 is an aromatic group or an alicyclic aliphatic group in which the -CONH- group and the -CONH- group are located at the ortho-position relative to each other. Specific examples of the tetravalent organic group represented by X9 include organic groups having 6 to 40 carbon atoms and containing an aromatic ring, such as those represented by the following general formula (14): [ka] {where, R 31 is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 monovalent hydrocarbon group, and a C1-C10 monovalent fluorine-containing hydrocarbon group, l is an integer selected from 0 to 2, m is an integer selected from 0 to 3, and n is an integer selected from 0 to 4. Examples of suitable groups include, but are not limited to, groups having a structure represented by the formula (14). Furthermore, X9 may be of one type or a combination of two or more types. An X9 group having a structure represented by the formula (14) above is particularly preferred from the viewpoint of achieving both heat resistance and photosensitivity.

[0020] As the X9 group, among the structures represented by the above formula (14), particularly, those represented by the following general formula (15): [ka] {where, R 31 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. A tetravalent organic group represented by the formula { is preferred from the viewpoints of the imidization rate during low-temperature heating, degassing properties, copper adhesion, chemical resistance, etc.

[0021] In the above general formula (11), 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 (16): [ka] {where, R 32 is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 monovalent hydrocarbon group, and a C1-C10 monovalent fluorine-containing hydrocarbon group, and l, m, and n are each independently an integer selected from 0 to 4. Examples of structures represented by the formula (16) include, but are not limited to, structures represented by the formula (16). The structure of Y1 may be one type or a combination of two or more types. A Y1 group having a structure represented by the formula (16) is particularly preferred from the viewpoint of achieving both heat resistance and photosensitive properties.

[0022] As the Y1 group, among the structures represented by the above formula (16), particularly, those represented by the following general formula (17): [ka] {where, R 32 is at least one selected from the group consisting of a fluorine atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a monovalent fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and l and m are each independently an integer selected from 0 to 4. A divalent group represented by the formula { is preferred from the viewpoints of the imidization rate during low-temperature heating, degassing properties, copper adhesion, chemical resistance, etc.

[0023] The monovalent organic group having 1 to 3 carbon atoms represented by L1, L2, and L3 in the general formula (13) 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.

[0024] In one embodiment, the polyimide precursor (A) is represented by the following general formula (18): [ka] {where, R 33 , R 34 , and n3 are R in the above general formula (11), 29 , R 30 , and n1 can be defined as It is preferable that the polyimide precursor has a structural unit represented by the following formula:

[0025] In general formula (18), R 33 and R 34 It is more preferable that at least one of the groups is a monovalent organic group represented by the above general formula (13). Furthermore, the polyimide precursor (A) is preferably a group represented by the following general formula (19): [ka] By including a polyimide precursor having a tetravalent structure represented by the following formula (I), chemical resistance is particularly enhanced.

[0026] In one embodiment, the polyimide precursor (A) is a polyimide precursor represented by the following general formula (20): [ka] {where, R 35 , R 36 , and n4 are R in the above general formula (11), 29 , R 30 , and n1 can be defined as From the viewpoint of thermal properties, it is preferable that the polyimide precursor has a structural unit represented by the following formula:

[0027] In general formula (20), R 35 and R 36 At least one of the above is more preferably a monovalent organic group represented by the above general formula (13).

[0028] The polyimide precursor (A) tends to have particularly high resolution when it contains both the structural unit represented by general formula (18) and the structural unit represented by general formula (20). For example, the polyimide precursor (A) may contain a copolymer of the structural unit represented by general formula (18) and the structural unit represented by general formula (20), or may be a mixture of the polyimide precursor represented by general formula (18) and the polyimide precursor represented by general formula (20).

[0029] The polyimide precursor (A) is a polyimide precursor represented by the following general formula (21): [ka] {where, R 37 , R 38 , and n5 are R in the above general formula (11), 29 , R 30 , and n1 can be defined as It is preferable that the polyimide precursor has a structural unit represented by the following formula:

[0030] The polyimide precursor (A) is a polyimide precursor represented by the following general formula (22): [ka] {where, R 39 , R 40 , and n6 are R in the above general formula (11), 29 , R 30 , and n1 can be defined as It is preferable that the polyimide precursor (A) contains a polyimide precursor represented by general formula (22), and thereby the chemical resistance is particularly improved.

[0031] The (A) polyimide precursor is contained in an amount of preferably 10 to 70% by mass, more preferably 20 to 65% by mass, based on the total mass of the photosensitive resin composition including the solvent.

[0032] (A) Preparation of polyimide precursor The polyimide precursor (A) is prepared by first reacting a tetracarboxylic acid dianhydride containing the aforementioned tetravalent organic group X9 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 a diamine containing the aforementioned divalent organic group Y1.

[0033] (Preparation of Acid / Ester Forms) (A) Examples of tetracarboxylic acid dianhydrides containing a tetravalent organic group X9 suitable for preparing the polyimide precursor include the tetracarboxylic acid dianhydride represented by the general formula (14) 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.

[0034] (A) Examples of alcohols having a photopolymerizable unsaturated double bond that are preferably used to prepare the polyimide precursor include 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-cyclopropyl acrylate, 2-hydroxy-3-methyl ... Examples of the methacryloyloxypropyl acrylate include 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

[0035] The above-mentioned photopolymerizable alcohols having an unsaturated double bond may be partially mixed with alcohols not having an unsaturated double bond, such as methanol, ethanol, 1-propanol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, and benzyl alcohol.

[0036] Alternatively, a non-photosensitive polyimide precursor prepared solely from the above-mentioned alcohols having no unsaturated double bonds may be mixed with the photosensitive polyimide precursor. From the viewpoint of resolution, the amount of the non-photosensitive polyimide precursor is preferably 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor. The above-mentioned suitable tetracarboxylic acid dianhydride and the above-mentioned alcohol are stirred, dissolved, and mixed in the presence of a basic catalyst such as pyridine in a solvent as described below at a temperature of 20 to 50°C for 4 to 24 hours, whereby the esterification reaction of the acid anhydride proceeds, and the desired acid / ester can be obtained.

[0037] (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 polyanhydride, to which a diamine containing a divalent organic group Y1, dissolved or dispersed in a separate solvent, is added dropwise to cause 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, followed by reaction with a diamine compound in the presence of a base such as pyridine, to obtain the desired polyimide precursor.

[0038] The diamines containing the divalent organic group Y1 include those represented by the following general formula (23): [ka] Examples of diamines include those having the structure shown in the following formula: p-phenylenediamine (1,4-phenylenediamine (pPD)), m-phenylenediamine, 4,4'-oxydianiline (ODA), 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, Aminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene (TPE-Q), 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene (APB), bis[4-(4-aminophenoxy)phenyl]sulfonyl sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoro Propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP), 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene (BAFL), and compounds in which some of the hydrogen atoms on the benzene ring have been substituted with methyl groups, ethyl groups, hydroxymethyl groups, hydroxyethyl groups, halogens, etc., such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,Examples of diamines include, but are not limited to, 2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof. Preferred diamines include 4,4'-oxydianiline (ODA), 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB), and 1,4-phenylenediamine (pPD). These diamines can be used alone or in combination.

[0039] After the amide polycondensation reaction is completed, the water-absorbing by-product of the dehydrating condensing agent coexisting in the reaction solution is filtered off as needed, and then a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is added to the resulting polymer component to precipitate the polymer component, and the polymer is purified by repeating redissolution and reprecipitation procedures, followed by vacuum drying to isolate the desired polyimide precursor. To improve the degree of purification, the polymer solution may be passed through a column packed with an anion and / or cation exchange resin swollen with an appropriate organic solvent to remove ionic impurities.

[0040] The molecular weight of the polyimide precursor (A), as measured by gel permeation chromatography in terms of polystyrene equivalent weight average molecular weight, is preferably 8,000 to 150,000, more preferably 9,000 to 50,000. A weight average molecular weight of 8,000 or more provides good mechanical properties, while a weight average molecular weight of 150,000 or less provides good dispersibility in a developer and good relief pattern resolution. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The weight average molecular weight 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.

[0041] (A) Polyimide resin The photosensitive resin composition of the present disclosure may contain (A) a polyimide resin together with or instead of (A) the polyimide precursor.

[0042] The polyimide resin (A) does not generate any resin-derived elimination components, and therefore can suppress the cure shrinkage of the photosensitive resin composition, thereby enabling the production of a photosensitive resin composition having a higher cure residual film rate and improved post-cure flatness compared to polyimide precursors.

[0043] The (A) polyimide resin may have a polymerizable group in the side chain, but preferably does not have a polymerizable group in the side chain from the viewpoint of the elongation and storage stability of the cured film. The polyimide resin preferably does not substantially contain a polyamic acid or polyamic acid ester structure. In the present disclosure, "substantially does not contain" means, for example, that the imidization rate of the polyimide resin is 90% or more, preferably 95% or more.

[0044] The imidization rate of a polyimide resin can be measured by a known method, but in the present disclosure, it is calculated by the following method. First, the infrared absorption spectrum of the polyimide resin is measured, and the absorption peak of the imide structure (1780 cm -1 Near 1377cm -1 Next, the polyimide resin was heat-treated at 350°C for 1 hour, and the infrared absorption spectrum after the heat treatment was measured. -1 The imidization rate of the polyimide resin is calculated by comparing the peak intensity in the vicinity with the peak intensity before the heat treatment.

[0045] From the viewpoints of solubility in a solvent and flatness during coating, the polyimide resin (A) preferably contains a structure represented by the following general formula (12). This structure is also suitable for a solvent-developable photosensitive resin composition. The polyimide resin (A) is preferably not alkali-soluble, and X in the general formula (12) 10It is also preferable that / Y2 does not have an acidic group such as a carboxylic acid or a phenolic hydroxyl group. It is also preferable that the polyimide resin (A) does not have a fluorine atom. This can further suppress copper migration of the polyimide. [ka] {where, X 10 is a tetravalent organic group, Y2 is a divalent organic group, and n2 is an integer of 2 to 150.}

[0046] X 10 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, chemical resistance, and solubility in solvents, it is preferable that the cured film has at least one structure represented by the following formulas (24) to (32). [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0047] In addition, X in general formula (12) 10 Preferably, X has at least one structure represented by formulas (24) to (31) 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 elongation and chemical resistance. 10 From the viewpoint of the heat resistance of the cured film obtained from the photosensitive resin composition of the present disclosure, it is more preferable that X has at least one structure represented by formulas (24) to (26) and (28) to (31). 10 It is particularly preferred that the photosensitive resin composition of the present disclosure have at least one structure represented by formulas (24) and (29) to (31), since this results in particularly excellent coating film uniformity and cured film elongation.

[0048] Y2 in general formula (12) 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, excellent copper migration suppression in the b-HAST test, elongation, and chemical resistance, and solubility in solvents, it is preferable that Y2 have at least one structure represented by the following formulas (33) to (41). [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0049] Furthermore, Y2 preferably has at least one structure represented by formulas (33) to (39) from the viewpoints of suppressing copper voids after a high-temperature storage test, suppressing copper migration in a b-HAST test, and improving elongation and chemical resistance of a cured film obtained from the photosensitive resin composition of the present disclosure. Furthermore, Y2 more preferably has at least one structure represented by formulas (33) to (38) from the viewpoint of the mechanical properties of a cured film obtained from the photosensitive resin composition of the present disclosure. Additionally, Y2 particularly preferably has at least one structure represented by formulas (35) to (38) because the coating film uniformity and cured film elongation of the negative-type photosensitive resin composition of the present disclosure are particularly excellent. The excellent solubility of the structures represented by formulas (35) to (38) in solvents is due to the fact that these structures have a pendant phenyl structure.

[0050] In formula (12), 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.

[0051] From the viewpoint of solubility in a solvent, it is preferable that the terminal of the polyimide resin (A), preferably the terminal of the main chain of the polyimide resin (A), 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 (42) to (44). [ka] {where, R 41 , R 42 are each independently selected from a hydrogen atom and a monovalent organic group having 1 to 3 carbon atoms; R 43 is a divalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and k is an integer of 1 or 2. 44 represents a hydrogen atom or an organic group having 1 to 4 carbon atoms, and * represents the bonding site with the end of the (A) polyimide resin.} [ka] {where, R 45 , R 46 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. Also, * indicates the bonding site with the end of the (A) polyimide resin.} [ka] {where, R 47 , R 48 , R 49 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and j is an integer of 2 to 10. In addition, * indicates the bonding site with the end of the (A) polyimide resin.}

[0052] It is preferred that the acid anhydride group is derived from the raw material tetracarboxylic acid anhydride, the carboxyl group is formed by ring-opening of the 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 (42) include structures represented by the following formulas (45) to (48). [ka] [ka] [ka] [ka] {In the formula, * indicates the bonding site with the terminal of the (A) polyimide resin.}

[0053] More specific examples of the structure represented by general formula (43) include structures represented by the following formulae (49) and (50). [ka] [ka] {In the formula, * indicates the bonding site with the terminal of the (A) polyimide resin.}

[0054] More specific examples of the structure represented by general formula (44) include structures represented by the following formulae (51) to (54). [ka] [ka] [ka] [ka] {In the formula, * indicates the bonding site with the terminal of the (A) polyimide resin.}

[0055] From the viewpoints of high copper adhesion of the cured film, suppression of copper voids after high-temperature storage test, suppression of copper migration in b-HAST test, elongation, chemical resistance, and solubility in solvents, X in general formula (12) 10 is preferably any of the structures represented by general formulas (24) to (32), and Y2 is preferably any of the structures represented by general formulas (33) to (41).

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

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

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

[0059] (A) Method for preparing polyimide resin (A) Polyimide resin is obtained by reacting a tetracarboxylic dianhydride with a diamine to obtain a polyamic acid, which is then subjected to dehydration ring closure to be imidized.

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

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

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

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

[0064] When the terminals of the (A) polyimide resin are an acid anhydride group, a carboxyl group, and an amino group, the (A) polyimide resin is a polyimide resin obtained by reacting a tetracarboxylic dianhydride with a diamine to obtain a polyamic acid, followed by dehydration and ring closure to imidize the polyamic acid. The terminals of the (A) polyimide resin may be converted to structures represented by the above general formulas (42) to (44) by reacting the acid anhydride groups, carboxyl groups, and amino groups with a predetermined compound.

[0065] Polyimide resin (A) whose terminal has a structure represented by general formula (42) can be obtained, for example, by reacting the amino group at the polyimide terminal with an isocyanate compound. Specific examples of the isocyanate compound include 2-methacryloyloxyethyl isocyanate (2-isocyanatoethyl methacrylate: MOI), 2-acryloyloxyethyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, and 2-(2-methacryloyloxyethyloxy)ethyl isocyanate. The method for reacting the isocyanate compound is not particularly limited. For example, the isocyanate compound can be added to a dehydrated, ring-closed polyimide solution and stirred at room temperature to react with the amino group of the dehydrated, ring-closed polyimide.

[0066] The polyimide resin (A) whose terminal has a structure represented by general formula (43) can be obtained, for example, by reacting the amino group at the polyimide terminal with a chloride compound. Examples of the chloride compound include acryloyl chloride and methacryloyl chloride. The method for reacting the chloride compound is not particularly limited, but the chloride compound can be reacted with the amino group of the dehydrated, ring-closed polyimide by ice-cooling the polyimide solution and adding the chloride compound dropwise.

[0067] Polyimide resin (A) whose terminals have a structure represented by general formula (44) can be obtained, for example, by reacting the acid anhydride 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 and carboxyl groups of the dehydrated, ring-closed polyimide can be reacted with the alcohol-based compound using a condensing agent such as N,N'-dicyclohexylcarbodiimide (DCC) or an esterification catalyst such as p-toluenesulfonic acid.

[0068] In the production of (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.

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

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

[0071] (B) Heterocyclic compounds The heterocyclic compound (B) is represented by the following general formula (1), (2), (3), (4) or (5). [ka] In the formula, X1 is a nitrogen atom or a carbon atom substituted with R4, and R1, R2, R3, and R4 are each independently a hydrogen atom or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, a nitro group, a halogen group, and an organic group. [ka] {In the formula, R5, R6, and R7 each independently represent a hydrogen atom or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, a nitro group, a halogen group, and an organic group.} [ka] {In the formula, R8 and R9 each independently represent a hydrogen atom or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, a nitro group, a halogen group, and an organic group.} [ka] wherein X3 is a nitrogen atom or R 11 is a carbon atom substituted with R 10 , R 11 and R 12 are each independently a hydrogen atom or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, a nitro group, a halogen group, and an organic group. [ka] wherein X4 is a nitrogen atom or R 13 is a carbon atom substituted with R 13 and R 14 are each independently a hydrogen atom or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, a nitro group, a halogen group, and an organic group.

[0072] R1 to R in general formulas (1) to (5) 14is not particularly limited as long as it is a hydrogen atom, a hydroxyl group, an amino group, an amide group, a nitro group, a halogen group, or an organic group. The organic group may be, for example, a branched or linear alkyl group, an aromatic group, or a carboxyl group, and the alkyl group or aromatic group may have a substituent. The number of carbon atoms in the alkyl group is not particularly limited and may be, for example, 1 to 10 or 1 to 5.

[0073] When the (B) heterocyclic compound contains a compound represented by formula (1), (2), (3), (4), or (5), excellent copper adhesion can be achieved not only with low-temperature curing but also with high-temperature curing. Furthermore, copper migration and copper void suppression effects can be achieved not only with high-temperature curing but also with low-temperature curing. The reason for this is unclear and we are not bound by theory; however, it is believed that the unshared electron pair associated with the nitrogen atom in the heterocyclic skeleton acts on copper, causing it to be unevenly distributed at the copper interface. Furthermore, the secondary amine formed by the presence of a ketone in the skeleton forms hydrogen bonds with the polyimide precursor or polyimide, allowing the resin to interact with copper and improve copper adhesion. Furthermore, the uneven distribution of the heterocyclic compound at the copper interface is thought to strongly suppress oxidation reactions at the copper interface, thereby suppressing copper migration and copper voids.

[0074] Specific examples of the heterocyclic compound (B) represented by general formula (1) include, but are not limited to, pyrido[2,3-d]pyrimidin-4-ol, pteridin-4-ol, 7-phenyl-pteridin-4-ol, pterin-6-carboxylic acid, and 6-nitro-3H-pyrido[2,3-d]pyrimidin-4-one. Among these, pterin-6-carboxylic acid is preferred from the viewpoints of copper adhesion and copper migration inhibition.

[0075] From the viewpoint of solubility, X1 in formula (1) is preferably a carbon atom substituted with R4.

[0076] Specific examples of the heterocyclic compound (B) represented by general formula (2) include, but are not limited to, 7-methyl-2,4-dioxo-1,2,3,4-tetrahydropyrido[2,3-d]pyrimidine-5-carboxylic acid, 1H,2H,3H,4H-pyrido[2,3-d]pyrimidine-2,4-dione, and 7-chloropyrido[2,3-d]pyrimidine-2,4(1H,3H)-dione.

[0077] Specific examples of the heterocyclic compound (B) represented by general formula (3) include, but are not limited to, xanthopterin and 2-amino-3,4a,5,8a-tetrahydropteridine-4,6-dione. Among these, xanthopterin is preferred from the viewpoints of copper adhesion and copper migration inhibition.

[0078] Specific examples of the heterocyclic compound (B) represented by general formula (4) include, but are not limited to, allopurinol, 4-[2-(2-amino-4,7-dihydro-4-oxo-3H-pyrrolo[2,3-d]pyrimidin-5-yl)ethyl]benzoic acid, 6-amino-1H-pyrazolo[3,4-d]pyrimidin-4(7H)-one, 7-deazahypoxanthine, 2-amino-4-oxo-4,7-dihydro-1H-pyrrolo[2,3-d]pyrimidine-5-carboxylic acid, and 6-(trifluoromethyl)-1H-pyrazolo[3,4-d]pyrimidin-4-ol. Among these, from the viewpoints of copper adhesion and copper migration inhibition, 4-[2-(2-amino-4,7-dihydro-4-oxo-3H-pyrrolo[2,3-d]pyrimidin-5-yl)ethyl]benzoic acid, 6-amino-1H-pyrazolo[3,4-d]pyrimidin-4(7H)-one, and 2-amino-4-oxo-4,7-dihydro-1H-pyrrolo[2,3-d]pyrimidine-5-carboxylic acid are preferred.

[0079] In addition, from the viewpoint of solubility, X3 in formula (4) is CR 11 In the case of R 10 , R 11 , or R 12At least one of these is preferably a hydroxyl group, an amino group, an amide group, a nitro group, a halogen group or an organic group.

[0080] Specific examples of the heterocyclic compound (B) represented by general formula (5) include, but are not limited to, 1H-pyrazolo[3,4-d]pyrimidine-4,6(2H,5H)-dione, 7-deazaxanthine, and 5-(4-iodophenyl)-1H-pyrrolo[2,3-d]pyrimidine-2,4(3H,7H)-dione. When these compounds are added to the resin composition, they may be in the form of a hydrate.

[0081] Particularly from the viewpoint of copper adhesion, the heterocyclic compound (B) is preferably a compound represented by the following formula (6), (7), (8), (9) or (10). [ka] wherein X5 is a nitrogen atom or R 18 is a carbon atom substituted with R 15 , R 16 , R 17 and R 18 are each independently a hydrogen atom, or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, and an organic group having 1 to 10 carbon atoms which may have at least one of a hydroxyl group, an amino group, an amide group, a carbonyl group, and a carboxyl group.} [ka] {where, R 19 , R 20 and R 21 are each independently a hydrogen atom, or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, and an organic group having 1 to 10 carbon atoms which may have at least one of a hydroxyl group, an amino group, an amide group, a carbonyl group, and a carboxyl group.} [ka] {where, R 22 and R 23are each independently a hydrogen atom, or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, and an organic group having 1 to 10 carbon atoms which may have at least one of a hydroxyl group, an amino group, an amide group, a carbonyl group, and a carboxyl group.} [ka] wherein X7 is a nitrogen atom or R 25 is a carbon atom substituted with R 24 , R 25 and R 26 are each independently a hydrogen atom, or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, and an organic group having 1 to 10 carbon atoms which may have at least one of a hydroxyl group, an amino group, an amide group, a carbonyl group, and a carboxyl group.} [ka] wherein X8 is a nitrogen atom or R 27 is a carbon atom substituted with R 27 and R 28 are each independently a hydrogen atom, or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, and an organic group having 1 to 10 carbon atoms which may have at least one of a hydroxyl group, an amino group, an amide group, a carbonyl group, and a carboxyl group.}

[0082] R in general formulas (6) to (10) 15 ~R 28 is not particularly limited as long as it is a hydrogen atom, a hydroxyl group, an amino group, an amide group, or an organic group having 1 to 10 carbon atoms, but may also be a carboxyl group, a branched or linear alkyl group or an aromatic group having the above-mentioned functional group, etc. Examples thereof include a hydroxymethyl group, a hydroxyethyl group, an acetyl group, an acetoxy group, and a p-carboxyphenyl group.

[0083] Specific examples of the heterocyclic compound (B) represented by general formula (6) include, but are not limited to, pyrido[2,3-d]pyrimidin-4-ol, pteridin-4-ol, 7-phenyl-pteridin-4-ol, and pterin-6-carboxylic acid. Among these, pterin-6-carboxylic acid is preferred from the viewpoints of copper adhesion and copper migration inhibition.

[0084] From the viewpoint of solubility, X5 in formula (6) is R 18 Preferably, it is a carbon atom substituted with .

[0085] Specific examples of the heterocyclic compound (B) represented by general formula (7) include, but are not limited to, 7-methyl-2,4-dioxo-1,2,3,4-tetrahydropyrido[2,3-d]pyrimidine-5-carboxylic acid and 1H,2H,3H,4H-pyrido[2,3-d]pyrimidine-2,4-dione.

[0086] Specific examples of the heterocyclic compound (B) represented by general formula (8) include, but are not limited to, xanthopterin and 2-amino-3,4a,5,8a-tetrahydropteridine-4,6-dione. Among these, xanthopterin is preferred from the viewpoints of copper adhesion and copper migration inhibition.

[0087] Specific examples of the heterocyclic compound (B) represented by general formula (9) include, but are not limited to, allopurinol, 4-[2-(2-amino-4,7-dihydro-4-oxo-3H-pyrrolo[2,3-d]pyrimidin-5-yl)ethyl]benzoic acid, 6-amino-1H-pyrazolo[3,4-d]pyrimidin-4(7H)-one, 7-deazahypoxanthine, and 2-amino-4-oxo-4,7-dihydro-1H-pyrrolo[2,3-d]pyrimidine-5-carboxylic acid. Among these, from the viewpoints of copper adhesion and copper migration inhibition, 4-[2-(2-amino-4,7-dihydro-4-oxo-3H-pyrrolo[2,3-d]pyrimidin-5-yl)ethyl]benzoic acid, 6-amino-1H-pyrazolo[3,4-d]pyrimidin-4(7H)-one, and 2-amino-4-oxo-4,7-dihydro-1H-pyrrolo[2,3-d]pyrimidine-5-carboxylic acid are preferred.

[0088] In addition, from the viewpoint of solubility, X7 in formula (9) is CR 25 In the case of R 24 , R 25 , or R 26 At least one of these is preferably a hydroxyl group, an amino group, an amide group, or an organic group having 1 to 10 carbon atoms.

[0089] Specific examples of the heterocyclic compound (B) represented by general formula (10) include, but are not limited to, 1H-pyrazolo[3,4-d]pyrimidine-4,6(2H,5H)-dione and 7-deazaxanthine. When these compounds are added to the resin composition, they may be in the form of a hydrate.

[0090] 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 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. From the viewpoints of copper adhesion, copper migration inhibition, and solubility in the composition, the content is preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less. While the reason for this is unclear and not limited by theory, it is presumed that by setting the content to 10 parts by mass or less, a brittle layer is less likely to form between the copper layer and the resin layer, resulting in good copper adhesion, and that the ionic components in the resin layer do not increase more than necessary, resulting in good copper migration.

[0091] (C) Photopolymerization initiator (C) Photopolymerization initiator will be explained. The photopolymerization initiator is preferably a photoradical polymerization initiator, and examples thereof include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone, acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexyl phenyl ketone, thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone, benzyl derivatives such as benzil, benzil dimethyl ketal, and benzyl-β-methoxyethyl acetal, benzoin derivatives such as benzoin and benzoin methyl ether, and 1-phenyl-1,2-butanedione. Preferred examples of the photopolymerization initiator include, but are not limited to, oximes such as 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, and 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime; N-arylglycines such as N-phenylglycine; aromatic biimidazoles; titanocenes; and photoacid generators such as α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide. Among the above photopolymerization initiators, oximes are more preferred, particularly in terms of photosensitivity.

[0092] The content of the (C) photopolymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 1 to 8 parts by mass, and even more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the (A) polyimide precursor or polyimide resin. The content is preferably 0.1 part by mass or more from the viewpoint of photosensitivity or patterning ability, and 20 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the photosensitive resin composition.

[0093] (D) Solvent The photosensitive resin composition may further contain (D) a solvent. (D) The solvent will be explained 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 them, 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.

[0094] Among these solvents, those that completely dissolve the polyimide precursor are particularly preferred, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, γ-butyrolactone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, etc. In particular, γ-butyrolactone and 3-methoxy-N,N-dimethylpropanamide are preferred from the viewpoint of in-plane uniformity when the photosensitive resin composition is applied onto a substrate.

[0095] The solvent may be one type or a mixture of two or more types, but from the viewpoint of appropriately adjusting the stability of the resin composition, two or more types are preferably used. When two or more types of solvents are used, from the viewpoint of in-plane uniformity, 50 wt % or more of the solvent is preferably either γ-butyrolactone or 3-methoxy-N,N-dimethylpropanamide, and more preferably γ-butyrolactone.

[0096] In the photosensitive resin composition, the amount of the solvent used is preferably 100 to 1000 parts by mass, more preferably 120 to 700 parts by mass, and even more preferably 125 to 500 parts by mass, relative to 100 parts by mass of the (A) polyimide precursor or polyimide resin.

[0097] (E) Photopolymerizable monomer The photosensitive resin composition may further contain (E) a photopolymerizable monomer. The use of (E) a photopolymerizable monomer promotes crosslinking of the photosensitive resin composition, improving resolution and reducing moisture permeability of the cured film, thereby suppressing copper migration. The photosensitive resin composition preferably contains 5 to 150 parts by mass of the photopolymerizable monomer per 100 parts by mass of (A) a polyimide precursor or polyimide resin. To achieve good resolution, the photosensitive resin composition preferably contains 5 or more parts by mass of the photopolymerizable monomer, more preferably 10 or more parts by mass, and even more preferably 20 or more parts by mass. On the other hand, if the photopolymerizable monomer is contained in an excessive amount, copper adhesion may be reduced. While the reason for this is unclear and not limited by theory, it is speculated that a high amount of the photopolymerizable monomer may cause a brittle layer to form between the copper layer and the resin layer, reducing copper adhesion. The upper limit, which can be arbitrarily combined with the above lower limit, is preferably 150 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 50 parts by mass or less, from the viewpoint of copper adhesion.

[0098] The photopolymerizable monomer 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 (55): [ka] {In formula (55), X 11 is an organic group, and L4, L5 and L6 each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. n7 is an integer of 1 to 10.

[0099] The 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 (56) and (57): [ka] [ka] Examples of the compound include, but are not limited to, compounds represented by the following formula:

[0100] In the present disclosure, when the number of radical polymerizable groups in a photopolymerizable monomer is one, it is referred to as monofunctional; when it is two or more, it is referred to as x-functional group according to the number x of radical polymerizable groups, but difunctional or higher functional groups may be collectively referred to as polyfunctional. The photopolymerizable monomer may be monofunctional or may be difunctional or higher. From the viewpoint of copper migration suppression, the 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, it is preferable that it be decafunctional or lower.

[0101] The 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 more preferably 800 or less. By setting the molecular weight of the photopolymerizable monomer within the above range, resolution is improved.

[0102] The photopolymerizable monomer may also contain a hydroxyl group or a urea group.

[0103] The photopolymerizable monomer having a hydroxyl group in the molecule includes a monomer having the following general formula (58): [ka] {In formula (58), X 12 is an organic group, and L7, L8, and L9 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. n8 is an integer of 1 to 10, and n9 is an integer of 1 to 10. Examples of structures represented by the following formula (58) are as follows: In terms of radical reactivity, it is preferred that L7 is a hydrogen atom or a methyl group, and L8 and L9 are hydrogen atoms. More specifically, examples of structures represented by the following formula (59): [ka] Examples include, but are not limited to, compounds represented by the following formula: Having a hydroxyl group in the molecular structure improves copper adhesion. The number of hydroxyl groups in the molecular structure is preferably one or more, more preferably two or more. The upper limit is preferably 10 or less, more preferably six or less, and even more preferably three or less. By keeping the number of hydroxyl groups in the molecular structure within the above range, copper adhesion to the substrate improves.

[0104] The photopolymerizable monomer having a urea group in the molecule is represented by the following general formula (60): [ka] {In formula (60), X 13 , X 14 , X 15 , X 16 are each independently a hydrogen atom, a monovalent organic group having a group represented by the following general formula (61), or a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and X 13 , X 14 , X 15 , X 16 At least one of the groups is a monovalent organic group having a group represented by the following general formula (61): [ka] {In formula (61), L 10 , L 11 and L 12 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms.} In the above formula (61), L 10 is a hydrogen atom or a methyl group, and L 11 , L 12 is preferably a hydrogen atom from the viewpoint of radical reactivity.

[0105] Examples of the heteroatom of the photopolymerizable monomer include an oxygen atom, a nitrogen atom, a phosphorus atom, and a sulfur atom.

[0106] In formula (60), X 13 , X 14 , X15 , X 16 When X is a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, it preferably contains an oxygen atom from the viewpoint of developability. The number of carbon atoms is not limited as long as it is 1 to 20, but from the viewpoint of heat resistance, it preferably has 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. 13 , X 14 , X 15 , X 16 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. 13 , X 14 , X 15 , X 16 When X are bonded to each other to form a ring structure, the degree of freedom of the bond angle of the urea group is lost, making it difficult to form a strong hydrogen bond. 13 , X 14 , X 15 , X 16 At least one of X is preferably a hydrogen atom. 13 , X 14 , X 15 , X 16 It is preferable that the number of hydrogen atoms in the formula (62) is two or less. [ka] Examples of the compound include compounds represented by the following formula:

[0107] The radical polymerizable compound 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 (63): [ka] {In formula (63), X 17 , X 18 , X 19 , X 20 are each independently a hydrogen atom, a monovalent organic group having a group represented by the following general formula (64), or a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and X 17 , X 18 , X19 , X 20 At least one of the groups is a monovalent organic group having a group represented by the following general formula (64), and at least one of the groups is a hydroxyl group.} [ka] {In formula (64), L 13 , L 14 and L 15 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms.} In the above formula (64), L 13 is a hydrogen atom or a methyl group, and L 14 , L 15 is preferably a hydrogen atom from the viewpoint of radical reactivity.

[0108] In formula (63), X 17 , X 18 , X 19 , X 20 When X is a monovalent organic group having 1 to 20 carbon atoms, which may contain a heteroatom, it preferably contains an oxygen atom from the viewpoint of developability. The number of carbon atoms is not limited as long as it is 1 to 20, but from the viewpoint of heat resistance, it preferably has 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. 17 , X 18 , X 19 , X 20 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. 17 , X 18 , X 19 , X 20 When X are bonded to each other to form a ring structure, the degree of freedom of the bond angle of the urea group is lost, making it difficult to form a strong hydrogen bond. 17 , X 18 , X 19 , X 20 At least one of X is preferably a hydrogen atom. 17 , X 18 , X 19 , X 20It is preferable that the number of hydrogen atoms in the formula (65) is two or less. [ka] Examples of the compound include compounds represented by the following formula:

[0109] The photopolymerizable monomer having a urea group can be obtained by, for example, reacting an isocyanate compound having a radical polymerizable group with an amine-containing compound, although the method for producing the same is not particularly limited. When the amine-containing compound contains a functional group such as a hydroxyl group that can react with isocyanate, a part of the isocyanate compound may contain a compound that has reacted with the functional group such as a hydroxyl group.

[0110] The photopolymerizable monomer may be used alone or in combination of two or more. When two or more photopolymerizable monomers are used in combination, the number of types is preferably six or less, and more preferably four or less, from the viewpoint of controlling the crosslink density.

[0111] When a mixture of multiple photopolymerizable monomers is used, it is preferable that at least one of the multiple photopolymerizable monomers has a different number of functional groups. When three or more photopolymerizable monomers are used, it is sufficient that at least one of them has a different number of functional groups, but it is preferable that all of the photopolymerizable monomers have different numbers of functional groups. When a mixture of multiple photopolymerizable monomers is used, it is preferable that at least one of the photopolymerizable monomers contains a monofunctional photopolymerizable monomer from the viewpoint of breaking elongation.

[0112] (F) Thermal crosslinking agent In order to suppress copper migration in the cured film, the photosensitive resin composition may optionally contain (F) a thermal crosslinking agent.

[0113] The thermal crosslinking agent is not particularly limited as long as it forms crosslinks when the relief pattern formed using the photosensitive resin composition of the present invention 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.

[0114] Examples of the thermal crosslinking agent include an alkoxymethyl compound, an epoxy compound, an oxetane compound, a bismaleimide compound, an allyl compound, and a blocked isocyanate compound. From the viewpoint of suppressing cure shrinkage, it is preferable that the thermal crosslinking agent (F) contains a nitrogen atom.

[0115] Examples of alkoxymethyl compounds include, but are not limited to, compounds of the following formula (66): [ka]

[0116] 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.).

[0117] Examples of epoxy compounds include 4-hydroxybutyl acrylate glycidyl ether, epoxy compounds containing a bisphenol A group, and hydrogenated bisphenol A diglycidyl ether. For example, Epolite 4000 (product name, manufactured by Kyoeisha Chemical Co., Ltd.) can be suitably used.

[0118] Examples of oxetane compounds include 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, bis[1-ethyl(3-oxetanyl)]methyl ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methyl]biphenyl, 4,4'-bis(3-ethyl-3-oxetanylmethoxy)biphenyl, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, diethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, bis(3 Examples of suitable oxetane derivatives include 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene, ...

[0119] Examples of bismaleimide compounds include 1,2-bis(maleimide)ethane, 1,3-bis(maleimide)propane, 1,4-bis(maleimide)butane, 1,5-bis(maleimide)pentane, 1,6-bis(maleimide)hexane, 2,2,4-trimethyl-1,6-bis(maleimide)hexane, N,N'-1,3-phenylenebis(maleimide), and 4-methyl-N,N'-1,3-phenylenebis(maleimide). N,N'-1,4-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.

[0120] Examples of the allyl compound include allyl alcohol, allyl anisole, allyl benzoate, allyl cinnamate, N-allyloxyphthalimide, allylphenol, allyl phenyl sulfone, allyl urea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl isocyanurate, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallylamine, triallyl 1,3,5-benzenetricarboxylate, triallyl trimellitate, triallyl phosphate, triallyl phosphite, and triallyl citrate.

[0121] Examples of the blocked isocyanate compound include hexamethylene diisocyanate-based blocked isocyanates (e.g., manufactured by Asahi Kasei Corporation under the trade names Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B, and WM44-L70G; manufactured by Mitsui Chemicals, Inc. under the trade name Takenate B-882N; and manufactured by Baxenden under the trade names 7960, 7961, 7982, 7991, and 7992); tolylene diisocyanate-based blocked isocyanates (e.g., manufactured by Mitsui Chemicals, Inc. under the trade name Takenate B-830); and 4,4'- Examples of such blocked isocyanates include diphenylmethane diisocyanate-based blocked isocyanates (e.g., Mitsui Chemicals, Inc., trade name: Takenate B-815N; Daiei Sangyo Co., Ltd., trade names: Bronate PMD-OA01 and PMD-MA01), 1,3-bis(isocyanatomethyl)cyclohexane-based blocked isocyanates (e.g., Mitsui Chemicals, Inc., trade name: Takenate B-846N; Tosoh Corporation, hereinafter trade names: Coronate BI-301, 2507, and 2554); and isophorone diisocyanate-based blocked isocyanates (e.g., Baxenden, hereinafter trade names: 7950, 7951, and 7990).

[0122] Among these, alkoxymethyl compounds are preferred from the viewpoint of copper adhesion.(F) The thermal crosslinking agents may be used alone or in combination of two or more.

[0123] The content of the (F) thermal crosslinking agent in the photosensitive resin composition of the present disclosure is preferably 0.2 to 40 parts by mass relative to 100 parts by mass of the (A) polyimide precursor or polyimide resin. From the viewpoint of suppressing copper migration, the lower limit of the thermal crosslinking agent is more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more. From the viewpoint of copper adhesion of the photosensitive resin composition of the present disclosure, the upper limit of the thermal crosslinking agent is more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less.

[0124] (G) Silane coupling agent In order to improve the copper adhesion of the cured film, the photosensitive resin composition may optionally contain (G) a silane coupling agent.

[0125] Examples of the silane coupling agent include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM803, manufactured by Chisso Corporation: trade name Sila-Ace S810), N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM573), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Corporation: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS1375, manufactured by Azmax Corporation: trade name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Corporation: trade name SIM6473.5C), and mercaptomethylmethyldimethoxysilane (manufactured by Azmax Corporation: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltrippropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltrippropoxysilane, 2-mercaptoethyltrippropoxysilane, 2-mercaptoethyltripropoxysilane Examples of the mercaptosilane include, but are not limited to, mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, (3-triethoxysilylpropyl)-t-butylcarbamate, 4,4-carbonylbis(2-(((3-triethoxysilyl)propyl)amino)carbonyl)benzoic acid, and 2-(3-triethoxysilylpropylcarbamoyl)benzoic acid.

[0126] Other examples of silane coupling agents include N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd. under the trade name LS3610, and Azmax Co., Ltd. under the trade name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Co., Ltd. under the trade name SIU9058.0), N-(3-diethoxymethoxysilylpropyl)urea, N-(3-ethoxydimethoxysilylpropyl)urea, N-(3-tripropoxysilylpropyl)urea, N-(3-diethoxypropoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-dimethoxypropoxysilylpropyl)urea, N-(3-methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea, N-(3-ethoxydimethoxysilylethyl )urea, N-(3-trippropoxysilylethyl)urea, N-(3-trippropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-trippropoxysilylbutyl)urea, 3-(m-aminophenoxy)propyltrimethoxysilane (manufactured by Azmax Corporation: trade name) Examples of the silane include, but are not limited to, m-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.1), and aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.2).

[0127] Further, 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, tetra-t-butoxysilane, tetrakis(methoxysilane), ethoxysilane), tetrakis(methoxy-n-propoxysilane), tetrakis(ethoxyethoxysilane), tetrakis(methoxyethoxyethoxysilane), bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane, bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane, bis(triethoxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide, bis[3-(triethoxysilyl)propyl]isothiazolinone ... [(xylsilyl)propyl]tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane, phenyl silanetriol, methyl phenyl silanediol, ethyl phenyl silanediol, n-propyl phenyl silanediol, isopropyl phenyl silanediol, n-butyldiphenyl silanediol, isobutylphenyl silanediol, tert-butylphenyl silanediol, diphenyl silanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethyl methyl phenyl silanol, n-propyl methyl phenyl silanol, isopropyl methyl phenyl silanol, n-butylmethyl phenyl silanol, isobutylmethyl phenyl silanol, tert-butylmethyl phenyl silanol, ethyl n-propyl phenyl silanol, ethyl isopropyl phenyl silanol, n-butylethyl phenyl silanol, isobutylethyl phenyl silanol, tert-butylethyl phenyl silanol, methyl diphenyl silanol,Examples of the silanol include, but are not limited to, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, and triphenylsilanol.

[0128] The 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 viewpoint of copper adhesion.

[0129] When a silane coupling agent is used, the content is preferably 0.01 to 20 parts by mass per 100 parts by mass of the (A) polyimide precursor or polyimide resin from the viewpoint of copper adhesion.

[0130] (H) Acid component The photosensitive resin composition may optionally contain an acid component (H) to improve the copper adhesion of the cured film and suppress copper migration. For example, by using component (H) in combination with a thermal crosslinking agent (F), the thermal crosslinking reaction of the thermal crosslinking agent (F) can be accelerated, thereby improving the suppression of copper migration.

[0131] Examples of (H) 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.

[0132] When (H) acid component is used, its content is preferably 0.001 to 5 parts by mass per 100 parts by mass of (A) polyimide precursor or polyimide resin. From the viewpoint of suppressing copper migration in the photosensitive resin composition of the present disclosure, the lower limit of (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 adhesion, the upper limit of (H) acid component is more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less.

[0133] The photosensitive resin composition may further contain components other than the above components (A) to (H). Examples of the components other than the 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.

[0134] (I) Thermal base generator The photosensitive resin composition may contain (I) a base generator. A base generator is a compound that generates a base when heated. By containing a thermal base generator, imidization of the photosensitive resin composition can be further promoted.

[0135] The thermal base generator is not particularly limited in type, but examples thereof include an amine compound protected by a tert-butoxycarbonyl group, or the thermal base generators disclosed in WO 2017 / 038598. However, the thermal base generator is not limited to these, and other known thermal base generators can also be used.

[0136] Examples of amine compounds protected by a tert-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, and 2-amino-1,3-propanediol. Diol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanolamine amine, 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 suitable tert-butoxycarbonyl compounds 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.

[0137] The content of the thermal base generator is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the (A) polyimide precursor or polyimide resin. The content is preferably 0.1 part 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.

[0138] (J) Hindered phenol compounds To inhibit discoloration on copper surfaces, the photosensitive resin composition may optionally contain a hindered phenol compound.

[0139] Examples of the hindered phenol compound include, but are not limited to, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t- butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, and the like.

[0140] Examples of the hindered phenol compound include 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1 ,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxybenzyl) 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-di 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,Examples of the hydroxybenzoates include, but are not limited to, 6-(1H,3H,5H)-trione and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0141] 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 and the like are particularly preferred.

[0142] The content of the hindered phenol compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of (A) polyimide precursor or polyimide resin, and from the viewpoint of photosensitivity, more preferably 0.5 to 10 parts by mass. When the content is 0.1 part by mass or more, for example, when the photosensitive resin composition is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented, while when the content is 20 parts by mass or less, excellent photosensitivity is achieved.

[0143] (K) Organotitanium compounds The photosensitive resin composition may contain an organotitanium compound. By containing an organotitanium compound, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at low temperatures.

[0144] Usable organotitanium compounds include those in which an organic chemical is bonded to a titanium atom via a covalent or ionic bond.

[0145] Specific examples of the organotitanium 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 improve the storage stability of the photosensitive resin composition and allow for the formation of good patterns. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), and titanium diisopropoxide bis(ethylacetoacetate).

[0146] 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.

[0147] 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.

[0148] IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.

[0149] V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.

[0150] VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate.

[0151] VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate.

[0152] Among them, the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of exhibiting better chemical resistance. 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 is preferred.

[0153] When an organotitanium compound is added, the content is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of (A) polyimide precursor or polyimide resin. When the content is 0.05 part by mass or more, good heat resistance and chemical resistance are exhibited, while when the content is 10 parts by mass or less, excellent storage stability is achieved.

[0154] (L) Sensitizer The photosensitive resin composition may optionally contain a sensitizer to improve photosensitivity.

[0155] 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-dimethylaminocinnamylideneindanone, p-di Methylaminobenzylidene 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-dimethylamino coumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, dimethylaminobenzoic acid isoa Examples of suitable mercaptobenzoates include 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, and 2,2'-(phenylimino)diethanol. These may be used alone or in combination of, for example, 2 to 5 types.

[0156] When the photosensitive resin composition contains a sensitizer, the content thereof is preferably 0.1 to 25 parts by mass per 100 parts by mass of the (A) polyimide precursor or polyimide resin.

[0157] (M) Polymerization inhibitor The photosensitive resin composition may optionally contain a polymerization inhibitor in order to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition during storage, particularly in the form of a solution containing a solvent.

[0158] Examples of 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.

[0159] <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.

[0160] (1) Resin layer formation process In this step, the 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, or the like, or spray application using a spray coater, can be used.

[0161] (2) Exposure process 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.

[0162] (3) Relief pattern formation process 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. Furthermore, 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.

[0163] The developer used for development is preferably, for example, a good solvent for the photosensitive resin composition, or a combination of the good solvent and a poor solvent. Examples of good solvents include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Examples of poor solvents include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When a mixture of a good solvent and a poor solvent is used, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the photosensitive resin composition. Furthermore, two or more types of each solvent, for example, several types, can be used in combination.

[0164] (4) Hardened relief pattern formation process In this step, the relief pattern obtained by the development is heat-treated to dissolve the photosensitive component and imidize the (A) polyimide precursor, thereby converting it into a cured relief pattern (cured film) composed of polyimide. Heat treatment can be performed using a variety of methods, including a hot plate, an oven, or a temperature-programmable heating oven. Heat treatment can be performed, for example, at 160°C to 350°C for 30 minutes to 5 hours. To further improve copper adhesion, the heat treatment temperature is preferably 350°C or 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 heat treatment temperature is preferably 170°C or higher, more preferably 250°C or higher. To achieve both copper adhesion and copper migration suppression, the heat treatment temperature is preferably 170°C to 350°C, more preferably 200°C to 280°C. The atmospheric gas during heat curing may be air, or an inert gas such as nitrogen or argon.

[0165] <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 (A) polyimide resin of the present disclosure based on the above-mentioned method for producing a cured relief pattern. Alternatively, a polyimide film can be produced by imidizing a photosensitive resin composition containing the (A) polyimide precursor of the present disclosure to form a cured polyimide product with an imidization rate of 80 to 100%. In this case, too, the polyimide film can be produced based on the above-mentioned method for producing a cured relief pattern. The structure of the polyimide contained in the cured relief pattern formed from the polyimide precursor composition is represented by the following general formula (68): [ka]

[0166] Preferred X9 and Y1 in formula (11), preferred X in formula (12) 10 For the same reason, Y2 is X in the structure represented by the general formula (68). 21 and Y3. In the general formula (68), the number of repeating units n9 is not particularly limited, but may be an integer of 2 to 150.

[0167] <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 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.

[0168] <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 directly on the display element, or may be laminated with another layer sandwiched therebetween. Examples of the cured film include surface protection films, insulating films, and planarizing films for TFT liquid crystal display elements and color filter elements, protrusions for MVA-type liquid crystal display devices, and partition walls for cathodes of organic EL elements.

[0169] The photosensitive resin composition of the present disclosure is preferably a photosensitive resin composition for forming an insulating member or an interlayer insulating film. The photosensitive resin composition can also be used to form a surface protective film, an interlayer insulating film, a rewiring insulating film, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure. In addition to being applied to the semiconductor device described above, the photosensitive resin composition of the present disclosure is also useful for applications such as an interlayer insulating film for a multilayer circuit, a cover coat for a flexible copper-clad board, a solder resist film, and a liquid crystal alignment film. [Example]

[0170] Examples of the present disclosure will be specifically described below, but the embodiments are not limited thereto. In the examples, comparative examples, and production examples, the physical properties of the polyimide precursor or the photosensitive resin composition were measured and evaluated according to the following methods.

[0171] <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℃ Column: Showa Denko Shodex KD-806M, two in series, or Showa Denko Shodex 805M / 806M series Standard monodisperse polystyrene: Shodex STANDARD SM-105 manufactured by Showa Denko K.K. Mobile phase: 0.1 mol / L LiBr / N-methyl-2-pyrrolidone (NMP) Flow rate: 1mL / min.

[0172] (2) Copper adhesion evaluation A 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputtered with a 200 nm thick titanium (Ti) and a 400 nm thick copper (Cu) in that order using a sputtering device (SME-200E model, manufactured by ULVAC Corporation). Next, the photosensitive resin composition was spin-coated onto the wafer using a coater developer (D-Spin60A model, manufactured by SOKUDO Co., Ltd.) so that the film thickness after curing would be approximately 8 μm. The composition was then pre-baked on a hot plate at 110°C for 240 seconds to form a coating film on the copper wafer. Subsequently, a parallel light mask aligner (PLA-501FA model, manufactured by Canon Inc.) was used to apply 800 mJ / cm of photosensitive resin composition to the wafer. 2 The entire surface was exposed to light. The film was then heated for 2 hours in a temperature-programmable curing oven (VF-2000 model, manufactured by Koyo Lindberg Co., Ltd.) under a nitrogen atmosphere at the temperatures shown in Tables 1 to 4 to obtain a cured relief pattern (thermo-cured polyimide coating film).

[0173] EVERCEL OPP tape (No. 830NEV, Sekisui Chemical Co., Ltd.) was applied to this sample, and the tape and polyimide coating were cut into 5 mm widths using a cutter. Then, using a Tensilon universal material testing machine (RTG-1210, A&D Co., Ltd.), the tape and polyimide coating were peeled at an angle of 180° at a speed of 50 mm / min for 60 mm, so as to separate the copper and polyimide. The load during this process was calculated as an integrated average, and this value was evaluated as the adhesion strength. A rating of C or higher indicated that the sample was suitable for use as a cured relief pattern for semiconductors. A: Adhesion strength is 0.4N / mm or more B: Adhesion strength is 0.3N / mm or more and less than 0.4N / mm C: Adhesion strength is 0.2N / mm or more and less than 0.3N / mm D: Adhesion strength is less than 0.2N / mm

[0174] (3) b-HAST test SiO on the surface xA TEG wafer was prepared by forming comb-shaped Cu wiring with a line / space of 10 μm / 10 μm and a height of 5 μm on a silicon wafer laminated with the above. The TEG wafer was immersed in a 1% acetic acid solution and ion-exchanged water for 1 minute each, then rinsed with running ion-exchanged water and dried with an air gun. An oxygen plasma treatment was then performed using an ashing device (NA-8000, manufactured by ULVAC Inc.) 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-Spin60A, manufactured by SOKUDO Co., Ltd.) to a film thickness of approximately 8 μm after curing. The coating was then pre-baked on a hot plate at 110°C for 240 seconds to form a coating film on the TEG wafer. Then, a parallel light mask aligner (PLA-501FA, Canon Inc.) was used to irradiate the laser beam at 800 mJ / cm. 2 The film was exposed to light. To ensure electrical continuity during the b-HAST test, the Cu electrode was masked to prevent exposure, and the unexposed areas were subsequently removed by development. After 30 minutes or more had elapsed since exposure, the film 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 1.4 times the time required for the unexposed areas to completely dissolve and disappear. This was followed by a rotary spray rinse with propylene glycol monomethyl ether acetate for 10 seconds. The film was then heated for 2 hours in a temperature-programmable curing oven (VF-2000, manufactured by Koyo Lindberg Co., Ltd.) under a nitrogen atmosphere at the temperatures listed in Tables 1 to 4, yielding a cured relief pattern.

[0175] This sample was subjected to a b-HAST test using an ion migration evaluation system (AMI-025-U-5, Espec Corp.) and a highly accelerated life test (HAST) chamber (EHS-222M, Espec Corp.) at 130°C and 85% RH with an applied voltage of 50 V. The insulation resistance between the copper wiring was measured at 30-minute intervals, and the resistance was 1 × 10 4The time from the start of the test to the breakdown was calculated and evaluated based on the following criteria. If the evaluation was C or higher, the product could be suitably used as a cured relief pattern for semiconductors. A: More than 500 hours until dielectric breakdown B: 300 hours or more but less than 500 hours until dielectric breakdown C: 100 hours or more but less than 300 hours until dielectric breakdown D: Less than 100 hours until breakdown

[0176] (4) Resolution evaluation A 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputtered with a 200 nm thick titanium (Ti) and a 400 nm thick copper (Cu) in that order using a sputtering device (Model SME-200E, manufactured by ULVAC Corporation). The photosensitive resin composition was then spin-coated onto the wafer using a coater developer (Model D-Spin 60A, manufactured by SOKUDO Co., Ltd.) to a film thickness of approximately 8 μm after curing, and the wafer was pre-baked on a hot plate at 110°C for 240 seconds to form a coating film on the copper wafer. This coating film was then irradiated with 50 mJ / cm using a lithography system (Ultratech AP-200, manufactured by Veeco) through circular masks with 9 μm, 10 μm, and 11 μmφ. 2 to 300 mJ / cm 2 Up to 25mJ / cm 2 The film was exposed to i-line light at a focus of 0 μm in a stepwise fashion. After 30 minutes or more, it was developed by rotary spray development using a coater developer (D-Spin 60A, manufactured by SOKUDO Co., Ltd.) at 23°C using cyclopentanone as the developer for 1.4 times the time required for the unexposed areas to completely dissolve and disappear, followed by a 10-second rotary spray rinse with propylene glycol monomethyl ether acetate. The film was then heated for 2 hours in a temperature-programmable curing oven (VF-2000, manufactured by Koyo Lindberg) under a nitrogen atmosphere at the temperatures listed in Tables 1 to 4, yielding a cured relief pattern.

[0177] The circular hole pattern obtained for this sample was observed for its pattern shape and width using a field emission scanning electron microscope S-4800 (manufactured by Hitachi High-Technologies Corporation). If the circular hole had no hollows at the bottom, a forward tapered opening, and the area of ​​the obtained circular hole opening was at least half the area of ​​the corresponding pattern mask opening, the pattern was deemed to have been resolved, and the smallest diameter of the exposure mask among the resolved openings was shown as the evaluation result.

[0178] <Production example> Production Example 1: (A) Synthesis of Polyimide Precursor A1 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was placed in a 2 L separable flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone (hereinafter GBL) were added, and the mixture was stirred at room temperature. 81.5 g of pyridine was added while 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.

[0179] Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 200 mL of γ-butyrolactone was added to the reaction mixture over 20 minutes with stirring, followed by the addition of 93.0 g of 4,4'-oxydianiline (ODA) suspended in 350 mL of γ-butyrolactone over 30 minutes with stirring. After further stirring at room temperature for 4 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour, followed by the addition of 400 mL of γ-butyrolactone. The precipitate that formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0180] 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. The resulting precipitate was filtered off and then vacuum dried to obtain a powdered polymer (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.

[0181] Production Example 2: (A) Synthesis of Polyimide Precursor A2 A polymer (Polyimide Precursor A2) was obtained by carrying out a reaction in the same manner as in the above-described Production Example 1, except that 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was used instead of 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA). The molecular weight of 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.

[0182] Production Example 3: (A) Synthesis of Polyimide Precursor A3 A polymer (Polyimide Precursor A3) was obtained by carrying out a reaction in the same manner as in the above-described Production Example 1, except that 124.0 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 29.4 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) were used instead of 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA). 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.

[0183] Production Example 4: (A) Synthesis of Polyimide Precursor A4 A polymer (Polyimide Precursor A4) was obtained by carrying out a reaction in the same manner as in Production Example 1, except that 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was used instead of 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 49.2 g of 1,4-phenylenediamine (pPD) was used instead of 93.0 g of 4,4'-oxydianiline (ODA). 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.

[0184] Production Example 5: (A) Synthesis of Polyimide Precursor A5 Polymer (A5) was obtained by carrying out a reaction in the same manner as in Production Example 1, except that 62 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 88.3 g of pyromellitic dianhydride (PMDA) were used instead of 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), and 98.6 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) was used instead of 93.0 g of 4,4'-oxydianiline (ODA). The molecular weight of polymer (A5) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 28,000.

[0185] Production Example 6: (A) Synthesis of Polyimide Resin A6 A three-neck flask equipped with a Dean-Stark extractor and purged with nitrogen was charged with 200 g of N-methyl-2-pyrrolidone (NMP) and 33.1 g (0.012 mol) of 6-(4-aminophenoxy)biphenyl-3-amine (PDPE). To this solution, 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 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 the polymer, which was then filtered and vacuum dried at 40 °C to obtain a powdered polymer (Polyimide Resin A6). The weight-average molecular weight of Polyimide Resin A6 was measured by gel permeation chromatography (standard polystyrene equivalent) to find Mw = 14,300.

[0186] 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 dissolved in a nitrogen-purged three-neck flask, 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 in the Dean-Stark extractor, heating was stopped and the mixture was cooled to room temperature.

[0187] 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 2000 g of ion-exchanged water to precipitate a polymer, which was then filtered and vacuum-dried at 40°C to obtain a powdered polymer (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.

[0188] Production Example 8: (A) Synthesis of Polyimide Resin 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.

[0189] Production Example 9: (A) Synthesis of Polyimide Resin 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.

[0190] 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) Polyimide precursors 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) 0.5 g of 7-methyl-2,4-dioxo-1,2,3,4-tetrahydropyrido[2,3-d]pyrimidine-5-carboxylic acid (manufactured by BLDpharm), (C) 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) photopolymerizable monomer E1: 5 g of NK Ester 4G (manufactured by Shin-Nakamura Chemical Co., Ltd.), (F) thermal crosslinker F1: 1 g of Nikalac MX-290 (manufactured by Sanwa Chemical Co., Ltd.), (G) silane coupling agent G1: 1 g of KBM573 (manufactured by Shin-Etsu Chemical Co., Ltd.), (K) organic titanium compound K1: Orgatix 0.5 g of TC-750 (Matsumoto Fine Chemical Co., Ltd.) and 10 g of (L) sensitizer L1: 2,2'-(phenylimino)diethanol (Kanto Chemical Co., Ltd.) were dissolved in a mixed solvent of (D) 80 g of solvent D1: γ-butyrolactone (hereafter referred to as GBL, Mitsubishi Chemical Corporation) and 20 g of solvent D2: dimethyl sulfoxide (hereafter referred to as DMSO, Toray Fine Chemicals Co., Ltd.). The viscosity of the resulting solution was adjusted to approximately 40 poise by adding the required amount of a solution of GBL:DMSO = 80:20 (mass ratio), to prepare a photosensitive resin composition. The composition was evaluated according to the method described above. The results are shown in Table 1.

[0191] <Examples 2 to 53 and Comparative Examples 1 to 8> Photosensitive resin compositions were prepared by adjusting the compounding ratios as shown in Tables 1 to 4, except for the solvent, and dissolving the other components in the solvent in the same manner as in Example 1 and adjusting the viscosity. The photosensitive resin compositions shown in Tables 1 to 3 were then evaluated for copper adhesion and copper migration performance. The photosensitive resin compositions shown in Table 4 were evaluated for resolution in addition to the evaluation of copper adhesion and copper migration performance. The results of the examples and comparative examples are shown in Tables 1 to 4. The compounds listed in Tables 1 to 4 are as follows:

[0192] (A) Polyimide precursor or its comparable 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 (an acid-modified epoxy acrylate having a biphenyl skeleton, manufactured by Nippon Kayaku Co., Ltd.)

[0193] (B) Heterocyclic compounds B1: 7-methyl-2,4-dioxo-1,2,3,4-tetrahydropyrido[2,3-d]pyrimidine-5-carboxylic acid (BLDpharm) B2: Xanthopterin (Tokyo Chemical Industry Co., Ltd.) B3: Allopurinol (Tokyo Chemical Industry Co., Ltd.) B4: 4-[2-(2-amino-4,7-dihydro-4-oxo-3H-pyrrolo[2,3-d]pyrimidin-5-yl)ethyl]benzoic acid (Tokyo Chemical Industry Co., Ltd.) B5: Pyrido[2,3-d]pyrimidin-4-ol (Fujifilm Wako Pure Chemical Industries, Ltd.) B6: 1H,2H,3H,4H-pyrido[2,3-d]pyrimidine-2,4-dione (Fujifilm Wako Pure Chemical Industries, Ltd.) B7: Pteridin-4-ol (Fujifilm Wako Pure Chemical Industries, Ltd.) B8: 7-phenyl-pteridin-4-ol (Sigma-Aldrich) B9: Pterin-6-carboxylic acid (Sigma-Aldrich) B10: 6-amino-1H-pyrazolo[3,4-d]pyrimidin-4(7H)-one (Combi-Blocks) B11: 1H-Pyrazolo[3,4-d]pyrimidine-4,6(2H,5H)-dione (Combi-Blocks) B12: 7-Deazahypoxanthine (Tokyo Chemical Industry Co., Ltd.) B13:7-Deazaxanthin (BLDpharm) B14: 2-amino-4-oxo-4,7-dihydro-1H-pyrrolo[2,3-d]pyrimidine-5-carboxylic acid (BLDpharm) B15: 6-nitro-3H-pyrido[2,3-d]pyrimidin-4-one (Combi-Blocks) B16: 7-Chloropyrido[2,3-d]pyrimidine-2,4(1H,3H)-dione (Fujifilm Wako Pure Chemical Industries, Ltd.) B17: 6-(trifluoromethyl)-1H-pyrazolo[3,4-d]pyrimidin-4-ol (Fujifilm Wako Pure Chemical Industries, Ltd.) B18: 5-(4-iodophenyl)-1H-pyrrolo[2,3-d]pyrimidine-2,4(3H,7H)-dione (BLDpharm) B1': 8-Azaadenine (Tokyo Chemical Industry Co., Ltd.) B2': 5-amino-1H-tetrazole (Chiyoda Chemical Co., Ltd.) B3': 1,2,3-benzotriazole (Tokyo Chemical Industry Co., Ltd.) B4': Hypoxanthine (Tokyo Chemical Industry Co., Ltd.) B5': Lumazine (Tokyo Chemical Industry Co., Ltd.)

[0194] (C) Photopolymerization initiator C1: 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime (Changzhou Strong Electronic New Materials Co., Ltd.)

[0195] (D) Solvent D1: GBL (Mitsubishi Chemical Corporation) D2: DMSO (Toray Fine Chemicals Co., Ltd.)

[0196] (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.)

[0197] (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.)

[0198] (G) Silane coupling agent G1: N-phenyl-3-aminopropyltrimethoxysilane (product name: KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.) G2: (3-triethoxysilylpropyl)-t-butylcarbamate (Gelest) G3: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Tokyo Chemical Industry Co., Ltd.)

[0199] (H) Acid component H1: (±)-Mandelic acid (Fujifilm Wako Pure Chemical Industries, Ltd.) H2: p-toluenesulfonic acid (Tokyo Chemical Industry Co., Ltd.)

[0200] (K) Organotitanium compounds K1: Diisopropoxytitanium bis(ethyl acetate) (product name: Orgatix TC-750, manufactured by Matsumoto Fine Chemical Co., Ltd.)

[0201] (L) Sensitizer L1: 2,2'-(phenylimino)diethanol (Kanto Chemical Co., Ltd.)

[0202] [Table 1]

[0203] [Table 2]

[0204] [Table 3]

[0205] [Table 4]

[0206] The results in Tables 1 to 3 show that Comparative Examples 1 to 8, which do not satisfy the requirements of the present disclosure, are unable to achieve both good copper adhesion and copper migration resistance (b-HAST test results). On the other hand, Examples 1 to 53, which satisfy the requirements of the present disclosure, exhibit excellent performance in both adhesion and copper migration resistance. Comparisons of Comparative Examples 2 to 4 and 6 with Examples 1 to 18, Comparative Example 5 with Example 42, and Comparative Example 8 with Example 44 reveal that the use of the (B) heterocyclic compound of the present disclosure improves copper adhesion and exhibits good adhesion even at a high cure temperature of 250°C. Furthermore, comparisons of Comparative Example 1 with Examples 22 to 25 reveal that the use of the (B) heterocyclic compound of the present disclosure improves copper migration resistance and adhesion even at a cure temperature of 200°C. Furthermore, comparisons of Comparative Example 7 with Example 43 reveal that the use of the (A) polyimide precursor and / or polyimide resin of the present disclosure improves both copper adhesion and copper migration resistance.

[0207] Next, looking at the Examples, a comparison of Examples 1 to 14 with Examples 15 to 18 reveals that those having the structures of general formulas (6) to (10) of the present disclosure are preferable in terms of copper adhesion over those having the structures of general formulas (1) to (5). Examples 4 and 19 to 21 have compositions with different contents of the (B) heterocyclic compound, but Examples 4 and 20, which have a content in the range of 0.01 to 10 parts by mass, have better copper adhesion or copper migration performance. While the reason for this is unclear and not limited by theory, it is presumed that by adjusting the content of the (B) heterocyclic compound to 10 parts by mass or less, the ionic components in the resin layer do not increase more than necessary, and copper migration is also improved.

[0208] In Examples 38 to 41, polyimide resin was used, but Examples 38, 39, and 41 did not contain fluorine, and therefore it is clear that the migration performance was better than that of Example 40.

[0209] Comparing Examples 52 and 53 in Table 4, the inclusion of the (E) photopolymerizable monomer reduces the minimum opening size and improves the resolution. It is presumed that the use of the (E) photopolymerizable monomer promotes crosslinking of the photosensitive resin composition, improving the resolution.

[0210] A comparison of Examples 4 and 51 shows that the inclusion of the thermal crosslinking agent (F) improves copper adhesion and copper migration resistance. A comparison of Examples 4 and 45 to 47 shows that the inclusion of the silane coupling agent (G) improves copper adhesion. A comparison of Examples 48 to 50 shows that the inclusion of the acid component (H) improves copper migration resistance. [Industrial Applicability]

[0211] 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 useful for producing electrical and electronic materials such as semiconductor devices and multilayer wiring boards. More specifically, it can be used, for example, in forming relief patterns for insulating materials for electronic components, as well as passivation films, buffer coating films, and interlayer insulating films in semiconductor devices.

Claims

1. Ingredients: (A) a polyimide precursor and / or a polyimide resin; (B) a heterocyclic compound; (C) a photopolymerization initiator; A photosensitive resin composition comprising: The heterocyclic compound (B) is represented by the following general formula (1): 【Chemistry 1】 {In the formula, X １ is a nitrogen atom or R ４ is a carbon atom substituted with R １ , R ２ , R ３ and R ４ are each independently a hydrogen atom or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, a nitro group, a halogen group, and an organic group. a compound represented by the following general formula (2): 【Chemistry 2】 {In the formula, R ５ , R ６ and R ７ are each independently a hydrogen atom or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, a nitro group, a halogen group, and an organic group. a compound represented by the following general formula (3): 【Transformation 3】 {In the formula, R ８ and R ９ are each independently a hydrogen atom or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, a nitro group, a halogen group, and an organic group. a compound represented by the following general formula (4): 【Chemistry 4】 {In the formula, X ３ is a nitrogen atom or R １１ is a carbon atom substituted with R １０ , R １１ and R １２ are each independently a hydrogen atom or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, a nitro group, a halogen group, and an organic group. or a compound represented by the following general formula (5): 【Transformation 5】 {In the formula, X ４ is a nitrogen atom or R １３ is a carbon atom substituted with R １３ and R １４ are each independently a hydrogen atom or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, a nitro group, a halogen group, and an organic group. A photosensitive resin composition comprising a compound represented by the formula:

2. The heterocyclic compound (B) is represented by the following general formula (6): 【Transformation 6】 {In the formula, X ５ is a nitrogen atom or R １８ is a carbon atom substituted with R １５ , R １６ , R １７ and R １８ are each independently a hydrogen atom, or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, and an organic group having 1 to 10 carbon atoms which may have at least one of a hydroxyl group, an amino group, an amide group, a carbonyl group, and a carboxyl group. a compound represented by the following general formula (7): 【Transformation 7】 {In the formula, R １９ , R ２０ and R ２１ are each independently a hydrogen atom, or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, and an organic group having 1 to 10 carbon atoms which may have at least one of a hydroxyl group, an amino group, an amide group, a carbonyl group, and a carboxyl group. a compound represented by the following general formula (8): 【Transformation 8】 {In the formula, R ２２ and R ２３ are each independently a hydrogen atom, or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, and an organic group having 1 to 10 carbon atoms which may have at least one of a hydroxyl group, an amino group, an amide group, a carbonyl group, and a carboxyl group. a compound represented by the following general formula (9): 【Chemistry 9】 {In the formula, X ７ is a nitrogen atom or R ２５ is a carbon atom substituted with R ２４ , R ２５ and R ２６ are each independently a hydrogen atom, or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, and an organic group having 1 to 10 carbon atoms which may have at least one of a hydroxyl group, an amino group, an amide group, a carbonyl group, and a carboxyl group. or a compound represented by the following general formula (10): 【Chemistry 10】 {In the formula, X ８ is a nitrogen atom or R ２７ is a carbon atom substituted with R ２７ and R ２８ are each independently a hydrogen atom, or a group selected from the group consisting of a hydroxyl group, an amino group, an amide group, and an organic group having 1 to 10 carbon atoms which may have at least one of a hydroxyl group, an amino group, an amide group, a carbonyl group, and a carboxyl group. The photosensitive resin composition according to claim 1, wherein the compound is a compound represented by the formula:

3. The photosensitive resin composition contains the polyimide precursor, and the polyimide precursor is represented by the following general formula (11): 【Chemistry 11】 {In the formula, X ９ is a tetravalent organic group, and Y １ is a divalent organic group, and n １ is an integer from 2 to 150, and R ２９ and R ３０ are each independently a hydrogen atom or a monovalent organic group. and / or the photosensitive resin composition contains the polyimide resin, and the polyimide resin has a structural unit represented by the following general formula (12): 【Chemistry 12】 {In the formula, X １０ is a tetravalent organic group, and Y ２ is a divalent organic group, and n ２ 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:

4. In the above general formula (11), R ２９ and R ３０ At least one of the following general formula (13): 【Chemistry 13】 {In the formula, L １ , L ２ and L ３ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m １ is an integer from 2 to 10. The photosensitive resin composition according to claim 3 , which has a structural unit represented by the following formula:

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

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

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

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

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

10. The photosensitive resin composition according to claim 1 or 2, further comprising an acid component (H).

11. 3. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition 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.

12. 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) heat-treating the relief pattern to form a hardened relief pattern; 1. A method for producing a cured relief pattern, comprising:

13. The method for producing a cured relief pattern according to claim 12, wherein the temperature in the heat treatment in the step (4) is 170°C or higher and 350°C or lower.

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

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

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