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

Abstract

The present disclosure provides a photosensitive resin composition which achieves high copper adhesion, while suppressing the occurrence of a copper void at the interface between a copper layer and a resin layer after a high temperature storage test and having little copper migration in a b-HAST test. A photosensitive resin composition according to the present disclosure contains the following components: (A) a polyimide precursor and / or a polyimide resin; (B) a tetrazole compound; (C) a photopolymerization initiator; and (D) a solvent. The tetrazole compound (B) has a pKa of 1.3 to 4.1, or is represented by general formula (1) or (2), or has a polar surface area (tPSA) of 81 to 200.

Description

[Technical Field]

[0001] This disclosure relates to a photosensitive resin composition, a method for producing a cured relief pattern using the same, and a method for producing a polyimide film, etc. This international application claims priority under Japanese Patent Application No. 2022-174360, filed on 31 October 2022, and the entire contents of said Japanese Patent Application are incorporated herein by reference. [Background technology]

[0002] Conventionally, polyimide resins, polybenzoxazole resins, phenolic resins, and the like have been used as insulating materials for electronic components, and as passivation films, surface protective films, and interlayer insulating films for semiconductor devices, possessing excellent heat resistance, electrical properties, and mechanical properties. Among these resins, those provided in the form of photosensitive resin compositions allow for the easy formation of heat-resistant relief pattern films through thermal imidization treatment by coating, exposure, development, and curing of the composition. Such photosensitive resin compositions have the advantage of significantly shortening the process compared to conventional non-photosensitive materials.

[0003] On the other hand, in recent years, the mounting methods (packaging structures) for semiconductor devices on printed circuit boards have also changed from the viewpoint of improving integration density and computing power, as well as miniaturizing chip size. From conventional mounting methods using metal pins and lead-tin eutectic solder, structures in which a polyimide coating directly contacts the solder bumps are now being used, such as BGA (Ball Grid Array) and CSP (Chip Size Packaging), which enable higher density mounting. Furthermore, structures such as FO (Fan Out) have been proposed, which have multiple redistribution layers on the surface of the semiconductor chip with an area larger than the area of ​​the semiconductor chip itself (see Patent Document 1).

[0004] Copper is commonly used for wiring in semiconductor devices, but in large-area packaging structures, the difference in thermal expansion coefficients between dissimilar materials causes stress, leading to delamination between the copper and the interlayer insulating material, which is a particularly problematic issue for electrical properties. Therefore, materials used as interlayer insulating films require high adhesion to copper.

[0005] Furthermore, in recent years, the application of semiconductor devices has been remarkable in automotive and mobile phone applications. Semiconductor devices in these fields require high reliability, and reliability tests are conducted under high-temperature environments. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] U.S. Patent No. 10658199 [Patent Document 2] Japanese Patent Publication No. 2012-194520 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] However, in conventional reliability tests, particularly high-temperature storage tests, voids due to migration (hereinafter also referred to as "copper voids" in this disclosure) sometimes occurred at the interface between the rewired copper layer and the resin layer after the test. When copper voids occur at the interface between the copper layer and the resin layer, the adhesion between the two decreases. Furthermore, when copper migrates to the resin layer (hereinafter also referred to as "copper migration" in this disclosure), it can cause short circuits between wirings, especially in semiconductor devices with fine wiring, preventing the insulating film from performing adequately. Therefore, a polyimide film that exhibits less copper migration and does not short circuit for long periods in reliability tests under high temperature and high humidity conditions (b-HAST: Biased Hughly Accelerated Stress Test) is desired.

[0008] One of the objectives of this disclosure is to provide a photosensitive resin composition that exhibits high copper adhesion, suppresses the generation of copper voids at the interface between the copper layer and the resin layer after high-temperature storage testing, and reduces copper migration in b-HAST testing. Suppression of copper migration in b-HAST testing leads to the formation of a polyimide film that is less prone to short circuits over long periods of time. Another objective is to provide a method for forming a cured relief pattern using the photosensitive resin composition of this disclosure, and a method for manufacturing a polyimide film. [Means for solving the problem]

[0009] The present inventors have found that the above problems can be solved by adding a specific tetrazole compound to a photosensitive resin composition. Examples of embodiments of this disclosure are listed in the following sections [1] to

[18] . [1] The following ingredients: (A) Polyimide precursor and / or polyimide resin, (B) Tetrazole compounds and (C) Photopolymerization initiator and (D) Solvent and A photosensitive resin composition comprising, A photosensitive resin composition having a pKa of 1.3 to 4.1 for the above (B) tetrazole compound. [2] The following ingredients: (A) Polyimide precursor and / or polyimide resin, (B) Tetrazole compounds and (C) Photopolymerization initiator and (D) Solvent and A photosensitive resin composition comprising, The above (B) tetrazole compound is the following general formula (1): [ka] {In formula (1), R1 is a hydrogen atom or a monovalent organic group selected from the group consisting of C1-C10 alkyl groups and C6-C10 aryl groups. The hydrogen atoms of the alkyl group and the aryl group may be independently substituted with at least one substituent selected from the group consisting of halogen atoms, hydroxyl groups, alkoxysilyl groups, and amino groups, or they may not be substituted.} Or the following general formula (2): [ka] {In formula (2), R2 is a hydrogen atom or a monovalent organic group selected from the group consisting of C1-C10 alkyl groups and C6-C10 aryl groups. R3 is a C1-C10 alkylene group. The hydrogen atoms of the alkyl group, the aryl group, and the alkylene group may each be independently substituted with at least one substituent selected from the group consisting of halogen atoms, hydroxyl groups, alkoxysilyl groups, and amino groups, or they may not be substituted.} A photosensitive resin composition comprising a compound represented by [formula]. [3] The following ingredients: (A) Polyimide precursor and / or polyimide resin, (B) Tetrazole compounds and (C) Photopolymerization initiator and (D) Solvent and A photosensitive resin composition comprising, A photosensitive resin composition having a polar surface area (tPSA) of 81 to 200 of the above (B) tetrazole compound. [4] A photosensitive resin composition according to any one of items 1 to 3, wherein the content of component (B) is 0.01 to 10 parts by mass per 100 parts by mass of component (A). [5] A photosensitive resin composition according to any one of items 1 to 4, wherein the above (B) tetrazole compound comprises a compound represented by the following general formula (3). [ka] {In formula (3), R4 is a hydrogen atom or a monovalent organic group selected from the group consisting of C1-C10 alkyl groups and C6-C10 aryl groups. The hydrogen atoms of the alkyl group and the aryl group may be independently substituted with at least one substituent selected from the group consisting of halogen atoms, hydroxyl groups, alkoxysilyl groups, and amino groups, or they may not be substituted.} [6] The photosensitive resin composition according to any one of items 1 to 5, wherein the above (B) tetrazole compound comprises a compound represented by the following formula. [ka] [7] (E) A photosensitive resin composition according to any one of items 1 to 6, further comprising a radical polymerizable compound. [8] The photosensitive resin composition according to item 7, wherein the content of component (E) is 20 to 80 parts by mass per 100 parts by mass of component (A). [9] The above photosensitive resin composition contains the above polyimide precursor, wherein the above polyimide precursor is of the following general formula (4): [ka] {In equation (4), X1 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer between 2 and 150, and R 11 and R 12 Each of these is independently either a hydrogen atom or a monovalent organic group. Represented by, and / or The above photosensitive resin composition comprises the above polyimide resin, wherein the above polyimide resin is of the following general formula (4'): [ka] {In equation (4'), X1 is a tetravalent organic group, Y1 is a divalent organic group, and n is an integer between 1 and 150.} A photosensitive resin composition according to any one of items 1 to 8, having a structural unit represented by .

[10] In the above general formula (4), R 11 and R 12 At least one of them is the following general formula (5): [ka] {In formula (5), L1, L2, and L3 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 is an integer from 2 to 10.} A photosensitive resin composition according to item 9, having a structural unit represented by .

[11] The photosensitive resin composition according to item 9 or 10, wherein X1 of the above general formula (4') is at least one selected from the structures represented by the following general formulas (6) to (14), or Y1 of the above general formula (4') is at least one selected from the structures represented by the following general formulas (15) to (23). [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[12] (F) A photosensitive resin composition according to any one of items 1 to 11, further comprising a thermal crosslinking agent.

[13] (K) A photosensitive resin composition according to any one of items 1 to 12, further comprising an adhesive aid.

[14] The above photosensitive resin composition is a photosensitive resin composition for forming a surface protective film, an interlayer insulating film, an insulating film for redistribution, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure, as described in any one of items 1 to 13.

[15] The following steps: (1) A step of applying a photosensitive resin composition described in any one of items 1 to 14 onto a substrate to form a photosensitive resin layer on the substrate, (2) A step of exposing the above photosensitive resin layer, (3) A step of developing the photosensitive resin layer after exposure to form a relief pattern, (4) A step of heat-treating the above relief pattern to form a hardened relief pattern. A method for manufacturing a hardened relief pattern, including [the specified element].

[16] The method for manufacturing a hardened relief pattern as described in item 15, wherein the heat treatment in step (4) above is a heat treatment at 350°C or lower.

[17] A cured film comprising a cured product of a photosensitive resin composition described in any one of items 1 to 14.

[18] A method for producing a polyimide film, comprising curing a photosensitive resin composition described in any one of items 1 to 14. [Effects of the Invention]

[0010] According to this disclosure, it is possible to provide a photosensitive resin composition that exhibits high copper adhesion, suppresses the generation of copper voids at the interface between the copper layer and the resin layer after high-temperature storage testing, and reduces copper migration in b-HAST testing. Furthermore, it is possible to provide a method for manufacturing a cured relief pattern using the photosensitive resin composition, and a method for manufacturing a polyimide film. [Modes for carrying out the invention]

[0011] The embodiments of this disclosure will be described in detail below. This disclosure is not limited to the embodiments described below, and can be implemented in various modifications within the scope of its gist. Throughout this disclosure, structures represented by the same reference numerals in the general formula may be identical or different when multiple such structures exist in a molecule. Furthermore, the upper and lower limits in each numerical range of this disclosure can be arbitrarily combined to form any numerical range.

[0012] <Photosensitive resin composition> The photosensitive resin composition of this disclosure comprises (A) a polyimide precursor and / or a polyimide resin, (B) a tetrazole compound, (C) a photopolymerization initiator, and (D) a solvent.

[0013] (A) Polyimide precursor (A) A polyimide precursor is a resin component contained in the photosensitive resin composition, and is converted into polyimide by being subjected to heat cyclization treatment. The structure of (A) the polyimide precursor is not limited as long as it is a resin that can be used in a photosensitive resin composition, but it is preferably not alkali-soluble. High chemical resistance can be obtained when the polyimide precursor is not alkali-soluble.

[0014] The polyimide precursor is represented by the following general formula (4):

Chemical Formula

[0015] In general formula (4), at least one of R 11 and R 12 is represented by the following general formula (5):

Chemical Formula

[0016] In general formula (4), the proportion of R 11 and R 12 being hydrogen atoms, based on the total moles of R 11 and R 12 as a whole, is more preferably 10% or less, further preferably 5% or less, and even more preferably 1% or less. In addition, the proportion of R 11 and R 12 in general formula (4) being the monovalent organic group represented by general formula (5), based on the total moles of R 11 and R 12It is preferable that the proportion of hydrogen atoms and the proportion of organic groups of general formula (5) be within the above range, more preferably 80% or more, and even more preferably 90% or more, based on the total number of moles.

[0017] In general formula (4), n1 is not limited to any integer between 2 and 150, but from the viewpoint of the photosensitive properties and mechanical properties of the photosensitive resin composition, an integer between 3 and 100 is preferred, and an integer between 5 and 70 is more preferred.

[0018] In general formula (4), the tetravalent organic group represented by X1 is preferably an organic group having 6 to 40 carbon atoms, and more preferably -COOR, from the viewpoint of achieving both heat resistance and photosensitive properties. 11 Base and -COOR 12 The group and the -CONH- group are in the ortho position relative to each other, and are aromatic or alicyclic aliphatic groups. Specifically, as a tetravalent organic group represented by X1, it is an organic group with 6 to 40 carbon atoms containing an aromatic ring, for example, the following general formula (24): [ka] Groups having the structure represented by the formula {wherein R6 is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group of C1 to C10, and a monovalent fluorine-containing hydrocarbon group of C1 to C10, 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.} are examples, but are not limited to these. Furthermore, the structure of X1 may be one type or a combination of two or more types. X1 groups having the structure represented by the above formula (24) are particularly preferred from the viewpoint of achieving both heat resistance and photosensitive properties.

[0019] As for the X1 group, among the structures represented by the above formula (24), in particular, the following formula: [ka]

[0020] The tetravalent organic group represented by {wherein R6 is at least one selected from the group consisting of a fluorine atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a monovalent fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and m is an integer selected from 0 to 3} is preferred from the viewpoint of imidization rate at low temperature heating, degassing properties, copper adhesion, and chemical resistance.

[0021] In the above general formula (4), 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, for example, the following formula (25): [ka] Examples of structures represented by {wherein R6 is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group of C1 to C10, and a monovalent fluorine-containing hydrocarbon group of C1 to C10, and n is an integer selected from 0 to 4.} include, but are not limited to, these. Furthermore, the structure of Y1 may be one type or a combination of two or more types. A Y1 group having the structure represented by the above formula (25) is particularly preferred from the viewpoint of achieving both heat resistance and photosensitive properties.

[0022] As for the Y1 group, among the structures represented by the above formula (25), in particular, the following formula: [ka] The divalent group represented by {wherein R6 is at least one selected from the group consisting of a fluorine atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a monovalent fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and n is an integer selected from 0 to 4.} is preferred from the viewpoint of imidization rate at low temperature heating, degassing properties, copper adhesion, and chemical resistance.

[0023] In the above general formula (5), the monovalent organic groups having 1 to 3 carbon atoms for L1, L2, and L3 are, for example, hydrocarbon groups having 1 to 3 carbon atoms, preferably alkyl groups. L1 is preferably a hydrogen atom or a methyl group, and L2 and L3 are preferably hydrogen atoms from the viewpoint of photosensitivity. Also, m1 is an integer between 2 and 10, preferably an integer between 2 and 4, from the viewpoint of photosensitivity.

[0024] In one embodiment, (A) the polyimide precursor is given by the following general formula (26): [ka] {where, R 11 , R 12 , and n1 are as defined above. It is preferable that the polyimide precursor has a structural unit represented by .

[0025] In general formula (26), R 11 and R 12 It is more preferable that at least one of the members is a monovalent organic group represented by the general formula (5) above. (A) The polyimide precursor contains a polyimide precursor represented by the general formula (6), which provides particularly high chemical resistance.

[0026] In one embodiment, (A) the polyimide precursor is given by the following general formula (27): [ka] {where, R 11 , R 12 , and n1 are as defined above. From the viewpoint of thermophysical properties, it is preferable that the polyimide precursor has a structural unit represented by .

[0027] In general formula (27), R 11 and R 12 It is more preferable that at least one of them is a monovalent organic group represented by the general formula (5) above.

[0028] (A) Polyimide precursors tend to have particularly high resolution when they contain both the structural unit represented by general formula (26) and the structural unit represented by general formula (27). For example, (A) polyimide precursor may contain a copolymer of the structural unit represented by general formula (26) and the structural unit represented by general formula (27), or it may be a mixture of the polyimide precursor represented by general formula (26) and the polyimide precursor represented by general formula (27).

[0029] (A) The polyimide precursor is given by the following general formula (28): [ka] {where, R 11 , R 12 , and n1 are as defined above. It is preferable that the polyimide precursor has a structural unit represented by .

[0030] (A) The polyimide precursor is given by the following general formula (29): [ka] {where, R 11 , R 12 , and n1 are as defined above. It is preferable that the polyimide precursor has a structural unit represented by (A). The presence of a polyimide precursor represented by general formula (29) in (A) the chemical resistance is particularly enhanced.

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

[0032] (A) Method for preparing polyimide precursors (A) The polyimide precursor is first prepared by reacting a tetracarboxylic dianhydride containing the aforementioned tetravalent organic group X1 with photopolymerizable alcohols having an unsaturated double bond, and optionally alcohols without an unsaturated double bond, to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as acid / ester). Subsequently, the partially esterified tetracarboxylic acid is obtained by amide polycondensation with the aforementioned diamines containing the divalent organic group Y1.

[0033] (Preparation of acid / ester compounds) (A) Examples of tetracarboxylic dianhydrides containing a tetravalent organic group X1 that are suitably used to prepare polyimide precursors include the tetracarboxylic dianhydride shown in the general formula (24) above, as well as pyromellitic dianhydride (PMDA), 4,4'-oxydiphthalic acid dianhydride (ODPA), benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA), diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc., but are not limited to these. Among these, preferred tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 4,4'-oxydiphthalic dianhydride (ODPA), and biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA). These can be used individually or in combination of two or more.

[0034] (A) Suitable photopolymerizable alcohols having unsaturated double bonds for preparing polyimide precursors include, for example, 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, and 2-hydroxy-3-t-butoxypropyl acrylate. Examples include chlorohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

[0035] In addition to the above-mentioned photopolymerizable alcohols having unsaturated double bonds, it is also possible to use a mixture of some alcohols without unsaturated double bonds, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, and benzyl alcohol.

[0036] Furthermore, as a polyimide precursor, a non-photosensitive polyimide precursor prepared only from the above-mentioned alcohols that do not have unsaturated double bonds may be used in combination with the photosensitive polyimide precursor. From the viewpoint of resolution, it is preferable that the non-photosensitive polyimide precursor be 200 parts by mass or less, based on 100 parts by mass of the photosensitive polyimide precursor. By stirring, dissolving, and mixing the above-mentioned suitable tetracarboxylic dianhydride and the above-mentioned alcohols in a solvent as described later, in the presence of a basic catalyst such as pyridine, at a temperature of 20 to 50°C for 4 to 24 hours, the esterification reaction of the acid anhydride proceeds, and the desired acid / ester product can be obtained.

[0037] (Preparation of polyimide precursors) To the above acid / ester mixture (typically a solution in a solvent described later), a suitable dehydrating 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, is added and mixed under ice cooling to form a polyacid anhydride from the acid / ester mixture. Then, a diamine containing a divalent organic group Y1, dissolved or dispersed separately in a solvent, is added dropwise to this mixture to perform amide polycondensation, thereby obtaining the desired polyimide precursor. Alternatively, the above acid / ester mixture can be acid-chlorinated using thionyl chloride or the like, and then reacted with a diamine compound in the presence of a base such as pyridine to obtain the desired polyimide precursor.

[0038] Diamines containing the divalent organic group Y1 include, for example, diamines having the structure shown in the general formula (21) above, as well as 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 Lufon, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene (TPE-Q), 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene (A PB), bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane Benzene, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP), 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene (BAFL), and those in which some of the hydrogen atoms on the benzene ring are substituted with methyl groups, ethyl groups, hydroxymethyl groups, hydroxyethyl groups, halogens, etc., for example, 3,Examples of diamines include, but are not limited to, 3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethitoxy-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 individually or in combination of two or more.

[0039] After the amide polycondensation reaction is complete, any water-absorbing by-products of the dehydrating condensation agent present in the reaction solution are filtered off as needed. Then, a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is added to the obtained polymer component to precipitate it. Further purification of the polymer is carried out by repeating the redissolution and reprecipitation operations, and the polymer is then vacuum-dried to isolate the target polyimide precursor. To improve the degree of purification, the solution of this polymer may be passed through a column packed with anion and / or cation exchange resin swollen with a suitable organic solvent to remove ionic impurities.

[0040] The molecular weight of the polyimide precursor (A) described above is preferably 8,000 to 150,000, and more preferably 9,000 to 50,000, when measured by weight-average molecular weight in terms of polystyrene equivalent using gel permeation chromatography. When the weight-average molecular weight is 8,000 or higher, the mechanical properties are good, and when it is 150,000 or lower, the dispersibility in the developer is good and the relief pattern resolution is good. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as the developing solvents for gel permeation chromatography. The weight-average molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended to select the standard monodisperse polystyrene from STANDARD SM-105, an organic solvent-based standard sample manufactured by Showa Denko Corporation.

[0041] (A) Polyimide resin The photosensitive resin composition of this disclosure may contain (A) polyimide resin together with (A) polyimide precursor, or in lieu thereof.

[0042] (A) Polyimide resin does not generate resin-derived desorbed components, thus suppressing curing shrinkage of the photosensitive resin composition. Therefore, a photosensitive resin composition with a higher cured film retention rate and improved post-curing flatness can be obtained compared to polyimide precursors.

[0043] (A) The polyimide resin may have polymerizable groups in its side chains, but it is preferable that it does not have polymerizable groups in its side chains from the viewpoint of elongation of the cured film and storage stability. It is preferable that the polyimide resin is substantially free of polyamic acid or polyamic acid ester structures. In this disclosure, "substantially free" means, for example, that the imidization rate of the polyimide resin is 90% or more, preferably 95% or more.

[0044] The imidization rate of polyimide resin can be measured by known methods, but in this 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) is determined. -1 Nearby, 1377cm -1 The presence of (in the vicinity) is confirmed. Next, the polyimide resin is heat-treated at 350°C for 1 hour, and the infrared absorption spectrum after heat treatment is measured, and 1377 cm⁻¹ is obtained. -1 The imidization rate of the polyimide resin is calculated by comparing the peak intensity in the vicinity with the peak intensity before heat treatment.

[0045] (A) The polyimide resin preferably contains a structure represented by general formula (4') from the viewpoint of solubility in solvents and flatness during coating. This structure is also suitable for solvent-developable photosensitive resin compositions. [ka] {In equation (4'), X1 is a tetravalent organic group, Y1 is a divalent organic group, and n is an integer between 1 and 150.}

[0046] X1 is a tetravalent organic group, and is not particularly limited as long as it is a structure derived from known tetracarboxylic dianhydrides. However, from the viewpoint of high copper adhesion of the cured film, suppression of copper voids after high-temperature storage tests, suppression of copper migration in b-HAST tests, excellent elongation and chemical resistance, and solubility in solvents described later, it is preferable that it has at least one structure represented by the following formulas (6) to (14). [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0047] Furthermore, it is preferable that X1 has at least one structure represented by formulas (6) to (13) from the viewpoint of suppressing copper voids after high-temperature storage tests of the cured film obtained from the photosensitive resin composition of this disclosure, suppressing copper migration in b-HAST tests, elongation, and chemical resistance. Moreover, it is even more preferable that X1 has at least one structure represented by formulas (6) to (8) and (10) to (13) from the viewpoint of heat resistance of the cured film obtained from the photosensitive resin composition of this disclosure. In addition, it is particularly preferable that X1 has at least one structure represented by formulas (6) and (11) to (13) because the uniformity of the coating film and the elongation of the cured film of the photosensitive resin composition of this disclosure are particularly excellent.

[0048] In formula (4'), Y1 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 viewpoint of high copper adhesion of the cured film, suppression of copper voids after high-temperature storage tests, suppression of copper migration in b-HAST tests, elongation, chemical resistance, and solubility in solvents, it is preferable that it has at least one structure represented by the following formulas (15) to (23). [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0049] Furthermore, Y1 preferably has at least one structure represented by formulas (15) to (21) from the viewpoint of suppressing copper voids after high-temperature storage tests of the cured film obtained from the photosensitive resin composition of this disclosure, suppressing copper migration in b-HAST tests, elongation, and chemical resistance. Moreover, Y1 is even more preferably having at least one structure represented by formulas (15) to (20) from the viewpoint of the mechanical properties of the cured film obtained from the photosensitive resin composition of this disclosure. In addition, Y1 is particularly preferably having at least one structure represented by formulas (17) to (20) because the coating film uniformity and cured film elongation of the negative-type photosensitive resin composition of this disclosure are particularly excellent. The excellent solubility of the structures represented by formulas (17) to (20) in solvents is due to the fact that these structures have a pendant phenyl structure.

[0050] In formula (4'), n is an integer between 2 and 150, preferably between 3 and 100, and more preferably between 5 and 70. It is preferable that n is an integer that satisfies the weight-average molecular weight of the polyimide resin (A) described later.

[0051] From the viewpoint of solubility in solvents described later, it is preferable that the terminal end of the (A) polyimide resin, preferably the main chain terminal end of the (A) polyimide resin, has at least one structure selected from the group consisting of an acid anhydride group, a carboxyl group, an amino group, and the following general formulas (30) to (32). [ka] {In formula (30), R1 and R2 are independently selected from a hydrogen atom and a monovalent organic group having 1 to 3 carbon atoms, R3 is an organic group having 1 to 20 carbon atoms which may contain a heteroatom, and k is an integer from 1 to 2. R4 is a hydrogen atom and an organic group having 1 to 4 carbon atoms, and * indicates a bonding site with the end of the (A) polyimide resin.} [ka] {In formula (31), R5 and R6 are independently a hydrogen atom and a monovalent organic group having 1 to 3 carbon atoms. Also, * indicates the bonding site with the end of the (A) polyimide resin.} [ka] {In formula (32), R7, R8, and R9 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and j is an integer from 2 to 10. Also, * indicates the bonding site with the end of the (A) polyimide resin.}

[0052] Preferably, the acid anhydride group is derived from the raw material tetracarboxylic anhydride, the carboxyl group is obtained by ring-opening the aforementioned acid anhydride group, and the amino group is derived from the raw material diamine. (A) More detailed specific examples of the case where the end of the polyimide resin has a structure represented by general formula (30) include the structures represented by the following formulas (33) to (36). [ka] [ka] [ka] [ka] {* in the formula indicates the bonding site with the end of (A) polyimide resin.}

[0053] More detailed specific examples of the structure represented by general formula (31) include the structures represented by the following formulas (37) and (38). [ka] [ka] {* in the formula indicates the bonding site with the end of (A) polyimide resin.}

[0054] More detailed specific examples of the structure represented by general formula (32) include the structures represented by the following formulas (39) to (42). [ka] [ka] [ka] [ka] {* in the formula indicates the bonding site with the end of (A) polyimide resin.}

[0055] From the viewpoint of high copper adhesion of the cured film, suppression of copper voids after high-temperature storage tests, suppression of copper migration in b-HAST tests, elongation, chemical resistance, and solubility in solvents, it is preferable that X1 of general formula (4') is one of the structures represented by general formulas (6) to (14), and Y1 is one of the structures represented by general formulas (15) to (23).

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

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

[0058] (A) The polyimide resin is preferably present in an amount of 10% to 70% by mass, more preferably 20% to 65% by mass, based on the total mass of the photosensitive resin composition containing 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 dehydrated, cyclized, and imidized.

[0060] There are no limitations on the method for dehydrating and cyclizing polyamic acids, but examples include the thermal imidation method, in which polyamic acids are heated at high temperatures to dehydrate and cyclize, and the chemical imidation method, in which acetic anhydride and a tertiary amine, which are dehydrating reducing agents, are added to dehydrate and cyclize.

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

[0062] While there are no particular limitations on tetracarboxylic dianhydrides, 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'-isopropylidene diphenoxy)diphthalic anhydride (BPADA), and 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BP Examples of dianhydrides include norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride (CpODA), bicyclo[2.2.2]octo-7-ene-2,3,5,6-tetracarboxylic dianhydride (BCD), 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA). Among these, bicyclo[2.2.2]octo-7-ene-2,3,5,6-tetracarboxylic dianhydride (BCD), 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), and 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride (6FDA) are preferred as tetracarboxylic dianhydrides.

[0063] While not specifically limited to diamines, concrete 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), and 3,3'-diphenyl Examples include 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, 6-(4-aminophenoxy)biphenyl-3-amine (PDPE) and 9,9'-bis(4-aminophenyl)fluorene (BAFL) are preferred as diamines.

[0064] (A) When the terminals of the polyimide resin are an acid anhydride group, a carboxyl group, and an amino group, the polyimide resin (A) is a polyimide resin obtained by dehydrating and cyclizing a polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine to form an imidized polyimide resin. The acid anhydride group, carboxyl group, and amino group at the terminals of the polyimide resin (A) may be reacted with a predetermined compound to form a structure represented by the above general formulas (30) to (32).

[0065] (A) Polyimide resins, whose terminals have a structure represented by general formula (30), can be obtained, for example, by reacting the amino groups at the polyimide terminals with isocyanate compounds. Specific examples of isocyanate compounds include 2-methacryloyloxyethyl isocyanate (2-isocyanatoethyl methacrylate: MOI), 2-acryloyloxyethyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, and 2-(2-methacryloyloxyethyloxy)ethyl isocyanate. The method for reacting the isocyanate compounds is not particularly limited, but they can be reacted with the amino groups of the dehydrated and cyclized polyimide by adding the isocyanate compound to a dehydrated and cyclized polyimide solution and stirring at room temperature.

[0066] (A) Polyimide resins, whose terminals have a structure represented by general formula (31), can be obtained, for example, by reacting the amino groups at the polyimide terminals with a chloride compound. Examples of chloride compounds include acryloyl chloride and methachloroyl chloride. There are no particular limitations on the method of reacting with the chloride compound, but the dehydrated and cyclized polyimide solution can be cooled with ice, and the chloride compound can be added dropwise to react with the amino groups of the dehydrated and cyclized polyimide.

[0067] Polyimide resin (A), whose terminal structure is represented by general formula (32), can be obtained, for example, by reacting the acid anhydride group and carboxyl group at the polyimide terminal 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. There are no particular limitations on the method of reacting with the alcohol-based compound, but a condensing agent such as N,N'-dicyclohexylcarbodiimide (DCC) or an esterification catalyst such as p-toluenesulfonic acid can be used to react the acid anhydride group and carboxyl group of the dehydrated and cyclized polyimide with the alcohol-based compound.

[0068] (A) In the production of polyimide resins, a reaction solvent may be used to carry out the reaction efficiently in a homogeneous system. The reaction solvent is not particularly limited as long as it can uniformly dissolve or suspend tetracarboxylic dianhydrides, diamines, and compounds having polymerizable functional groups at their terminal ends. Examples of reaction solvents include γ-butyrolactone (GBL), dimethyl sulfoxide, N,N-dimethylacetacetamide, 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] (A) When using the heat imidation method in the production of polyimide resins, an azeotropic solvent may be used to accelerate the imidation reaction. The azeotropic solvent is not particularly limited as long as it is a solvent that forms an azeotrope with water, but examples include toluene, ethyl acetate, N-dichlorohexylpyrrolidone, orthodichlorobenzene, xylene, and benzene.

[0070] (A) The polyimide resin may be purified by methods described in Patent Document 2 (Japanese Patent Publication No. 2012-194520), etc. For example, purification methods include removing unreacted substances by dropping the (A) polyimide resin solution into water and reprecipitation, removing condensing agents and the like that are insoluble in the reaction solvent by filtration, and removing the catalyst with an ion exchange resin. After these purification methods, the (A) polyimide resin may be dried by known methods and isolated in powder form.

[0071] (B) Tetrazole compounds (B) The tetrazole compound has a pKa of 1.3 to 4.1, is represented by formula (1) or (2) described later, or has a polar surface area (tPSA) of 81 to 200, and possesses one or a combination of these characteristics. By including such a (B) tetrazole compound, copper adhesion and copper migration suppression effects can be obtained. Furthermore, since copper voids are presumed to be formed as a result of copper migration, suppressing copper migration is also effective in suppressing copper voids.

[0072] In one embodiment, the (B) tetrazole compound has an acid dissociation constant (pKa) of 1.3 to 4.1. From the viewpoint of adhesion to copper and copper migration, a pKa of 2.0 to 3.6 is preferable. The reason why the above effects are achieved by using such a (B) tetrazole compound is not clear and is not limited to theory, but the inventors believe the following: That is, the tetrazole compound is thought to exert its effect by coordinating to the copper of the substrate, and in this case, it is presumed that if the pKa of the tetrazole compound is 4.1 or less, the interaction with the resin will be strengthened and copper adhesion will be improved. On the other hand, if the pKa of the tetrazole compound is 1.3 or higher, the interaction will not be too strong and copper migration will be suppressed. Therefore, it is presumed that the tetrazole compound has an appropriate acidity so that both adhesion to copper and copper migration can be achieved. For pKa, the calculated value was obtained using Advanced Chemistry Software V11.02 (1994-2018 ACD / Labs).

[0073] Examples of (B) tetrazole compounds having an acid dissociation constant (pKa) of 1.3 to 4.1 include, but are not limited to, 1H-tetrazole-5-carboxylic acid, 1H-tetrazole-5-acetic acid, 1H-tetrazole-5-ethyl carboxylate, 1H-tetrazole-5-methyl acetate, 1H-tetrazole-5-propionic acid, 2-[4-(1H-1,2,3,4-tetrazole-5-yl)phenyl]acetic acid, 2-(2H-tetrazole-5-yl)butanediic acid, 2,2-bis(2-2H-tetrazole-5-yl)ethyl)propanedioic acid, and 4-(1H-tetrazole-5-yl)benzoic acid. Furthermore, when adding these compounds to the resin composition, they may be in the form of hydrates.

[0074] In one embodiment, (B) the tetrazole compound is represented by the following formula (1) or (2). [ka] {In formula (1), R1 is a hydrogen atom or a monovalent organic group selected from the group consisting of C1-C10 alkyl groups and C6-C10 aryl groups. The hydrogen atoms of the alkyl group and the aryl group may be independently substituted with at least one substituent selected from the group consisting of halogen atoms, hydroxyl groups, alkoxysilyl groups, and amino groups, or they may not be substituted.} [ka] {In formula (2), R2 is a hydrogen atom or a monovalent organic group selected from the group consisting of C1-C10 alkyl groups and C6-C10 aryl groups, and R3 is a C1-C10 alkylene group. The hydrogen atoms of the alkyl group, aryl group, and alkylene group may each be independently substituted with at least one substituent selected from the group consisting of halogen atoms, hydroxyl groups, alkoxysilyl groups, and amino groups, or they may not be substituted.}

[0075] (B) By including the tetrazole compound represented by formula (1) or (2) above, excellent copper adhesion, copper migration suppression, and copper void suppression can be obtained. The reason for this is not clear and is not bound by theory, but it is thought that the lone pair of electrons attached to the nitrogen atom in the tetrazole acts on the copper and becomes concentrated at the copper interface, and the constituent atoms of the carboxylic acid and ester can form hydrogen bonds with the polyimide precursor, so that the resin can interact with the copper and improve copper adhesion. Furthermore, it is thought that the concentration of the tetrazole compound at the copper interface strongly suppresses oxidation reactions at the copper interface, thereby suppressing copper migration and copper voids. In addition, it is speculated that if R3 in general formula (2) has 1 to 10 carbon atoms, the molecular boiling point is higher than that of the compound in general formula (1), so it does not volatilize easily during pre-baking when coating the substrate and can remain in the film, and furthermore it moves easily within the film and tends to concentrate at the interface, so it is more effective in improving copper adhesion and suppressing copper voids.

[0076] Furthermore, from the viewpoint of copper adhesion in particular, it is preferable that the (B) tetrazole compound includes a compound represented by the following general formula (3). [ka] {In the formula, R4 is a hydrogen atom or a monovalent organic group selected from the group consisting of C1-C10 alkyl groups and C6-C10 aryl groups. The hydrogen atoms of the alkyl group and the aryl group may be independently substituted with at least one substituent selected from the group consisting of halogen atoms, hydroxyl groups, alkoxysilyl groups, and amino groups, or they may not be substituted.}

[0077] The C1-C10 alkyl groups R1, R2, and R4 in general formulas (1) to (3) may be branched or linear. Preferably, C1-C5 alkyl groups, such as methyl, ethyl, and propyl groups. Examples of C6-C10 aryl groups R1, R2, and R4 in general formulas (1) to (3) include phenyl, tolyl, xylyl, and naphthyl groups. The C1-C10 alkylene group R3 in general formula (3) may be branched or linear. Preferably, C1-C5 alkylene groups, such as methylene, ethylene, and propylene groups. The hydrogen atoms of these organic groups may or may not be independently substituted with at least one substituent selected from the group consisting of halogen atoms, hydroxyl groups, alkoxysilyl groups, and amino groups. However, the number of carbon atoms in the organic group does not include the number of carbon atoms of the alkoxysilyl group if one is present. Examples of halogen atoms include chlorine, fluorine, bromine, and iodine atoms. Examples of alkoxysilyl groups include trialkoxysilyl, dialkoxysilyl, and monoalkoxysilyl groups, specifically trimethoxysilyl, triethoxysilyl, dimethoxysilyl, and methoxysilyl groups. Compounds in general formula (3) in which R4 is a hydrogen atom are more preferred from the viewpoint of copper adhesion and copper voids and copper migration.

[0078] Examples of (B) tetrazole compounds represented by general formulas (1) to (2) include, but are not limited to, 1H-tetrazole-5-carboxylic acid, α,α-difluoro-2H-tetrazole-5-acetic acid, α-hydroxy-2H-tetrazole-5-acetic acid, α-amino-2H-tetrazole-5-acetic acid, 1H-tetrazole-5-methyl carboxylate, 1H-tetrazole-5-ethyl carboxylate, 1H-tetrazole-5-acetic acid, 1H-tetrazole-5-methyl acetate, 1H-tetrazole-5-ethyl acetate, and 1H-tetrazole-5-propyl acetate. Among these, 1H-tetrazole-5-carboxylic acid, 1H-tetrazole-5-ethyl carboxylate, 1H-tetrazole-5-acetic acid, and 1H-tetrazole-5-ethyl acetate are preferred from the viewpoint of copper adhesion and copper migration, and 1H-tetrazole-5-acetic acid is more preferred. When these compounds are added to the resin composition, they may be in the form of hydrates.

[0079] In one embodiment, (B) the tetrazole compound has a topological polar surface area (tPSA) of 81 to 200. Topological polar surface area (tPSA) is the area of ​​the polar portion of a molecule's surface and is an index mainly used in medicinal chemistry to evaluate the cell membrane permeability of drugs. By including a tetrazole compound with a tPSA of 81 to 200 in a photosensitive resin composition, copper adhesion and copper migration inhibition effects can be obtained. The reason for this is not clear and is not limited to theory, but it is thought that the tetrazole compound having a moderate polarity of 81 to 200 allows for moderate interaction with the resin when coordinated to copper, as mentioned in the section on pKa, thus enabling both copper adhesion and copper migration inhibition. Furthermore, since the molecular weight is smaller when the tPSA is 200 or less, the dispersibility of the tetrazole compound in the photosensitive resin composition is improved, which is thought to contribute to the copper adhesion and copper migration inhibition effects.

[0080] The tPSA was calculated using software called "RDKit." RDKit is an open-source Python library used in the field of cheminformatics. For details on RDKit, see, for example, "G. Landrum, RDKit: Open-Source Cheminformatics (http: / / www.rdkit.org)." The following program was used to calculate the tPSA in this disclosure. Python 3.8.8 RDkit 2023.03.3

[0081] Examples of (B) tetrazole compounds having a tPSA of 81 to 200 include, but are not limited to, 1H-tetrazole-5-carboxylic acid, 1H-tetrazole-5-acetic acid, 1H-tetrazole-5-propionic acid, 2-[4-(1H-1,2,3,4-tetrazole-5-yl)phenyl]acetic acid, 2-(2H-tetrazole-5-yl)butanediic acid, 2,2-bis(2-2H-tetrazole-5-yl)ethyl)propanedioic acid, 4-(1H-tetrazole-5-yl)benzoic acid, and 1H-tetrazole-5-butanoic acid. Among these, 1H-tetrazole-5-carboxylic acid, 1H-tetrazole-5-acetic acid, and 4-(1H-tetrazole-5-yl)benzoic acid are preferred from the viewpoint of copper adhesion and copper migration, and 1H-tetrazole-5-acetic acid is more preferred. Furthermore, when adding these compounds to the resin composition, they may be in the form of hydrates.

[0082] (B) The amount of tetrazole compound blended is preferably 0.001 parts by mass to 20 parts by mass, more preferably 0.01 parts by mass to 10 parts by mass, and more preferably 0.01 parts by mass to 5 parts by mass, per 100 parts by mass of (A) polyimide precursor or polyimide resin. The above blending amount is preferably 0.01 parts by mass or more in order to exert a sufficient effect from the viewpoint of copper adhesion and suppression of copper migration, preferably 10 parts by mass or less in the viewpoint of copper adhesion, suppression of copper migration and solubility in the composition, and even more preferably 5 parts by mass or less. By setting it to 10 parts by mass or less, although the reason is not clear and is not limited to theory, it is presumed that a brittle layer is less likely to form between the copper layer and the resin layer, resulting in good copper adhesion, and the ionic component in the resin layer does not increase more than necessary, resulting in good copper migration.

[0083] (C) Photopolymerization initiator (C) Photopolymerization initiators will be described. The photopolymerization initiator is preferably a photoradical polymerization initiator, and includes benzophenone derivatives such as benzophenone, o-benzoyl methyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzyl derivatives such as benzyl, benzyldimethyl ketal, and benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin and benzoin methyl ether; and 1-phenyl-1,2-butanedione-2-(o-methoxy Preferred photopolymerization initiators include, but are not limited to, oximes such as carbonyl 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, 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime, N-arylglycines such as N-phenylglycine, peroxides such as benzoyl perchloride, aromatic biimidazoles, titanocenes, and photoacid generators such as α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide. Among the above photopolymerization initiators, oximes are particularly preferred in terms of photosensitivity.

[0084] (C) The amount of photopolymerization initiator added is preferably 0.1 parts by mass to 20 parts by mass, more preferably 1 part by mass to 8 parts by mass, and even more preferably 1 part by mass to 5 parts by mass, per 100 parts by mass of (A) polyimide precursor or polyimide resin. The above amount is preferably 0.1 parts by mass or more from the viewpoint of photosensitivity or patternability, and preferably 20 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the photosensitive resin composition.

[0085] (D) Solvent (D) Solvents will be explained. Examples of solvents include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, alcohols, etc. For example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyrol 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, morpholin, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene, etc. can be used. Among these, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenyl glycol, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, and tetrahydrofurfuryl alcohol are preferred from the viewpoint of resin solubility, resin composition stability, and adhesion to the substrate.

[0086] Among such solvents, those that completely dissolve the polyimide precursor are particularly preferred, and examples include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, γ-butyrolactone, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide. In particular, from the viewpoint of in-plane uniformity when the photosensitive resin composition is coated onto a substrate, γ-butyrolactone and 3-methoxy-N,N-dimethylpropanamide are preferred.

[0087] The solvent may be one type or a mixture of two or more solvents, but from the viewpoint of appropriately adjusting the stability of the resin composition, it is preferable to use two or more types. When two or more solvents are included, 50% by weight or more of the solvent is preferably either γ-butyrolactone or 3-methoxy-N,N-dimethylpropanamide, and more preferably γ-butyrolactone, from the viewpoint of in-plane uniformity.

[0088] In the photosensitive resin composition, the amount of 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, per 100 parts by mass of (A) polyimide precursor or polyimide resin.

[0089] (E) Radical polymerizable compounds The photosensitive resin composition may further contain (E) a radical polymerizable compound. When (E) a radical polymerizable compound is used, crosslinking of the photosensitive resin composition progresses, and the moisture permeability of the cured film decreases, thereby providing a copper migration suppression effect. The photosensitive resin composition preferably contains 5 to 150 parts by mass of the radical polymerizable compound per 100 parts by mass of (A) a polyimide precursor or polyimide resin. To obtain good chemical resistance, the photosensitive resin composition preferably contains 5 parts by mass or more of the radical polymerizable compound, more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more. If the radical polymerizable compound is included in too large an amount, copper adhesion may decrease. However, it has been found that the photosensitive resin composition of this disclosure, by containing the above-mentioned specific tetrazole compound, can obtain high copper adhesion even when it contains a relatively large amount of the radical polymerizable compound. The upper limit, which can be arbitrarily combined with the lower limit above, is preferably 150 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 80 parts by mass or less, from the viewpoint of patterning characteristics.

[0090] A radical polymerizable compound is not particularly limited as long as it is a compound that undergoes radical polymerization reaction with a photopolymerization initiator and a thermal polymerization initiator, but it is preferably a (meth)acrylic compound, for example, the following general formula (43): [ka] {In formula (43), X 11 L is an organic group. 11 , L 12 and L 13 Each of these is independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. 11 It is an integer between 1 and 10. It is represented as}.

[0091] Radical polymerizable compounds 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; diacrylate and dimethacrylate of 1,6-hexanediol. Examples of compounds include diacrylates and dimethacrylates of neopentyl glycol, mono- or diacrylates and methacrylates 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, formulas (44) and (45) below: [ka] [ka] Examples of compounds represented by [the formula shown] include, but are not limited to, those described above.

[0092] In this disclosure, a radical polymerizable compound is referred to as monofunctional when it has one radical polymerizable group, and as x-functional when it has two or more radical polymerizable groups, according to the number x of radical polymerizable groups. However, compounds with two or more functional groups are sometimes collectively referred to as polyfunctional. Radical polymerizable compounds may be monofunctional or have two or more functional groups. From the viewpoint of chemical resistance, radical polymerizable compounds are preferably triplicate or more, more preferably quadruple-functional or more, and even more preferably hecafunctional or more. On the other hand, from the viewpoint of elongation at break, they are preferably ten-functional or less.

[0093] The molecular weight of the radical polymerizable compound 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 keeping it within the above range, chemical resistance and patterning properties are improved.

[0094] Preferably, at least one of the radical polymerizable compounds is a radical polymerizable compound having at least one hydroxyl group or a urea group.

[0095] Examples of radical polymerizable compounds having a hydroxyl group in the molecule include the following general formula (46): [ka] {In formula (46), X 11 L is an organic group. 11 , L 12 and L 13 Each of these is independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. 11 n is an integer between 1 and 10. 12 L is an integer from 1 to 10. A structure represented by} can be given. In the above equation (46), L 11 L is a hydrogen atom or a methyl group. 12 , L 13 From the viewpoint of radical reactivity, it is preferable that the atom is a hydrogen atom. More specifically, the following formula (47): [ka] Examples of compounds represented by the formula are, but are not limited to, those shown above. Having hydroxyl groups in the molecular structure provides particularly good chemical resistance. The number of hydroxyl groups in the molecular structure is preferably one or more, and more preferably two or more. The upper limit is preferably 10 or less, more preferably 6 or less, and even more preferably 3 or less. By keeping it within the above range, good chemical resistance and adhesion to the substrate are achieved.

[0096] Radical polymerizable compounds having a urea group in the molecule are defined by the following general formula (48): [ka] {In formula (48), X 20 , X 21 , X 22 , X 23 Each of these is independently a hydrogen atom, a monovalent organic group having a group represented by the following general formula (49), or a monovalent organic group having 1 to 20 carbon atoms which may also contain a heteroatom, and X 20 , X 21 , X 22 , X 23 At least one of them is a monovalent organic group having a group represented by the following general formula (49). [ka] {In formula (49), L 11 , L 12 and L 13 Each is independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. It can be represented as}. In the above formula (49), L 11 L is a hydrogen atom or a methyl group. 12 , L 13 From the viewpoint of radical reactivity, it is preferable that the atom is a hydrogen atom.

[0097] Examples of heteroatoms include oxygen atoms, nitrogen atoms, phosphorus atoms, and sulfur atoms.

[0098] X in formula (48) 20 , X 21 , X22 , X 23 However, if it is a monovalent organic group having 1 to 20 carbon atoms, which may also contain heteroatoms, it is more preferable to include an oxygen atom from the viewpoint of developability. The number of carbon atoms is not limited to 1 to 20, but from the viewpoint of heat resistance, 1 to 10 carbon atoms are preferred, and 3 to 10 carbon atoms are more preferred. X in formula (48) 20 , X 21 , X 22 , X 23 These elements may be bonded together to form a cyclic structure, but from the viewpoint of chemical resistance, it is preferable that they do not have a cyclic structure. 20 , X 21 , X 22 , X 23 When the molecules bond to each other to form a cyclic structure, the degree of freedom of the bond angles of the urea group is lost, making it difficult to form strong hydrogen bonds. From the perspective of forming hydrogen bonds with other molecules, X 20 , X 21 , X 22 , X 23 Preferably, at least one of them is a hydrogen atom. On the other hand, from the viewpoint of solubility, X 20 , X 21 , X 22 , X 23 Preferably, the hydrogen atoms are two or less. Specifically, the following formula: [ka] Examples of compounds represented by this formula are given.

[0099] Radical polymerizable compounds preferably have at least one hydroxyl group and at least one urea group in their molecule. A radical polymerizable compound having at least one hydroxyl group and at least one urea group in its molecule is, for example, the following general formula (50): [ka] {In formula (50), X 30 , X 31 , X 32 , X 33each independently represents a hydrogen atom, a monovalent organic group having a group represented by the following general formula (51), or a monovalent organic group having 1 to 20 carbon atoms which may contain a hetero atom, and X 30 , X 31 , X 32 , X 33 is at least one a monovalent organic group having a group represented by the following general formula (51), and at least one is a hydroxyl group.}

Chemical Formula

[0100] In formula (50), X 30 , X 31 , X 32 , X 33 when is a monovalent organic group having 1 to 20 carbon atoms which may contain a hetero atom, it is more preferable to contain 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, 1 to 10 carbon atoms are preferable, and 3 to 10 carbon atoms are more preferable. X in formula (51) 30 , X 31 , X 32 , X 33 may be bonded to each other to form a cyclic structure, but from the viewpoint of chemical resistance, it is preferable not to have a cyclic structure. X 30 , X 31 , X 32 , X 33 are bonded to each other to form a cyclic structure, the degree of freedom in the bonding angle of the urea group is lost, making it difficult to form strong hydrogen bonds. From the viewpoint of forming hydrogen bonds with other molecules, X 30 , X 31 , X 32 , X 33Preferably, at least one of them is a hydrogen atom. On the other hand, from the viewpoint of solubility, X 30 , X 31 , X 32 , X 33 Preferably, the hydrogen atoms are two or less. Specifically, the following formula: [ka] Examples of compounds represented by this formula are given.

[0101] The method for producing radical polymerizable compounds having a urea group is not particularly limited, but can be obtained, for example, by reacting an isocyanate compound having a radical polymerizable group with an amine-containing compound. If the amine-containing compound contains a functional group such as a hydroxyl group that can react with the isocyanate, a portion of the isocyanate compound may contain a compound that has reacted with the functional group such as the hydroxyl group.

[0102] While a single radical polymerizable compound may be used, it is preferable to use a mixture of two or more. Using a mixture of two or more improves chemical resistance and in-plane uniformity. The reason for the improved in-plane uniformity is speculative, but it is thought that when a large amount of only one radical polymerizable compound is added, microphase separation occurs with the polyimide precursor component in the varnish. For the above reasons, when using a single radical polymerizable compound, it is preferable to use 60 parts by mass or less, and more preferably 40 parts by mass or less, per 100 parts by mass of polyimide precursor.

[0103] When using a mixture of two or more radical polymerizable compounds, it is preferable to use six or fewer compounds, and more preferably four or fewer compounds, from the viewpoint of controlling the crosslinking density.

[0104] When a mixture of a plurality of radically polymerizable compounds is used, it is preferable that the number of functional groups of at least one radically polymerizable compound among the plurality of radically polymerizable compounds is different. When three or more radically polymerizable compounds are used, it is sufficient that at least one of them has a different number of functional groups, but it is preferable that all radically polymerizable compounds have different numbers of functional groups. When a plurality of radically polymerizable compounds are used, it is preferable to include at least one monofunctional radically polymerizable compound from the viewpoint of elongation at break.

[0105] When two or more types of radically polymerizable compounds are used in combination, it is preferable to contain at least one nitrogen atom-containing radically polymerizable compound and at least one nitrogen atom-free radically polymerizable compound. The nitrogen atom-containing radically polymerizable compound is preferably a urea group-containing radically polymerizable compound. Since nitrogen atom-containing radically polymerizable compounds can form strong hydrogen bonds, they provide excellent chemical resistance; however, when a plurality of nitrogen atom-containing radically polymerizable compounds are added, they form a complex hydrogen bond network, resulting in insufficient solubility.

[0106] The photosensitive resin composition may further contain components other than the above components (A) to (E). Examples of components other than components (A) to (E) include, but are not limited to, (F) a thermal crosslinking agent, (G) a heterocyclic compound, (H) a thermal base generator, (I) a hindered phenol compound, (J) an organic titanium compound, (K) an adhesion aid, (L) a sensitizer, and (M) a polymerization inhibitor.

[0107] (F) Thermal crosslinking agent In order to improve the copper adhesion of the polyimide film and suppress copper migration, the photosensitive resin composition may optionally contain a thermal crosslinking agent.

[0108] The term "thermal crosslinking agent" refers to a compound that causes an addition reaction or a condensation polymerization reaction upon heating. These reactions occur in combinations of (A) the polyimide resin and (F) the thermal crosslinking agent, between (F) the thermal crosslinking agent molecules, and between (F) the thermal crosslinking agent and other components described later, and the reaction temperature is preferably 150°C or higher.

[0109] Examples of thermal crosslinking agents include alkoxymethyl compounds, epoxy compounds, oxetane compounds, bismaleimide compounds, allyl compounds, and blocked isocyanate compounds. From the viewpoint of suppressing curing shrinkage, it is preferable that the (F) thermal crosslinking agent contains nitrogen atoms.

[0110] Examples of alkoxymethyl compounds include, but are not limited to, the compounds shown in the following formulas. [ka]

[0111] Other commercially available alkoxymethyl compounds include alkylated urea resin (product name MX290, manufactured by Nikalac Corporation) and 1,3,4,6-tetrakis(methoxymethyl) glycoluryl (product name MX270, manufactured by Nikalac Corporation).

[0112] Examples of epoxy compounds include 4-hydroxybutyl acrylate glycidyl ether, epoxy compounds containing a bisphenol A type group, and hydrogenated bisphenol A diglycidyl ether. For example, Epolite 4000 (product name, manufactured by Kyoeisha Chemical Co., Ltd.) can be suitably used.

[0113] 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 include ethyl-3-oxetanylmethyl)diphenoate, trimethylolpropanetris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritoltetrakis(3-ethyl-3-oxetanylmethyl) ether, poly[[3-[(3-ethyl-3-oxetanyl)methoxy]propyl]silasesquioxane] derivatives, oxetanyl silicates, phenol novolac type oxetanes, and 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene. For example, OXT121 (product name, manufactured by Toagosei Co., Ltd.) and OXT221 (product name, manufactured by Toagosei Co., Ltd.) can be suitably used.

[0114] 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). Examples include nilenbis(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-maleimidephenoxy)phenyl]propane.

[0115] Examples of allyl compounds include allyl alcohol, allylanisole, allyl benzoate, allyl cinnamate, N-alyloxyphthalimide, allylphenol, allylphenylsulfone, allylurea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl isocyanurate, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallylamine, 1,3,5-benzenetricarboxylic acid triallyl, trimellitate triallyl, triallyl phosphate, triallyl phosphite, and triallyl citrate.

[0116] Examples of blocked isocyanate compounds include hexamethylene diisocyanate-based blocked isocyanates (e.g., manufactured by Asahi Kasei Corporation, trade names: Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B, and WM44-L70G; manufactured by Mitsui Chemicals, Inc., trade name: Takenate B-882N; manufactured by Baxenden, trade names: 7960, 7961, 7982, 7991, and 7992, etc.); tolylene diisocyanate-based blocked isocyanates (e.g., manufactured by Mitsui Chemicals, Inc., trade name: Takenate B-830, etc.); 4,4'- Examples 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, etc.), 1,3-bis(isocyanatemethyl)cyclohexane-based blocked isocyanates (e.g., Mitsui Chemicals, Inc., trade name: Takenate B-846N; Tosoh Corporation, trade names below: Coronate BI-301, 2507 and 2554, etc.); and isophorone diisocyanate-based blocked isocyanates (e.g., Baxenden, trade names below: 7950, 7951 and 7990, etc.).

[0117] Among these, blocked isocyanate compounds and bismaleimide compounds are preferred from the viewpoint of storage stability. (F) The thermal crosslinking agent may be used alone or in combination of two or more types.

[0118] The content of (F) the thermal crosslinking agent in the photosensitive resin composition of this disclosure is preferably 0.2 parts by mass to 40 parts by mass per 100 parts by mass of (A) the polyimide precursor or polyimide resin. The lower limit of the thermal crosslinking agent is more preferably 1 part by mass or more, and even more preferably 5 parts by mass or more, from the viewpoint of chemical resistance. The upper limit of the thermal crosslinking agent is more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less, from the viewpoint of the storage stability of the photosensitive resin composition of this disclosure.

[0119] (G) Heterocyclic compounds The photosensitive resin composition of this disclosure may contain heterocyclic compounds in addition to the (B) tetrazole compound for purposes such as improving copper adhesion, developability, and copper migration suppression. Examples of heterocyclic compounds include imidazole derivatives, triazole derivatives, tetrazole derivatives other than (B), and purine derivatives.

[0120] Specific examples of purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8- Examples include minoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine, and their derivatives. These heterocyclic compounds may be used individually or as a mixture of two or more.

[0121] When the photosensitive resin composition contains a heterocyclic compound, the amount blended is preferably 0.1 to 10 parts by mass per 100 parts by mass of (A) polyimide precursor or polyimide resin, and more preferably 0.5 to 5 parts by mass from the viewpoint of copper adhesion. When the blending amount is 0.1 parts by mass or more, discoloration of the copper is suppressed when the photosensitive resin composition is formed on copper, while when it is 10 parts by mass or less, excellent copper adhesion is achieved.

[0122] (H) Thermobase Generator The photosensitive resin composition may contain a base-generating agent. A base-generating agent is a compound that generates a base when heated. Including a thermal base-generating agent can further promote the imidization of the photosensitive resin composition.

[0123] Examples of thermal base generators include amine compounds protected by a tert-butoxycarbonyl group, or thermal base generators disclosed in International Publication No. 2017 / 038598, although no specific type is defined. However, they are not limited to these, and other known thermal base generators can be used.

[0124] Examples of amine compounds protected by the tert-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, and 2-amino-1,3-propanediol. Diol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanol Luamine, diisopropanolamine, 3-pyrrolidinel, 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-butanol bis(3-aminopropyl)ether Examples 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 its derivative is protected by a tert-butoxycarbonyl group.

[0125] The blending amount of the thermal base generator is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, relative to 100 parts by mass of (A) the polyimide precursor or polyimide resin. From the viewpoint of the imidization promotion effect, the blending amount is preferably 0.1 part by mass or more, and from the viewpoint of the physical properties of the photosensitive resin layer after curing of the photosensitive resin composition, the blending amount is preferably 20 parts by mass or less.

[0126] (I) Hindered phenol compound In order to suppress discoloration on the copper surface, the photosensitive resin composition may optionally contain a hindered phenol compound. The hindered phenol compound is not limited, and examples include 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butylhydroquinone, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, isooctyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 4,4'-butylidene-bis(3-methyl-6-tert-butylphenol), triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2'-thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and the like.

[0127] Furthermore, examples of hindered phenol compounds include 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1 ,3,5-Tris[4-(1-ethylpropyl)-3-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-H Droxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-di Methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,Examples 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.

[0128] Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione is particularly preferred.

[0129] The amount of hindered phenol compound blended is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of (A) polyimide precursor or polyimide resin. When the blending amount is 0.1 parts 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 it is 20 parts by mass or less, the photosensitivity is excellent.

[0130] (J) Organic titanium compounds The photosensitive resin composition may contain an organotitanium compound. By including an organotitanium compound, a photosensitive resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0131] Examples of usable organotitanium compounds include those in which an organic chemical substance is bonded to a titanium atom via covalent or ionic bonds.

[0132] Specific examples of organotitanium compounds are shown in I) to VII) below: I) Titanium chelate compounds: Among these, titanium chelates having two or more alkoxy groups are more preferred because they provide good storage stability and a good pattern for the photosensitive resin composition. Specific examples include titanium bis(triethanolamine)diisopropoxide, titanium di(n-butoxide)bis(2,4-pentanedione), titanium diisopropoxidebis(2,4-pentanedione), titanium diisopropoxidebis(tetramethylheptanedione), and titanium diisopropoxidebis(ethylacetoacetate).

[0133] II) Tetraalkoxy titanium 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 tetrastearaloxide, titanium tetrakis[bis{2,2-(alyloxymethyl)butoxide}], etc.

[0134] III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, etc.

[0135] IV) Monoalkoxy titanium compounds: For example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.

[0136] V) Titanium oxide compounds: For example, titanium oxide bis(pentanedione), titanium oxide bis(tetramethylheptanedione), phthalocyanine titanium oxide, etc.

[0137] VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate.

[0138] VII) Titanate coupling agents: For example, isopropyltridodecylbenzenesulfonyl titanate.

[0139] In particular, the organotitanium 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 achieving better chemical resistance. Titanium diisopropoxide bis(ethyl acetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium are especially preferred.

[0140] When incorporating an organotitanium compound, the amount is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of (A) polyimide precursor or polyimide. When the amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited, while when it is 10 parts by mass or less, excellent storage stability is achieved.

[0141] (K) Adhesion aid To improve the adhesion between the film formed using the photosensitive resin composition and the substrate, the photosensitive resin composition may optionally contain adhesive aids. Examples of adhesive aids include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamidic acid, and benzophenone-3,3'-bis(N-[3-triethoxysilyl Examples include silane coupling agents such as propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and 3-(trialkoxysilyl)propylsuccinic anhydride, as well as aluminum-based adhesive aids such as aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0142] Of these adhesive aids, silane coupling agents are more preferable in terms of adhesive strength. When the photosensitive resin composition contains an adhesive aid, the amount of the adhesive aid is preferably in the range of 0.5 to 25 parts by mass per 100 parts by mass of (A) polyimide precursor.

[0143] Silane coupling agents are not limited to these, but examples include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: product name KBM803, manufactured by Chisso Corporation: product name Cyra Ace S810), N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: product name KBM573), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Co., Ltd.: product name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: product name LS1375, manufactured by Azmax Co., Ltd.: product name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Co., Ltd.: product name SIM6473.5C), and mercaptomethylmethyldimethoxysilane (manufactured by Azmax Co., Ltd.: product name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxy Examples include silane, 2-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.

[0144] Furthermore, while not limited to silane coupling agents, examples include N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: product name LS3610, manufactured by Azmax Co., Ltd.: product name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Co., Ltd.: product 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) Examples include urea, N-(3-tripropoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-tripropoxysilylbutyl)urea, 3-(m-aminophenoxy)propyltrimethoxysilane (manufactured by Azmax Co., Ltd.: product name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: product name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: product name SLA0599.1), aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: product name SLA0599.2), etc.

[0145] Furthermore, examples of silane coupling agents include 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax Co., Ltd.: product 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, and tetrax(me Toxiethoxysilane), tetrakis(methoxy-n-propoxysilane), tetrakis(ethoxyethoxysilane), tetrakis(methoxyethoxyethoxysilane), bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane, bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane, bis(triethoxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide, bis[ 3-(triethoxysilyl)propyl]tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylsiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyln-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol,Examples include, but are not limited to, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, and triphenylsilanol.

[0146] The silane coupling agents listed above may be used individually or in combination. Among the silane coupling agents listed above, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and the following formula: [ka] A silane coupling agent having the structure represented by is preferred.

[0147] When using a silane coupling agent, the preferred amount is 0.01 to 20 parts by mass per 100 parts by mass of (A) polyimide precursor or polyimide resin.

[0148] (L) Sensitizer The photosensitive resin composition may optionally contain a sensitizer to improve photosensitivity. Examples of such sensitizers include Michla'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-dimethylaminocinnamyrideneindanone, p- Dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethyl Minocoumarin, 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, isopropyl dimethylaminobenzoate Examples include mil, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazol, 2-mercaptobenzothiazole, 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 can be used individually or in combinations of, for example, 2 to 5 types.

[0149] When the photosensitive resin composition contains a sensitizer, the amount added is preferably 0.1 to 25 parts by mass per 100 parts by mass of (A) polyimide precursor or polyimide resin.

[0150] (M) Polymerization inhibitor The photosensitive resin composition may optionally contain polymerization inhibitors to improve the viscosity and photosensitivity stability of the photosensitive resin composition, especially when stored in a solvent-containing solution. Examples of polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic 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.

[0151] <Method for manufacturing a hardened relief pattern and semiconductor device> The method for manufacturing a cured relief pattern according to 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 resin layer to light; (3) developing the exposed resin layer to form a relief pattern; and (4) heat-treating the relief pattern to form a cured relief pattern.

[0152] (1) Resin layer formation process In this process, a photosensitive resin composition is applied to a substrate and, if necessary, subsequently dried to form a photosensitive resin layer. Conventional application methods for photosensitive resin compositions can be used, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, or spray application using a spray coater.

[0153] (2) Exposure process In this process, the resin layer formed above is exposed to ultraviolet light or the like using an exposure device such as a contact aligner, mirror projection, or stepper, either through a patterned photomask or reticle or directly.

[0154] (3) Relief pattern formation process In this process, the unexposed portion of the photosensitive resin layer after exposure is developed and removed. The development method for developing the photosensitive resin layer after exposure (irradiation) can be selected from any of the conventionally known photoresist development methods, such as the rotary spray method, the paddle method, or the immersion method with ultrasonic treatment. Furthermore, after development, a post-development bake may be performed using any combination of temperature and time, if necessary, for purposes such as adjusting the shape of the relief pattern.

[0155] The developer used for development is preferably, for example, a good solvent for the photosensitive resin composition, or a combination of the good solvent and a poor solvent. Preferred good solvents include, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Preferred poor solvents include, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When using a mixture of the good solvent and the poor solvent, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the photosensitive resin composition. In addition, two or more types of solvents, for example, several types, can be used in combination.

[0156] (4) Hardened relief pattern formation process In this process, the relief pattern obtained by the above development is heat-treated to dilute the photosensitive component and the (A) polyimide precursor is imidized, thereby converting it into a cured relief pattern (cured film) made of polyimide. Various methods can be selected for the heat treatment, such as using a hot plate, using an oven, or using a heating oven with a temperature program that can be set. The heat treatment can be carried out, for example, at 160°C to 350°C for 30 minutes to 5 hours. To further improve copper adhesion, the 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 temperature is preferably 200°C or higher, more preferably 230°C or higher. Air may be used as the atmospheric gas during heat curing, or an inert gas such as nitrogen or argon may be used.

[0157] <Polyimide film> The polyimide film (cured film) of this disclosure can be produced by curing the photosensitive resin composition of this disclosure, and this disclosure also provides a cured film formed from a cured product of the photosensitive resin composition of this disclosure. For example, a photosensitive resin composition containing the (A) polyimide resin of this disclosure can be used to produce a polyimide film based on the method for producing the cured relief pattern described above. Alternatively, for example, a polyimide film may be produced by imidizing the photosensitive resin composition containing the (A) polyimide precursor of this disclosure to form a polyimide cured product with an imidization rate of 80-100%. In this case as well, the polyimide film can be produced based on the method for producing the cured relief pattern described above. The structure of the polyimide contained in the cured relief pattern formed from the above polyimide precursor composition is represented by the following general formula. [ka]

[0158] The preferred X1 and Y1 in general formulas (4) and (4') are also preferred in polyimides of the structure represented by the above general formulas for the same reasons. In the above general formulas, the number of repeating units m is not particularly limited, but may be an integer from 2 to 150.

[0159] <Semiconductor device> It is preferable that the semiconductor device has a cured relief pattern obtained by the cured relief pattern manufacturing method described above. It is preferable that the semiconductor device has a substrate which is a semiconductor element and a cured relief pattern of polyimide formed on the substrate by the cured relief pattern manufacturing method described above. The semiconductor device can be manufactured using a semiconductor element as the substrate and the cured relief pattern manufacturing method of this disclosure as part of the process. More specifically, the semiconductor device can be manufactured by a method for manufacturing a semiconductor device in which the cured relief pattern formed by the cured relief pattern manufacturing method of this disclosure is formed as a surface protective film, an interlayer insulating film, a redistribution insulating film, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure.

[0160] <Display device> The display device comprises a display element and a cured film provided on the upper part of the display element, wherein the cured film is preferably the cured relief pattern described above. Here, the cured relief pattern may be laminated in direct contact with the display element, or it may be laminated with another layer in between. For example, the cured film can be a surface protective film, insulating film, and planarization film for TFT liquid crystal display elements and color filter elements, a projection for MVA type liquid crystal display devices, and a partition wall for the cathode of an organic EL element.

[0161] The photosensitive resin composition of this disclosure is preferably a photosensitive resin composition for forming insulating members or interlayer insulating films. Furthermore, the photosensitive resin composition can be used to form surface protective films, interlayer insulating films, redistribution insulating films, protective films for flip-chip devices, or protective films for semiconductor devices having a bump structure. In addition to applications to semiconductor devices as described above, the photosensitive resin composition of this disclosure is also useful for applications such as interlayer insulating films for multilayer circuits, cover coats for flexible copper-clad boards, solder resist films, and liquid crystal alignment films. [Examples]

[0162] The following describes specific examples of the present disclosure, but the embodiments are not limited to these. In the examples, comparative examples, and manufacturing examples, the physical properties of the polyimide precursor or photosensitive resin composition were measured and evaluated according to the following methods.

[0163] <Measurement and Evaluation Methods> (1) Weight average molecular weight The weight-average molecular weight (Mw) of each resin was measured using gel permeation chromatography (on a standard polystyrene basis) under the following conditions. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Columns: Two Shodex KD-806M columns manufactured by Showa Denko Corporation, in series, or Showa Denko Corporation Shodex 805M / 806M in series Standard monodisperse polystyrene: Shodex STANDARD SM-105, manufactured by Showa Denko Corporation. Mobile phase: 0.1 mol / L LiBr / N-methyl-2-pyrrolidone (NMP) Flow rate: 1mL / min.

[0164] (2) Preparation of hardened relief patterns for copper void evaluation On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industries, Ltd., thickness 625±25μm), 200nm thick titanium (Ti) and 400nm thick copper (Cu) were sputtered in that order using a sputtering apparatus (L-440S-FHL model, manufactured by Canon Anelva Corporation). Subsequently, a photosensitive resin composition prepared by the method described later was rotary coated onto this wafer using a coater developer (D-Spin60A model, manufactured by SOKUDO Corporation), and pre-baked on a hot plate at 110°C for 180 seconds to form a coating film approximately 10μm thick. This coating film was irradiated with an i-line energy of 650mJ / cm2 using a Prisma GHI (manufactured by Ultratech) with a test pattern mask. Next, this coating film was spray-developed using cyclopentanone as the developer for a period of time equal to 1.4 times the time it took for the unexposed areas to completely dissolve and disappear, using a coater developer (D-Spin 60A, manufactured by SOKUDO). A relief pattern on Cu was then obtained by rotating spray rinsing with propylene glycol methyl ether acetate for 10 seconds.

[0165] A wafer on which the relief pattern was formed on Cu was heated in a nitrogen atmosphere at 230°C for 2 hours using a temperature-boosting programmable curing furnace (VF-2000 model, manufactured by Koyo Lindbergh), thereby obtaining a cured relief pattern on Cu consisting of resin with a thickness of approximately 6 to 9 μm.

[0166] (3) High-temperature storage test of hardened relief patterns on Cu and subsequent evaluation of void area

[0167] A wafer on which the cured relief pattern was formed on Cu was heated in air at 150°C for 168 hours using a temperature-boosting programmable curing furnace (VF-2000 model, manufactured by Koyo Lindbergh). Subsequently, the resin layer on Cu was completely removed by plasma etching using a plasma surface treatment device (EXAM model, manufactured by Shinko Seiki Co., Ltd.), and the area where the resin originally existed was observed under the conditions described below to evaluate copper voids. The plasma etching conditions are as follows. Output: 133W Gas type and flow rate: O2: 40 mL / min + CF4: 1 mL / min Gas pressure: 50 Pa Mode: Hard Mode Etching time: 4200 seconds

[0168] The Cu surface, from which the resin layer had been completely removed, was observed using an FE-SEM (S-4800 model, manufactured by Hitachi High-Technologies Corporation) under the following conditions, and the area of ​​voids on the surface of the Cu layer was calculated using image analysis software (A-zo-kun, manufactured by Asahi Kasei Corporation). <Observation conditions> • Acceleration voltage: 20kV • SE detector: mixed, BSE-L (LA 5) • Probe current: High Working Distance: 8mm Tilt: 0° • Magnification: 1000x

[0169] When evaluating the photosensitive resin composition described in Comparative Example 1, the total area of ​​voids was set to 100%, and those with a total void area ratio of less than 50% were judged as "A", those with a ratio of 50% or more but less than 70% as "B", those with a ratio of 70% or more but less than 100% as "C", and those with a ratio of 100% or more as "D". If the evaluation is B or higher, it can be suitably used as a cured relief pattern for semiconductors.

[0170] (4) Evaluation of copper adhesion On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industries, Ltd., thickness 625±25μm), 200nm thick titanium (Ti) and 400nm thick copper (Cu) were sputtered in that order using a sputtering apparatus (L-440S-FHL model, manufactured by Canon Anelva Corporation). Subsequently, a photosensitive resin composition was rotary coated and dried onto this wafer to a cured film thickness of approximately 9μm, and then subjected to 800mJ / cm² light emission using a parallel light mask aligner (PLA-501FA model, manufactured by Canon Corporation). 2The entire surface was exposed to light. Using a temperature-boosting programmable curing furnace (VF-2000 model, manufactured by Koyo Lindbergh), the surface was heated under a nitrogen atmosphere for 2 hours at the temperatures listed in Tables 1-4 to obtain a cured relief pattern (thermally cured polyimide coating). The adhesion characteristics between the copper substrate and the cured resin coating were evaluated on the film after heat treatment according to the cross-cut method of JIS K 5600-5-6 standard, based on the following criteria. If the evaluation is B or higher, it can be suitably used as a cured relief pattern for semiconductors. A: The number of grid cells in the cured resin coating adhered to the substrate is 100. B: The number of grid cells in the cured resin coating adhered to the substrate is 80 or more but less than 100. C: The number of grid cells in the cured resin coating adhered to the substrate is 40 or more but less than 80. D: The number of grid cells in the cured resin coating adhered to the substrate is less than 40.

[0171] (5) b-Hast test A TEG wafer was prepared by forming comb-shaped Cu wiring with a line / space of 10 μm / 10 μm and a height of 5 μm on a silicon wafer. The TEG wafer was immersed in a 1% acetic acid aqueous solution for 1 minute, then washed with deionized water and dried with an air gun. Then, oxygen plasma was applied for 20 seconds at 40 mL / min, 133 W, and 50 Pa using a low-pressure plasma (EXAM, manufactured by Shinko Seiki Co., Ltd.). Subsequently, a photosensitive resin composition was rotary coated using a coater developer (D-Spin 60A, manufactured by SOKUDO Co., Ltd.) to a film thickness of 10 μm, and pre-baked on a hot plate at 110°C for 180 seconds to form a coating on the TEG wafer. Finally, it was exposed to 800 mJ / cm2 using a parallel light mask aligner (PLA-501FA, manufactured by Canon Inc.). At this time, in order to ensure conductivity during the b-HAST test, the Cu electrode portion was masked to prevent light irradiation during exposure, and the unexposed areas were removed in the subsequent development. After exposure, more than 30 minutes had elapsed, and rotary spray development was performed using a coater developer (D-Spin 60A, SOKUDO) at 23°C with cyclopentanone as the developer for 1.4 times the time required for the unexposed areas to completely dissolve and disappear. Subsequently, a rotary spray rinse with propylene glycol monomethyl ether acetate was performed for 10 seconds. After that, a cured relief pattern was obtained by heating in a temperature-boosting programmable curing furnace (VF-2000, Koyo Lindbergh) under a nitrogen atmosphere at the temperatures listed in Tables 2-4 for 2 hours.

[0172] The b-HAST test was conducted using an ESPEC Corporation-manufactured advanced accelerated life testing (HAST) chamber (EHS-222M, ESPEC Corporation) at 130°C and 85% RH with an applied voltage of 50V. The insulation resistance between copper wires was measured at 30-minute intervals, and dielectric breakdown was defined as the resistance falling below 1 × 10⁴ Ω. The time from the start of the test to dielectric breakdown was calculated and evaluated based on the following criteria. If the evaluation is D or higher, it can be suitably used as a cured relief pattern for semiconductors. A: More than 250 hours until dielectric breakdown. B: Dielectric breakdown occurs between 200 hours and less than 250 hours. C: Dielectric breakdown occurs between 150 hours and less than 200 hours. D: Dielectric breakdown occurs between 100 hours and less than 150 hours. E: Less than 100 hours until dielectric breakdown

[0173] <Manufacturing example> Manufacturing Example 1: (A) Synthesis of Polyimide Precursor A1 124.0 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) and 29.4 g of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) were placed in a 2 L separable flask. 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone (GBL) were added, and the mixture was stirred at room temperature. While stirring, 81.5 g of pyridine was added to obtain the reaction mixture. After the exothermic reaction was complete, the reaction mixture was allowed to cool to room temperature and left for 16 hours.

[0174] 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. Subsequently, 93.0 g of 4,4'-oxydianiline (ODA) suspended in 350 mL of γ-butyrolactone was added over 30 minutes with stirring. After further stirring at room temperature for 4 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour, and then 400 mL of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0175] The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of crude polymer. The crude polymer was filtered off and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 L of water to precipitate the polymer, and 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 (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 24,000.

[0176] Manufacturing Example 2: (A) Synthesis of Polyimide Precursor A2 The reaction was carried out in the same manner as described in Production Example 1 above, except that 147.1 g of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) was used instead of 124.0 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) and 29.4 g of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), to obtain a polymer (polyimide precursor A2). The weight-average molecular weight (Mw) of polyimide precursor A2 was measured by gel permeation chromatography (on a standard polystyrene basis) and was found to be 24,000.

[0177] Manufacturing Example 3: (A) Synthesis of Polyimide Precursor A3 The reaction was carried out in the same manner as described in Production Example 1 above, except that 155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) was used instead of 124.0 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) and 29.4 g of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), to obtain a polymer (polyimide precursor A3). The weight-average molecular weight (Mw) of polyimide precursor A3 was measured by gel permeation chromatography (on a standard polystyrene basis) and was found to be 21,000.

[0178] Manufacturing Example 4: (A) Synthesis of Polyimide Precursor A4 The reaction was carried out in the same manner as described in Production Example 1 above, except that 155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) was used instead of 124.0 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) and 29.4 g of 3,3',4,4'-biphenyltetracarboxylic acid 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), to obtain polymer (A4). The weight-average molecular weight (Mw) of polymer (A4) was measured by gel permeation chromatography (on a standard polystyrene basis) and was found to be 21,000.

[0179] Manufacturing Example 5: (A) Synthesis of Polyimide Precursor A5 The reaction was carried out in the same manner as described in Production Example 1 above, except that 155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) was used instead of 124.0 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) and 29.4 g of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), and 49.2 g of 1,4-phenylenediamine (pPD) was used instead of 93.0 g of 4,4'-oxydianiline (ODA), to obtain a polymer (polyimide precursor A5). The weight-average molecular weight (Mw) of polyimide precursor A5 was measured by gel permeation chromatography (on a standard polystyrene basis) and was found to be 21,000.

[0180] Manufacturing Example 6: (A) Synthesis of Polyimide Precursor A6 The reaction was carried out in the same manner as described in Production Example 1, except that 62 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) and 88.3 g of pyromellitic acid dianhydride (PMDA) were used instead of 155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) in Production Example 4, to obtain a polymer (polyimide precursor A6). The weight-average molecular weight (Mw) of polyimide precursor A6 was measured by gel permeation chromatography (on a standard polystyrene basis) and found to be 28,000.

[0181] Manufacturing Example 7: (A) Synthesis of Polyimide Resin A7 A Dean-Stark extractor was attached, and 200 g of N-methyl-2-pyrrolidone (hereinafter NMP) and 33.1 g (0.012 mol) of 6-(4-aminophenoxy)biphenyl-3-amine (PDPE) were added to a nitrogen-purged three-necked flask and dissolved. To this, 24.8 g (0.1 mol) of bicyclo[2.2.2]octo-7-ene-2,3,5,6-tetracarboxylic dianhydride (BCD) and 50.0 g of toluene were added, and the mixture was heated to 180°C. After confirming that the theoretical amount of water and the added toluene had been extracted into the Dean-Stark extractor, heating was stopped and the mixture was cooled to room temperature. The resulting reaction solution was added dropwise to 2000 g of deionized water to precipitate the polymer, filtered, and then 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 (in terms of standard polystyrene), and the result was Mw = 14,300.

[0182] Manufacturing Example 8: (A) Synthesis of Polyimide Resin A8 Polyimide resin A8 was obtained in the same manner as in Production Example 7, except that NMP was replaced with GBL, the amount of PDPE added was changed to 23.0 g (0.083 mol), and BCD was changed to 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) 44.4 g (0.1 mol). The weight-average molecular weight of polyimide resin A8 was measured by gel permeation chromatography (in terms of standard polystyrene) and found to be Mw = 14,000.

[0183] Manufacturing Example 9: (A) Synthesis of Polyimide Resin A9 Polyimide resin A9 was obtained in the same manner as in Production Example 7, except that NMP was replaced with GBL, PDPE was replaced with 30.1 g (0.088 mol) of 9,9'-bis(4-aminophenyl)fluorene (BAFL), and BCD was replaced with 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 (on a standard polystyrene basis) and found to be Mw = 29,000.

[0184] Manufacturing Example 10: (A) Synthesis of polyimide resin A10 (MOI-modified BCD-PDPE) A Dean-Stark extractor was attached, and 200 g of GBL and 33.1 g (0.12 mol) of PDPE were added to a nitrogen-purged three-necked flask and dissolved. Then, 24.8 g (0.1 mol) of BCD and 50.0 g of toluene were added, and the mixture was heated to 180°C. After confirming that the theoretical amount of water and the added toluene had been extracted into the Dean-Stark extractor, heating was stopped and the mixture was allowed to cool to room temperature.

[0185] Next, 6.2 g of 2-isocyanatoethyl methacrylate (MOI) was added at room temperature and the mixture was reacted at room temperature for 12 hours. The resulting reaction solution was added dropwise to 2000 g of deionized water to precipitate the polymer, which was then filtered off and vacuum-dried at 40°C to obtain a powdered polymer (polyimide resin A10). The weight-average molecular weight of polyimide resin A10 was measured by gel permeation chromatography (in terms of standard polystyrene), and the result was Mw = 15,200.

[0186] <Example 1> A photosensitive resin composition was prepared using polyimide precursor A1 by the following method, and the prepared composition was evaluated. (A) Polyimide precursor A1: 100 g of the polyimide precursor described in Production Example 1, (B) Tetrazole compound B1: 3 g of 1H-tetrazole-5-carboxylic acid (manufactured by Advanced ChemBlocks), (C) Photopolymerization initiator C1: 3 g of TR-PBG-3057 (manufactured by TRONLY), (E) Radical polymerizable compound E1: 10 g of NK ester A-9300 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) were dissolved in a mixed solvent of (D) Solvent D1: 80 g of γ-butyrolactone (hereinafter referred to as GBL, manufactured by Mitsubishi Chemical Corporation) and Solvent D2: 20 g of dimethyl sulfoxide (hereinafter referred to as DMSO, manufactured by Toray Fine Chemicals). The viscosity of the obtained solution was adjusted to approximately 40 poise by adding the required amount of GBL:DMSO = 80:20 (mass ratio) solution to obtain a photosensitive resin composition. This composition was evaluated according to the method described above. The results are shown in Table 1.

[0187] <Examples 2-51, Comparative Examples 1-13> Except for the solvent, the composition was adjusted according to the mixing ratios shown in Tables 1 to 4. The remaining components were dissolved in the solvent and the viscosity was adjusted in the same manner as in Example 1 to prepare the photosensitive resin composition. Then, copper adhesion and copper void evaluation or b-HAST testing was performed to evaluate copper adhesion and copper migration performance. The results are shown in Tables 1 to 4. The compounds listed in Tables 1 to 4 are as follows:

[0188] (A) Polyimide precursor or 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 Manufacturing Example 4 A5: Polyimide precursor described in Production Example 5 A6: Polyimide precursor described in Production Example 6 A7: Polyimide resin as described in Manufacturing Example 7 A8: Polyimide resin as described in Manufacturing Example 8 A9: Polyimide resin as described in Manufacturing Example 9 A10: Polyimide resin as described in Manufacturing Example 10 A1': ZCR-1797H (Acid-modified epoxy acrylate with a biphenyl skeleton, manufactured by Nippon Kayaku Co., Ltd.)

[0189] (B) Tetrazole compounds B1: 1H-tetrazole-5-carboxylic acid (manufactured by Advanced ChemBlocks) B2: 1H-tetrazole-5-carboxylate ethyl (manufactured by Tokyo Chemical Industry Co., Ltd.) B3: 1H-tetrazole-5-acetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) B4: 1H-tetrazole-5-ethyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) B5: 2-(2H-tetrazole-5-yl)butanediate (manufactured by Enamine Building Blocks) B6: 2,2-Bis(2-2H-tetrazole-5-yl)ethyl)propanidioic acid (manufactured by Chemieliva Pharmaceuticals) B7: 4-(1H-tetrazole-5-yl)benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) B8: 1H-tetrazole-5-propionic acid (manufactured by Enamine Building Blocks) B1': 5-amino-1H-tetrazol (manufactured by Tokyo Chemical Industry Co., Ltd.) B2': 5-Phenyltetrazol (manufactured by Tokyo Chemical Industry Co., Ltd.) B3': 1-Methyltetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0190] (C) Photopolymerization initiator C1:TR-PBG3057 (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.) C2: 1-Phenyl-1,2-propanedione-2-(O-benzoyl)oxime (Product name KZ-941, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) C3: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) (Product name Irgacure OXE02, manufactured by BASF)

[0191] (D) Solvent D1: GBL (manufactured by Mitsubishi Chemical Corporation) D2: DMSO (manufactured by Toray Fine Chemicals Co., Ltd.)

[0192] (E) Radical polymerization initiator E1: Tris-(2-acryloxyethyl) isocyanurate (Product name: NK Ester A-9300, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) E2: Tetraethylene glycol dimethacrylate (product name: NK Ester 4G, manufactured by Shin Nakamura Chemical Industry Co., Ltd.) E3: Methoxynonaethylene glycol monomethacrylate (Product name PME-400, manufactured by NOF Corporation) E4: Pentaerythritol tetraacrylate (Product name A-TMMT, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) E5: Dipentaerythritol polyacrylate (product name A-DPH, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0193] (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)glycoluryl (Product name: Nikalac MX-270, manufactured by Sanwa Chemical Co., Ltd.)

[0194] (G) Heterocyclic compounds G1: Benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.) G2: 5-carboxybenzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.) G3:8-Azaadenine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0195] (J) Organic titanium compounds J1: Diisopropoxytitanium bis(ethyl acetate) (Product name: Orgatics TC-750, manufactured by Matsumoto Fine Chemical Co., Ltd.)

[0196] (K) Adhesion aid K1: N-phenyl-3-aminopropyltrimethoxysilane (product name KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.) K2: (3-triethoxysilylpropyl)-t-butylcarbamate (manufactured by Gelest) K3: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) K4: 4,4-Carbonylbis(2-(((3-triethoxysilyl)propyl)amino)carbonyl)benzoic acid (proprietary product) K5: 2-(3-triethoxysilylpropylcarbamoyl)benzoic acid (proprietary product)

[0197] (L) Sensitizer L1: 2,2'-(phenylimino)diethanol (manufactured by Kanto Chemical Co., Ltd.)

[0198] [Table 1]

[0199] [Table 2]

[0200] [Table 3]

[0201] [Table 4]

[0202] As shown in Table 1, the photosensitive resin compositions of Examples 3, 8, and 11-14 showed copper adhesion of A and copper void suppression of A. The photosensitive resin compositions of Examples 4 and 9 showed copper void suppression of A, but copper adhesion of B. The photosensitive resin compositions of Examples 1-2, 5-7, and 10 all showed copper adhesion and copper void suppression of B. On the other hand, Comparative Examples 1-2 showed copper adhesion and copper void suppression of C, and Comparative Examples 3-6 showed copper void suppression and copper adhesion of D.

[0203] As can be seen from the results in Tables 2-4, Comparative Examples 7-13, which do not meet the requirements of this disclosure, are unable to achieve good results in both copper adhesion and copper migration performance (b-HAST test results). On the other hand, Examples 15-51 show excellent performance in both adhesion and copper migration performance. From the comparison of Comparative Examples 7-11 and Comparative Example 13 with Example 16, and from the comparison of Comparative Example 12 with Example 47, it can be seen that using the (B) tetrazole compound in this disclosure improves copper adhesion and copper migration performance. Comparative Examples 7-10 contain tetrazole compounds, but they do not have the structure of general formula (1) or (2), and their pKa and tPSA do not meet the preferred range of this disclosure, so sufficient effects are not obtained. Comparative Examples 11-13 contain heterocyclic compounds that meet the preferred range of this disclosure in terms of pKa and / or tPSA, but since these heterocyclic compounds are not tetrazole compounds, sufficient effects are not obtained.

[0204] Next, looking at the examples, Examples 16-20 have different compositions with varying amounts of (B) tetrazole compound, but Examples 16, 18, and 19, which have a content in the range of 0.01-10 parts by mass, exhibit superior copper adhesion and copper migration performance. Furthermore, comparing Example 16 with Example 23, or Example 18 with Examples 24-28, it can be seen that increasing the curing temperature improves copper migration performance, however, copper adhesion is better at temperatures below 230°C, and even better at temperatures below 200°C. Comparing Example 31 with Example 30, it can be seen that the inclusion of (E) radical polymerizable compound improves copper migration. Also, comparing Example 34 with Example 33, it can be seen that the inclusion of (F) thermal crosslinking agent improves copper migration. Comparing Example 38 with Example 16, it can be seen that the inclusion of (G) adhesive aid improves copper adhesion. Furthermore, comparing Example 33 and Example 32, it can be seen that Example 32, in which the content of (E) radical polymerizable compound is in the range of 20 to 80 parts by mass, exhibits better copper migration. [Industrial applicability]

[0205] By using the photosensitive resin composition according to this disclosure, a cured relief pattern can be obtained that exhibits excellent copper adhesion and copper void suppression, and low copper migration in b-HAST tests. The photosensitive resin composition according to this disclosure can be suitably used in the field of photosensitive materials useful for the manufacture of electrical and electronic materials such as semiconductor devices and multilayer wiring boards. More specifically, it can be used, for example, as an insulating material for electronic components, and for forming relief patterns such as passivation films, buffer coat films, and interlayer insulating films in semiconductor devices.

Claims

1. The following ingredients: (A) Polyimide precursor and / or polyimide resin, (B) Tetrazole compounds and (C) Photopolymerization initiator and (D) Solvent and A photosensitive resin composition comprising, The pKa of the (B) tetrazole compound is 1.3 to 4.

1. The photosensitive resin composition comprises the polyimide precursor, wherein the polyimide precursor is of the following general formula (4): 【Chemistry 1】 {In formula (4), X1 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer between 2 and 150, and R11 and R12 are independently a hydrogen atom or a monovalent organic group.} Represented by, and / or The photosensitive resin composition comprises the polyimide resin, wherein the polyimide resin is of the following general formula (4'): 【Chemistry 2】 {In equation (4'), X1 is a tetravalent organic group, Y1 is a divalent organic group, and n is an integer between 1 and 150.} A photosensitive resin composition having a structural unit represented by .

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

3. The photosensitive resin composition according to claim 1 or 2, wherein the (B) tetrazole compound comprises a compound represented by the following general formula (3). 【Transformation 3】 {In formula (3), R ４ This is a hydrogen atom, or a monovalent organic group selected from the group consisting of C1-C10 alkyl groups and C6-C10 aryl groups. The hydrogen atoms of the alkyl group and the aryl group may be independently substituted with at least one substituent selected from the group consisting of halogen atoms, hydroxyl groups, alkoxysilyl groups, and amino groups, or they may not be substituted.

4. The photosensitive resin composition according to claim 1 or 2, wherein the (B) tetrazole compound comprises a compound represented by the following formula. 【Chemistry 4】

5. (E) The photosensitive resin composition according to claim 1 or 2, further comprising a radical polymerizable compound.

6. The photosensitive resin composition according to claim 5, wherein the content of component (E) is 20 to 80 parts by mass relative to 100 parts by mass of component (A).

7. In the above general formula (4), R １１ and R １２ At least one of them is the following general formula (5): 【Transformation 5】 {In formula (5), L １ , L ２ and L ３ Each is independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m １ This is an integer between 2 and 10. A photosensitive resin composition according to claim 1 or 2, having a structural unit represented by .

8. X in the aforementioned general formula (4') １ is at least one selected from structures represented by the following general formulas (6) to (14), or Y in the aforementioned general formula (4') １ is at least one selected from structures represented by the following general formulas (15) to (23), the photosensitive resin composition according to claim 1 or 2. 【Transformation 6】 【Transformation 7】 【Transformation 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 【Chemistry 16】 【Chemistry 17】 [Chemistry 18] 【Chemistry 19】 【Chemistry 20】 【Chemistry 21】 【Chemistry 22】 【Chemistry 23】

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

10. (K) The photosensitive resin composition according to claim 1 or 2, further comprising an adhesive aid.

11. The photosensitive resin composition according to claim 1 or 2, wherein the photosensitive resin composition is a photosensitive resin composition for forming a surface protective film, an interlayer insulating film, an insulating film for redistribution, 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 claim 1 or 2 onto a substrate to form a photosensitive resin layer on the substrate, (2) A step of exposing the photosensitive resin layer, (3) A step of developing the photosensitive resin layer after exposure to form a relief pattern, (4) A step of heat-treating the relief pattern to form a hardened relief pattern. A method for manufacturing a hardened relief pattern, including the method described above.

13. The method for manufacturing a cured relief pattern according to claim 12, wherein the heat treatment in step (4) is a heat treatment at 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 described in claim 1 or 2.

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