Photosensitive resin composition, method for manufacturing a hardened embossed pattern using the same, and method for manufacturing a polyimide film.

Abstract

According to the present invention, a photosensitive resin composition is provided that exhibits high copper adhesion, suppresses the formation of copper voids at the interface between the copper layer and the resin layer after high-temperature storage testing, and shows less copper migration in the b-HAST test. The photosensitive resin composition of the present invention contains the following components: (A) a polyimide precursor and / or a polyimide resin, (B) a tetrazolium compound, (C) a photopolymerization initiator, and (D) a solvent. Regarding (B) the tetrazolium compound, the pKa is 1.3 to 4.1, or is represented by general formula (1) or (2), or the polar surface area (tPSA) is 81 to 200.

Description

Technical Field

[0001] This invention relates to a photosensitive resin composition, a method for manufacturing a hardened embossed pattern using the same, and a method for manufacturing a polyimide film. This international application claims priority to Japanese Patent Application No. 2022-174360, filed October 31, 2022, the entire contents of which are incorporated herein by reference. Prior Technology

[0002] Previously, insulating materials for electronic components and passivation films, surface protective films, and interlayer insulating films for semiconductor devices have used polyimide resins, polybenzoxazole resins, phenolic resins, etc., which possess excellent heat resistance, electrical properties, and mechanical properties. Among these resins, those provided in the form of photosensitive resin compositions can easily form heat-resistant embossed pattern films through coating, exposure, development, and thermoimidization treatment using the composition for curing. This type of photosensitive resin composition has the following characteristics: compared to previous non-photosensitive materials, the number of steps can be significantly reduced.

[0003] On the other hand, in recent years, from the perspective of increasing integration and computing power, as well as miniaturizing chip size, the method of mounting semiconductor devices onto printed wiring substrates (packaging structure) is also changing. The previous mounting method using metal leads and lead-tin eutectic bonding has shifted to a structure using polyimide coatings and solder bumps in direct contact, such as BGA (Ball Grid Array) and CSP (Chip Scale Package), which allow for higher density mounting. Furthermore, structures such as FO (fan out) have been proposed, which have multiple rewiring layers on the surface of the semiconductor chip with an area larger than that of the semiconductor chip (see Patent Document 1).

[0004] Copper is commonly used in the wiring of semiconductor devices. However, in large-area package structures, the stress caused by the difference in thermal expansion coefficients of dissimilar materials, coupled with the degradation of electrical properties due to the peeling of copper from the interlayer insulating material, becomes a particular problem. Therefore, the materials used as interlayer insulating films require high adhesion to copper.

[0005] Furthermore, in recent years, the application of semiconductor devices has become particularly prominent in automotive and mobile phone applications. Semiconductor devices in this field require high reliability and undergo reliability testing under high-temperature environments. [Previous Technical Documents] [Patent Literature]

[0006] [Patent Document 1] US Patent No. 10,658,199 [Patent Document 2] Japanese Patent Application Publication No. 2012-194520 Summary of the Invention

[0007] [The problem the invention aims to solve]

[0008] However, in the high-temperature storage test of the aforementioned reliability test, after the test, voids (hereinafter also referred to as "copper voids") due to migration occurred at the interface between the copper layer and the resin layer in the rewiring. If copper voids occur at the interface between the copper layer and the resin layer, the adhesion between the two decreases. Furthermore, if copper migrates to the resin layer (hereinafter also referred to as "copper migration" in this invention), it becomes a cause of short circuits between wirings, especially in semiconductor devices with fine wiring, and cannot fully perform its function as an insulating film. Therefore, it is desirable to have a polyimide film with less copper migration and no short circuits for a long time in the high-temperature and high-humidity reliability test (b-HAST: Biased Hughly Accelerated Stress Test).

[0009] One objective of this invention is to provide a photosensitive resin composition that achieves high copper adhesion, suppresses the formation of copper voids at the interface between the copper layer and the resin layer after high-temperature storage testing, and exhibits less copper migration during b-HAST testing. The suppression of copper migration during b-HAST testing is related to the formation of a polyimide film that is less prone to short circuits over long periods. Furthermore, another objective is to provide a method for forming a hardened embossed pattern using the photosensitive resin composition of this invention, and a method for manufacturing a polyimide film. [Technical means to solve the problem]

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

[18] . [1] A photosensitive resin composition comprising the following components: (A) Polyimide precursors and / or polyimide resins, (B) Tetrazol compounds, (C) Photopolymerization initiators, and (D) Solvent, Furthermore, the pKa of the aforementioned (B) tetrazolium compound is 1.3 to 4.1. [2] A photosensitive resin composition comprising the following components: (A) Polyimide precursors and / or polyimide resins, (B) Tetrazol compounds, (C) Photopolymerization initiators, and (D) Solvent, Furthermore, the above-mentioned (B) tetrazolium compound contains the following general formula (1): [Chemistry 1] {In formula (1), R1 is a hydrogen atom, or a monovalent organogroup selected from the group consisting of alkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 10 carbon atoms; the hydrogen atoms of the aforementioned alkyl and aryl groups may be independently substituted by at least one substituent selected from the group consisting of halogen atoms, hydroxyl groups, alkoxysilyl groups, and amino groups, or may not be substituted.} Or the following general formula (2): [Chemistry 2] {In formula (2), R2 is a hydrogen atom, or a monovalent organogroup selected from the group consisting of alkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 10 carbon atoms; R3 is an alkyl group having 1 to 10 carbon atoms; the hydrogen atoms of the above-mentioned alkyl, aryl, and alkyl groups may be independently substituted by at least one substituent selected from the group consisting of halogen atoms, hydroxyl groups, alkoxysilyl groups, and amino groups, or may not be substituted.} The compound represented. [3] A photosensitive resin composition comprising the following components: (A) Polyimide precursors and / or polyimide resins, (B) Tetrazol compounds, (C) Photopolymerization initiators, and (D) Solvent, Furthermore, the polar surface area (tPSA) of the aforementioned (B) tetrazolium compound is 81~200. [4] The photosensitive resin composition of any one of items 1 to 3, wherein the content of component (B) is 0.01 to 10 parts by mass relative to 100 parts by mass of component (A). [5] The photosensitive resin composition of any one of items 1 to 4, wherein the above-mentioned (B) tetrazolium compound contains a compound represented by the following general formula (3); [Chemistry 3] {In formula (3), R4 is a hydrogen atom or a monovalent organic group selected from the group consisting of alkyl groups with 1 to 10 carbon atoms and aryl groups with 6 to 10 carbon atoms; the hydrogen atoms of the alkyl and aryl groups may be independently substituted by at least one substituent selected from the group consisting of halogen atoms, hydroxyl groups, alkoxysilyl groups and amino groups, or may not be substituted}. [6] The photosensitive resin composition of any one of items 1 to 5, wherein the above-mentioned (B) tetrazolium compound contains a compound represented by the following formula; [Chemistry 4] . [7] The photosensitive resin composition of any one of items 1 to 6 further contains (E) free radical polymerizable compounds. [8] For example, in the photosensitive resin composition of Item 7, the content of component (E) is 20 to 80 parts by mass relative to 100 parts by mass of component (A). [9] The photosensitive resin composition of any one of items 1 to 8, wherein the photosensitive resin composition contains the polyimide precursor, the polyimide precursor being represented by the following general formula (4): [Chemistry 5] {In formula (4), X1 is a tetravalent organogroup, Y1 is a divalent organogroup, n1 is an integer from 2 to 150, and R11 and R12 are independently hydrogen atoms or monovalent organogroups, respectively} and / or The above-mentioned photosensitive resin composition contains the above-mentioned polyimide resin, which has the structural unit represented by the following general formula (4'): [Chemistry 6] {In formula (4'), X1 is a tetravalent organic group, Y1 is a divalent organic group, and n is an integer from 1 to 150}.

[10] For example, in the photosensitive resin composition of Project 9, at least one of R 11 and R 12 in the above general formula (4) has the structural unit represented by the following general formula (5): [Chemistry 7] {In formula (5), L1, L2 and L3 are each a hydrogen atom or an organic group with one to three carbon atoms, and m1 is an integer from 2 to 10}.

[11] For example, in the photosensitive resin composition of item 9 or 10, X1 of the above general formula (4') is selected from at least one of the structures represented by general formulas (6) to (14) below, or Y1 of the above general formula (4') is selected from at least one of the structures represented by general formulas (15) to (23) below; [Chemistry 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] [Chemistry 24] [Chemistry 25] .

[12] The photosensitive resin composition of any one of items 1 to 11 further contains (F) a thermal crosslinking agent.

[13] The photosensitive resin composition of any one of items 1 to 12 further contains (K) adhesive additive.

[14] The photosensitive resin composition of any one of items 1 to 13, wherein the photosensitive resin composition is a photosensitive resin composition used to form a surface protective film, an interlayer insulating film, a rewiring insulating film, a protective film for flip-chip devices, or a protective film for a semiconductor device having a bump structure.

[15] A method for manufacturing a hardened embossed pattern includes the following steps: (1) The step of coating a photosensitive resin composition of any one of items 1 to 14 onto a substrate to form a photosensitive resin layer on the substrate; (2) The step of exposing the above-mentioned photosensitive resin layer; (3) The step of developing the exposed photosensitive resin layer to form a raised pattern; and (4) The step of heating the above-mentioned raised pattern to form a hardened raised pattern.

[16] For example, in the manufacturing method of the hardened embossed pattern in Project 15, the heat treatment in step (4) above is a heat treatment below 350°C.

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

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

[0011] According to the present invention, a photosensitive resin composition is provided that exhibits high copper adhesion, suppresses the formation of copper voids at the interface between the copper layer and the resin layer after high-temperature storage testing, and shows less copper migration in the b-HAST test. Furthermore, a method for manufacturing a hardened embossed pattern using the photosensitive resin composition and a method for manufacturing a polyimide film are also provided. Implementation

[0012] The embodiments of the present invention will now be described in detail. The present invention is not limited to the embodiments described below, and various variations can be made within its scope. Furthermore, throughout the present invention, when multiple structures represented by the same symbol exist in the molecule, they may be identical or different. Also, the upper and lower limits of the numerical ranges of the present invention can be arbitrarily combined to form any numerical range.

[0013] <Photosensitive Resin Composition> The photosensitive resin composition of the present invention contains (A) a polyimide precursor and / or a polyimide resin, (B) a tetrazolium compound, (C) a photopolymerization initiator, and (D) a solvent.

[0014] (A) Polyimide precursor (A) The polyimide precursor is a resin component contained in the photosensitive resin composition, which is converted into polyimide through a thermal cyclization treatment. (A) The structure of the polyimide precursor is not limited as long as it is a resin that can be used in the photosensitive resin composition, but it is preferably non-alkali-soluble. By making the polyimide precursor non-alkali-soluble, higher chemical resistance can be obtained.

[0015] The polyimide precursor is preferably a polyimide having the structure represented by the following general formula (4): [Chemistry 26] {In formula (4), X1 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer from 2 to 150, and R11 and R12 are hydrogen atoms or monovalent organic groups, respectively}.

[0016] In general formula (4), it is preferable that at least one of R 11 and R 12 has the structural unit represented by the following general formula (5): [Chemistry 27] {In formula (5), L1, L2 and L3 are each a hydrogen atom or an organic group with one to three carbon atoms, and m1 is an integer from 2 to 10}.

[0017] In general formula (4), the ratio of hydrogen atoms R11 and R12, based on the total mole number of R11 and R12, is preferably 10% or less, more preferably 5% or less, and even more preferably 1% or less. Furthermore, the ratio of monovalent organic groups R11 and R12 in general formula (4), based on the total mole number of R11 and R12, is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. When the ratio of hydrogen atoms and the ratio of organic groups in general formula (5) are within the above ranges, it is preferable from the viewpoint of photosensitivity and storage stability.

[0018] In general formula (4), n1 is not limited to an integer from 2 to 150. From the point of view of the photosensitivity and mechanical properties of the photosensitive resin composition, it is more preferably an integer from 3 to 100, and even more preferably an integer from 5 to 70.

[0019] In general formula (4), the tetravalent organogroup represented by X1 is preferably an organogroup with 6 to 40 carbon atoms, considering both heat resistance and photosensitivity. More preferably, it is an aromatic group with -COOR 11 and -COOR 12 groups adjacent to -CONH- groups, or an alicyclic aliphatic group. Examples of the tetravalent organogroup represented by X1 include: organogroups with 6 to 40 carbon atoms containing an aromatic ring, such as those with the structure represented by the following general formula (24): [Chemistry 28] {In the formula, R6 is selected from at least one of the group consisting of hydrogen atoms, fluorine atoms, monovalent hydrocarbon groups of C1 to C10, and monovalent fluorinated hydrocarbon groups 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}, but is not limited to these. Furthermore, the structure of X1 can be one or a combination of two or more. The X1 group having the structure represented by the above formula (24) is particularly advantageous from the viewpoint of balancing heat resistance and photosensitivity.

[0020] As an X1 base, the structure represented by the above equation (24), especially the tetravalent organic group represented by the following equation: [Chemistry 29]

[0021] {In the formula, R6 is selected from at least one of the groups consisting of fluorine atoms, hydrocarbon groups with one valence of carbon 1 to 10, and fluorinated hydrocarbon groups with one valence of carbon 1 to 10, and m is an integer selected from 0 to 3}. From the perspective of aceimidization rate, degassing, copper adhesion, and chemical resistance during low-temperature heating, it is better.

[0022] In the above general formula (4), the divalent organic group represented by Y 1 is preferably an aromatic group with 6 to 40 carbon atoms, from the viewpoint of balancing heat resistance and photosensitivity. For example, the structure represented by the following formula (25) can be cited: [Chemistry 30] {In the formula, R6 is selected from at least one of the group consisting of hydrogen atoms, fluorine atoms, monovalent hydrocarbon groups of C1 to C10, and monovalent fluorinated hydrocarbon groups of C1 to C10, and n is an integer selected from 0 to 4}, but is not limited to these. Furthermore, the structure of Y1 can be one type or a combination of two or more types. Y1 groups having the structure represented by the above formula (25) are particularly advantageous from the viewpoint of balancing heat resistance and photosensitivity.

[0023] As a Y1 basis, in the structure represented by the above equation (25), especially the divalent basis represented by the following equation: [Chemistry 31] {In the formula, R6 is selected from at least one of the groups consisting of fluorine atoms, hydrocarbon groups with one valence of carbon 1 to 10, and fluorinated hydrocarbon groups with one valence of carbon 1 to 10, and n is an integer selected from 0 to 4}. From the perspective of aceimidization rate, degassing, copper adhesion, and chemical resistance during low-temperature heating, it is better.

[0024] As the monovalent organic groups with 1 to 3 carbons in L1, L2, and L3 of the above general formula (5), for example, they are hydrocarbon groups with 1 to 3 carbons, 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 of 2 to 10 from the viewpoint of photosensitivity, preferably an integer of 2 to 4.

[0025] In one embodiment, (A) the polyimide precursor is preferably a polyimide precursor having the structural unit represented by the following general formula (26): [Chemistry 32] {In the formula, R11, R12 and n1 are defined above}.

[0026] In general formula (26), it is preferable that at least one of R11 and R12 is a monovalent organic group represented by general formula (5). By including the polyimide precursor represented by general formula (6) in (A), the chemical resistance is particularly improved.

[0027] In one embodiment, it is preferable from a thermophysical point of view when (A) the polyimide precursor is a polyimide precursor having the structural unit represented by the following general formula (27): [Chemistry 33] {In the formula, R11, R12 and n1 are defined above}.

[0028] In general formula (27), it is more preferable that at least one of R11 and R12 is a monovalent organic group represented by the above general formula (5).

[0029] (A) Polyimide precursors tend to have particularly high resolution by containing both structural units represented by general formula (26) and structural units represented by general formula (27). For example, (A) polyimide precursors may contain copolymers of structural units represented by general formula (26) and structural units represented by general formula (27), or mixtures of polyimide precursors represented by general formula (26) and polyimide precursors represented by general formula (27).

[0030] (A) The polyimide precursor is preferably a polyimide precursor having the structural unit represented by the following general formula (28): [Chemistry 34] {In the formula, R11, R12 and n1 are defined above}.

[0031] (A) The polyimide precursor is preferably a polyimide precursor having the structural unit represented by the following general formula (29): [Chemistry 35] {In the formula, R11, R12 and n1 are defined above}. (A) Polyimide precursors contain polyimide precursors represented by general formula (29), which have particularly high chemical resistance.

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

[0033] (A) Preparation method of polyimide precursor (A) The polyamide precursor is prepared by first reacting a tetracarboxylic acid dianhydride containing the aforementioned tetravalent organic group X1 with an alcohol having photopolymerizable unsaturated double bonds and any alcohol without unsaturated double bonds to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester body). Subsequently, it is obtained by amide polycondensation of the partially esterified tetracarboxylic acid with a diamine containing the aforementioned divalent organic group Y1.

[0034] (Preparation of acid / ester body) As a preferred tetracarboxylic dianhydride containing a tetravalent organic group X1 for preparing (A) polyimide precursors, the tetracarboxylic dianhydride represented by the above general formula (24) is the first example, such as: pyromellitic dianhydride (PMDA), 4,4'-oxophthalic dianhydride (ODPA), benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA), diphenyl tannin-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. However, it is not limited to these. Among these, preferred examples of tetracarboxylic dianhydrides include: pyromellitic dianhydride (PMDA), 4,4'-oxophthalic dianhydride (ODPA), and biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA). These can be used alone or in combination of two or more.

[0035] Alcohols with photopolymerizable unsaturated double bonds that are preferably used to prepare (A) polyimide precursors include, for example: 2-acryloyloxyethanol, 1-acryloyloxy-3-propanol, 2-acryloylamine ethanol, hydroxymethyl 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-tert-butoxypropyl acrylate, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-tert-butoxypropyl acrylate, 2-hydroxy-3-methoxypropyl acrylate. 3-Cyclohexyloxypropyl ester, 2-methacryloxyethanol, 1-methacryloxy-3-propanol, 2-methacrylamide ethanol, hydroxymethyl 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-tert-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, etc.

[0036] Alternatively, a portion of alcohols without unsaturated double bonds, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tributanol, 1-pentanol, 2-pentanol, 3-pentanol, neopentanol, 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, benzyl alcohol, etc., can be mixed into the aforementioned alcohols with photopolymerizable unsaturated double bonds for use.

[0037] Furthermore, as a polyimide precursor, a non-photosensitive polyimide precursor prepared solely from alcohols lacking unsaturated double bonds can be mixed with a photosensitive polyimide precursor for use. From a resolution perspective, the non-photosensitive polyimide precursor is preferably 200 parts by mass or less, based on 100 parts by mass of the photosensitive polyimide precursor. The aforementioned preferred tetracarboxylic dianhydride and the aforementioned alcohol are dissolved and mixed in a solvent as described below in the presence of an alkaline catalyst such as pyridine, and stirred at a temperature of 20–50°C for 4–24 hours to carry out an esterification reaction of the anhydride, thereby obtaining the desired acid / ester body.

[0038] (Preparation of polyimide precursors) In the aforementioned acid / ester body (typically a solution in the solvents described below), under ice bath cooling, a suitable dehydrating condensing agent is added, such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-dibutyldiimide carbonate, etc., to convert the acid / ester body into a polyanhydride. Then, a diamine containing a divalent organic group Y1, separately dissolved or dispersed in a solvent, is added dropwise to induce amide polycondensation, thereby obtaining the target polyamide precursor. Alternatively, thionyl chloride or similar substances are used to amide-chlorinate the acid portion of the aforementioned acid / ester body, and then reacted with a diamine compound in the presence of a base such as pyridine, thereby obtaining the target polyamide precursor.

[0039] As diamines containing a divalent organic group Y1, diamines having the structure shown in the above general formula (21) are the most common, for example: p-phenylenediamine (1,4-phenylenediamine (pPD)), m-phenylenediamine, 4,4'-oxodiphenylamine (ODA), 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminodiphenyl sulfide Biphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene (TPE-Q), 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene (APB), bis[4-(4-aminophenoxy)phenyl] ion, bis[4-(3-aminophenoxy)phenyl] ion, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3- (aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP), 1,4-bis(3-aminopropyldimethylsilyl)benzene, bi-o-methyl Aniline benzoxide, 9,9-bis(4-aminophenyl)benzoxide (BAFL), and those in which a portion of the hydrogen atoms on the benzene ring are substituted with methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen, etc., such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof, but not limited thereto. Preferred diamines include 4,4'-oxodiphenylamine (ODA), 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB), and 1,4-phenylenediamine (pPD). These diamines can be used alone or in combination of two or more.

[0040] After the polyamide condensation reaction is completed, the water-absorbing byproducts of the dehydrating condensing agent coexisting in the reaction solution are filtered and separated as needed. Water, aliphatic lower alcohols, or mixtures thereof, or other unsuitable solvents, are then added to the obtained polymer components to precipitate the polymer. This process of redissolving and reprecipitating is repeated to purify the polymer. Vacuum drying is then performed to isolate the target polyamide precursor. To improve purification, the polymer solution can be passed through a column filled with anion and / or cation exchange resins swelled with a suitable organic solvent to remove ionic impurities.

[0041] The molecular weight of the polyimide precursor (A) described above, when determined by converting the weight-average molecular weight of polystyrene using gel permeation chromatography, is preferably 8,000 to 150,000, more preferably 9,000 to 50,000. When the weight-average molecular weight is 8,000 or higher, the mechanical properties are good; when it is below 150,000, the dispersibility with the developer is good, and the resolution of the raised pattern is good. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. Furthermore, the weight-average molecular weight is obtained from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, the recommended organic solvent is Standard SM-105 manufactured by Showa Denko Corporation.

[0042] (A) Polyimide resin The photosensitive resin composition of the present invention may contain (A) polyimide resin together with or in place of (A) polyimide precursor.

[0043] (A) Polyimide resins do not produce resin-derived detachment components, thus inhibiting the curing shrinkage of the photosensitive resin composition. Therefore, compared with polyimide precursors, a photosensitive resin composition with a higher cured film yield and improved post-curing flatness can be obtained.

[0044] (A) Polyimide resins may have polymerizable groups on their side chains, but from the viewpoint of elongation and storage stability of the cured film, it is preferable that they do not have polymerizable groups on their side chains. Polyimide resins are preferably substantially free of polyamide or polyamide ester structures. In this invention, "substantially free" means, for example, that the amide content of the polyimide resin is 90% or more, preferably 95% or more.

[0045] The amide content of polyimide resin can be determined by known methods, but in this invention it is calculated using the following method. First, the infrared absorption spectrum of the polyimide resin is measured to confirm the presence of absorption peaks of the amide structure (around 1780 cm⁻¹ and 1377 cm⁻¹). Second, the polyimide resin is heat-treated at 350°C for 1 hour, and the infrared absorption spectrum after heat treatment is measured. The peak intensity around 1377 cm⁻¹ is compared with the peak intensity before heat treatment, thereby calculating the amide content of the polyimide resin.

[0046] (A) From the viewpoint of solvent solubility and coating flatness, polyimide resins preferably contain the structure represented by general formula (4'). Furthermore, it is a structure suitable for solvent-developable photosensitive resin compositions. [Chemistry 36] {In equation (4'), X1 is a tetravalent organogroup, Y1 is a divalent organogroup, and n is an integer from 1 to 150}

[0047] X 1 is a tetravalent organic group, and there are no particular limitations as long as it is derived from a known tetracarboxylic acid dianhydride structure. From the viewpoint of the high copper adhesion of the hardened film, the suppression of copper voids after high temperature storage test, the suppression of copper migration in the b-HAST test, excellent elongation, excellent chemical resistance, and solubility in the following solvents, it is preferred to have at least one structure represented by the following formulas (6) to (14). [Chemistry 37] [Chemistry 38] [Chemistry 39] [Chemistry 40] [Chemistry 41] [Chemistry 42] [Chemistry 43] [Chemistry 44] [Chemistry 45]

[0048] Furthermore, from the viewpoint of the inhibition of copper voids after high-temperature storage test, the inhibition of copper migration in b-HAST test, elongation, and chemical resistance of the hardened film obtained from the photosensitive resin composition of the present invention, X1 preferably has at least one structure represented by formulas (6) to (13). Furthermore, from the viewpoint of the heat resistance of the hardened film obtained from the photosensitive resin composition of the present invention, X1 preferably has at least one structure represented by formulas (6) to (8) and (10) to (13). Moreover, from the viewpoint of the particularly excellent coating uniformity and elongation of the hardened film of the photosensitive resin composition of the present invention, X1 preferably has at least one structure represented by formulas (6) and (11) to (13).

[0049] In formula (4'), Y1 is a divalent organic group. As long as it is derived from a known diamine, there is no particular limitation. From the point of view of the high copper adhesion of the hardened film, the suppression of copper voids after high temperature storage test, the suppression of copper migration in the b-HAST test, the elongation, the excellent chemical resistance, and the solubility in solvents, it is preferred to have at least one of the structures represented by the following formulas (15) to (23). [Chemistry 46] [Chemistry 47] [Chemistry 48] [Chemistry 49] [Transformation 50] [Chemistry 51] [Chemistry 52] [Chemistry 53] [Chemistry 54]

[0050] Furthermore, from the viewpoint of the inhibition of copper voids after high-temperature storage test, the inhibition of copper migration in b-HAST test, elongation, and chemical resistance of the hardened film obtained from the photosensitive resin composition of the present invention, Y1 preferably has at least one structure represented by formula (15) to (21). Furthermore, from the viewpoint of the mechanical properties of the hardened film obtained from the photosensitive resin composition of the present invention, Y1 preferably has at least one structure represented by formula (15) to (20). Moreover, from the viewpoint of the particularly excellent coating uniformity and elongation of the hardened film of the negative photosensitive resin composition of the present invention, Y1 particularly preferably has at least one structure represented by formula (17) to (20). The reason why the structures represented by formulas (17) to (20) have excellent solvent solubility is that these structures have side-chain phenyl structures.

[0051] In formula (4'), n is an integer from 2 to 150, preferably from 3 to 100, and even more preferably from 5 to 70. n is preferably an integer that satisfies the following (A) of the weight average molecular weight of the polyimide resin.

[0052] With regard to the solubility of the following solvents, the end of (A) polyimide resin is preferably the main chain end of (A) polyimide resin having at least one structure selected from the group consisting of an anhydride group, a carboxyl group, an amino group, and the following general formulas (30) to (32). [Chemistry 55] {In formula (30), R1 and R2 are independently selected from hydrogen atoms and monovalent organic groups with carbon numbers of 1 to 3, R3 is an organic group with carbon numbers of 1 to 20 that may contain heteroatoms, and k is an integer from 1 to 2; R4 is a hydrogen atom and an organic group with carbon numbers of 1 to 4, and * indicates the bonding site with the end of (A) polyimide resin} [Chemistry 56] {In formula (31), R5 and R6 are respectively hydrogen atoms and monovalent organic groups with carbon numbers of 1 to 3; and * indicates the bonding site with the end of (A) polyimide resin} [Chemistry 57] {In formula (32), R7, R8, and R9 are each independently a hydrogen atom or a monovalent organic group with 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}

[0053] Preferably, the anhydride group is derived from the tetracarboxylic anhydride of the raw material, the carboxyl group is obtained by ring opening of the above-mentioned anhydride group, and the amine group is derived from the diamine of the raw material. As a more detailed specific example of the case where the end of (A) polyimide resin is the structure represented by general formula (30), the structures represented by the following formulas (33) to (36) can be cited. [Chem.58] [Chemistry 59] [Transformation 60] [Chemistry 61] {The asterisk (*) in the formula indicates the bonding site at the end of the polyimide resin (A)} [Chemistry 62] As a more detailed specific example of the structure represented by general formula (31), the structures represented by the following formulas (37) and (38) can be cited. [Chemistry 63] [Chemistry 64] {The asterisk (*) in the formula indicates the bonding site at the end of the polyimide resin (A)}

[0054] As a more detailed specific example of the structure represented by general formula (32), the structures represented by the following formulas (39) to (42) can be cited. [Chemistry 65] [Chemistry 66] [Chemistry 67] [Chemistry 68] {The asterisk (*) in the formula indicates the bonding site at the end of the polyimide resin (A)}

[0055] From the perspective of the high copper adhesion of the hardened film, the suppression of copper voids after high temperature storage test, the suppression of copper migration in b-HAST test, elongation, chemical resistance and solvent solubility, it is preferable that X1 of general formula (4') is any structure represented by general formula (6) to (14), and Y1 is any structure represented by general formula (15) to (23).

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

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

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

[0059] (A) Preparation method of polyimide resin (A) The polyimide resin is obtained by amide-imidizing polyamide obtained by reacting tetracarboxylic dianhydride with diamine.

[0060] There are no limitations on the methods for dehydrating and clotting polyamides. Examples include: thermal acetylation, which involves heating polyamides at high temperatures to dehydrate and close the ring, and chemical acetylation, which involves adding acetic anhydride as a dehydrating reducing agent and a tertiary amine to dehydrate and close the ring.

[0061] There is no particular limitation on the temperature in the heating aceimide method. From the viewpoint of promoting the ring-closure 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] There are no particular limitations on what constitutes a tetracarboxylic dianhydride. Specific examples include: pyromellitic dianhydride (PMDA), 4,4'-oxophthalic anhydride (ODPA), 3,4'-oxophthalic anhydride, 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 3,4'-biphenyltetracarboxylic dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)phthalic anhydride (BPADA), and 9,9-bis(3,4-diphenyltriphenyl)phthalic anhydride. Carboxyphenyl dianhydride (BPAF), northoalkyl-2-spiro-α-cyclopentanone-α'-spiro-2''-northoalkyl-5,5'',6,6''-tetracarboxylic dianhydride (CpODA), bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BCD), 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), and 4,4'-(hexafluoroisopropylidene)phthalic anhydride (6FDA), etc. Among these, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BCD), 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), and 4,4'-(hexafluoroisopropylidene)phthalic anhydride (6FDA), etc., are preferred as tetracarboxylic dianhydrides.

[0063] As a diamine, there are no particular limitations. Specific examples include: 4,4'-diaminodiphenyl ether (DADPE), 3,4'-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene (APB), 1,4-bis(4-aminophenoxy)benzene (TPE-Q), 2-phenoxybenzene-1,4-diamine (PND), 9,9-bis(4-aminophenyl)benzene (BAFL), 6-(4-aminophenoxy)biphenyl-3-amine (PDPE), 3,3'-di... Phenyl-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-(methacryloxy)ethyl-3,5-diaminobenzoate (MAEDAB), etc. Among these, 6-(4-aminophenoxy)biphenyl-3-amine (PDPE) and 9,9'-bis(4-aminophenyl)benzoyl (BAFL), etc., are preferred as diamines.

[0064] When the terminal groups of polyimide resin (A) are anhydride, carboxyl, and amine groups, polyimide resin (A) is obtained by amide imidization of polyamide obtained by reacting tetracarboxylic dianhydride with diamine to achieve dehydration and ring closure. The terminal anhydride, carboxyl, and amine groups of polyimide resin (A) can be reacted with specified compounds to make the terminal groups form the structures represented by the above general formulas (30) to (32).

[0065] (A) polyimide resins with a structure represented by general formula (30) at the end are obtained, for example, by reacting the amino groups at the end of the polyimide with isocyanate compounds. Specific examples of isocyanate compounds include: 2-methacryloxyethyl isocyanate (2-isocyanoethyl methacrylate: MOI), 2-acryloxyethyl isocyanate, 1,1-(bisacryloxymethyl)ethyl isocyanate, and 2-(2-methacryloxyethoxy)ethyl isocyanate. The method of reaction with isocyanate compounds is not particularly limited; the reaction can be achieved by adding an isocyanate compound to a solution of dehydrated, ring-closed polyimide and stirring at room temperature, thereby reacting with the amino groups of the dehydrated, ring-closed polyimide.

[0066] (A) polyimide resins with the structure represented by general formula (31) at the end are obtained, for example, by reacting the amino groups at the end of the polyimide with a chloride-based compound. Examples of chloride-based compounds include acrylonitrile chloride and methacrylonitrile chloride. There are no particular limitations on the method of reacting with the chloride-based compound. The dehydrated ring-closed polyimide solution can be cooled in an ice bath, and the chloride-based compound can be added dropwise, thereby reacting with the amino groups of the dehydrated ring-closed polyimide.

[0067] Polyimide resins of type (A) with the structure represented by general formula (32) at the end are obtained, for example, by reacting the anhydride and carboxyl groups at the end of the polyimide with an alcohol compound. Examples of alcohol 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 reaction with the alcohol compound. Condensing agents such as N,N'-dicyclohexylcarbodiimide (DCC) or esterification catalysts such as p-toluenesulfonic acid can be used to react the anhydride and carboxyl groups of the dehydrated and ring-closed polyimide with the alcohol compound.

[0068] In the manufacture of (A) polyimide resin, a reaction solvent can be used to efficiently carry out the reaction in a homogeneous environment. There are no particular limitations on the reaction solvent, as long as it can uniformly dissolve or suspend tetracarboxylic dianhydride, diamine, and compounds with polymerizable functional groups at the ends. Examples of reaction solvents include: γ-butyrolactone (GBL), dimethyl sulfoxide, N,N-dimethylacetyl acetylamine, 1,3-dimethyl-2-imidazolidineone, 3-methoxy-N,N-dimethylpropionic acid, 3-butoxy-N,N-dimethylpropionic acid, N,N-dimethylmethoxylamine, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N,N-dimethylacetylamine.

[0069] In the manufacture of (A) polyimide resin, when the heating amide method is used, an azeotropic solvent can be used to promote the amide reaction. As an azeotropic solvent, there are no particular limitations as long as it is a solvent that azeotropically reacts with water, and examples include: toluene, ethyl acetate, N-dicyclohexylpyrrolidone, o-dichlorobenzene, xylene, and benzene.

[0070] (A) Polyimide resin can be purified by methods described in Patent Document 2 (Japanese Patent Application Publication No. 2012-194520). For example, purification methods include: removing unreacted substances by adding a solution of (A) polyimide resin dropwise to water for redeposition; removing condensing agents insoluble in the reaction solvent by filtration; and removing catalysts by using an ion exchange resin. After such purification, the (A) polyimide resin can be dried by known methods and isolated as a powder.

[0071] (B) Tetrazol compounds Regarding (B) tetrazolium compounds, a combination of one or more of these characteristics is present, having a pKa of 1.3 to 4.1, or as represented by formula (1) or (2) below, or a polar surface area (tPSA) of 81 to 200. By containing such (B) tetrazolium compounds, copper adhesion and copper migration inhibition effects are obtained. Furthermore, since it is presumed that copper voids are a result of copper migration, the inhibition of copper migration also exerts an effect of inhibiting copper voids.

[0072] In the first-state sample, the acid dissociation constant (pKa) of the (B) tetrazolium compound is 1.3 to 4.1. From the viewpoint of copper affinity and copper migration, a pKa of 2.0 to 3.6 is preferred. The reason for achieving the above-mentioned effect by using this (B) tetrazolium compound is uncertain and not limited to theory, but the inventors have considered the following: It is speculated that the tetrazolium compound exerts its effect by coordinating with copper in the substrate, and if the pKa of the tetrazolium compound is 4.1 or lower, the interaction with the resin becomes stronger, and the copper affinity is improved. On the other hand, it is speculated that if the pKa of the tetrazolium compound is 1.3 or higher, the interaction will not be too strong, and copper migration can be suppressed. Therefore, it is speculated that by giving the tetrazolium compound a moderate acidity, both copper affinity and copper migration can be balanced. Regarding pKa, the calculated value is used using Advanced Chemistry Software V11.02 (1994-2018 ACD / Labs).

[0073] Examples of (B) tetrazolium compounds with 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, ethyl 1H-tetrazole-5-carboxylic acid, methyl 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)succinic acid, 2,2-bis(2-2H-tetrazole-5-yl)ethyl)malonic acid, and 4-(1H-tetrazole-5-yl)benzoic acid. Of these, from the viewpoint of copper adhesion and copper migration, 1H-tetrazole-5-carboxylic acid, 1H-tetrazole-5-acetic acid, and 4-(1H-tetrazole-5-yl)benzoic acid are preferred, with 1H-tetrazole-5-acetic acid being even more preferred. Furthermore, when these compounds are added to the resin composition, they can be in the form of hydrates.

[0074] In a single-state sample, (B) tetrazolium compounds are represented by the following formula (1) or (2). [Chemistry 69] {In formula (1), R1 is a hydrogen atom or a monovalent organogroup selected from the group consisting of alkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 10 carbon atoms; the hydrogen atoms of the alkyl and aryl groups may be independently substituted by at least one substituent selected from the group consisting of halogen atoms, hydroxyl groups, alkoxysilyl groups, and amino groups, or they may remain unsubstituted.} [Chemistry 70] {In formula (2), R2 is a hydrogen atom or a monovalent organogroup selected from the group consisting of alkyl groups with 1 to 10 carbon atoms and aryl groups with 6 to 10 carbon atoms; R3 is an alkyl group with 1 to 10 carbon atoms; the hydrogen atoms of alkyl, aryl, and alkyl groups may be independently substituted by at least one substituent selected from the group consisting of halogen atoms, hydroxyl groups, alkoxysilyl groups, and amino groups, or they may remain unsubstituted.}

[0075] (B) Tetraazole compounds containing the compounds represented by formula (1) or (2) above can achieve excellent copper adhesion, copper migration inhibition, and copper void suppression effects. The reasons are uncertain and not limited to theory, but it is believed that the non-shared electron pairs attached to the nitrogen atom in tetraazole act on copper, are segregated at the copper interface, and the constituent atoms of carboxylic acid and ester can form hydrogen bonds with polyimide precursors. Therefore, the resin interacts with copper, thereby improving the copper adhesion. In addition, it is believed that by making the tetraazole compound segregate at the copper interface, the oxidation reaction at the copper interface can be strongly inhibited, thereby inhibiting copper migration and copper voids. Furthermore, it is speculated that if R3 in general formula (2) has 1 to 10 carbon atoms, compared with the compound in general formula (1), the molecule has a higher boiling point. It is not easy to volatilize during the pre-baking when coated on the substrate and can remain in the film. It is also easy to move in the film and segregate at the interface, thus being more effective in copper adhesion or copper void suppression.

[0076] Furthermore, especially from the viewpoint of copper adhesion, (B) tetrazolium compounds are preferably compounds containing the general formula (3) below. [Chemistry 71] {In the formula, R4 is a hydrogen atom or a monovalent organogroup selected from the group consisting of alkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 10 carbon atoms; the hydrogen atoms of the alkyl and aryl groups may be independently substituted by at least one substituent selected from the group consisting of halogen atoms, hydroxyl groups, alkoxysilyl groups, and amino groups, or they may remain unsubstituted.}

[0077] The alkyl groups R1, R2, and R4 in general formulas (1) to (3) that have 1 to 10 carbon atoms can be branched or linear. Examples of preferred alkyl groups are alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, and propyl. Examples of aryl groups R1, R2, and R4 that have 6 to 10 carbon atoms in general formulas (1) to (3) include phenyl, tolyl, xylyl, and naphthyl. The alkyl groups R3 in general formula (3) that have 1 to 10 carbon atoms can be branched or linear. Examples of preferred alkyl groups are alkyl groups having 1 to 5 carbon atoms, such as methylene, ethyl, and propyl. The hydrogen atoms of these organogroups can be independently substituted by at least one substituent selected from the group consisting of halogen atoms, hydroxyl groups, alkoxysilyl groups, and amino groups, or they can remain unsubstituted. In the presence of an alkoxysilyl group, the number of carbon atoms in the organic group is not included. Examples of halogen atoms include chlorine, fluorine, bromine, and iodine. Examples of alkoxysilyl groups include trialkoxysilyl, dialkoxysilyl, and monoalkoxysilyl; specifically, examples include trimethoxysilyl, triethoxysilyl, dimethoxysilyl, and methoxysilyl. In general formula (3), compounds where R4 is a hydrogen atom are preferred from the viewpoints of copper adhesion, copper porosity, and copper migration.

[0078] As for the (B) tetrazolium compounds represented by general formulas (1) to (2), examples include, for instance, 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, methyl 1H-tetrazole-5-carboxylic acid, ethyl 1H-tetrazole-5-carboxylic acid, methyl 1H-tetrazole-5-acetic acid, ethyl 1H-tetrazole-5-acetic acid, and propyl 1H-tetrazole-5-acetic acid, but are not limited to these. Among these, from the viewpoint of copper adhesion and copper migration, 1H-tetrazole-5-carboxylic acid, ethyl 1H-tetrazole-5-carboxylic acid, ethyl 1H-tetrazole-5-acetic acid, and ethyl 1H-tetrazole-5-acetic acid are preferred, and 1H-tetrazole-5-acetic acid is even more preferred. Furthermore, when these compounds are added to a resin composition, they can be in the form of hydrates.

[0079] In the first-state sample, (B) the topological polar surface area (tPSA) of the tetrazolium compound was 81-200. Topological polar surface area (tPSA) refers to the area of ​​the polar portion of a molecule's surface, primarily used in pharmaceutical chemistry to evaluate the cell membrane permeability of drugs. By containing a tetrazolium compound with a tPSA of 81 to 200 in the photosensitive resin composition, both copper adhesion and copper migration inhibition effects can be achieved. The rationale is uncertain and not limited to theory, but it is believed that the tetrazolium compound, possessing a moderate polarity of 81 to 200 (as described in the pKa section), exhibits moderate interaction with the resin during copper coordination, thus achieving both copper adhesion and copper migration inhibition. Furthermore, it is believed that if the tPSA is below 200, the molecular weight decreases, resulting in better dispersibility of the tetrazolium compound in the photosensitive resin composition, thereby exerting both copper adhesion and copper migration inhibition effects.

[0080] The tPSA is calculated using software called "RDKit". "RDKit" is an open-source Python library used in the field of chemical information. Detailed information about "RDKit" can be found, for example, in "G. Landrum, RDKit: Open-Source Cheminformatics (http: / / www.rdkit.org.)". The following program is used in the tPSA calculation of this invention. Python 3.8.8 RDkit 2023.03.3

[0081] Examples of (B) tetrazolium compounds with a tPSA of 81 to 200 include: 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)succinic acid, 2,2-bis(2-2H-tetrazole-5-yl)ethyl)malonic acid, 4-(1H-tetrazole-5-yl)benzoic acid, and 1H-tetrazole-5-butyric acid, but are not limited to these. Among these, from the viewpoint of copper adhesion and copper migration, 1H-tetrazole-5-carboxylic acid, 1H-tetrazole-5-acetic acid, and 4-(1H-tetrazole-5-yl)benzoic acid are preferred, and 1H-tetrazole-5-acetic acid is even more preferred. Furthermore, when these compounds are added to a resin composition, they can be in the form of hydrates.

[0082] The amount of the tetrazolium compound in (B) relative to 100 parts by weight of the polyimide precursor or polyimide resin in (A) is preferably 0.001 parts by weight to 20 parts by weight, more preferably 0.01 parts by weight to 10 parts by weight, and even more preferably 0.01 parts by weight to 5 parts by weight. As for the above-mentioned amount, considering the need for sufficient effect in terms of copper adhesion and copper migration inhibition, it is preferably 0.01 parts by weight or more, and from the viewpoint of copper adhesion, copper migration inhibition, and solubility in the composition, it is preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less. The reason for setting it to 10 parts by weight or less is uncertain and not limited to theory, but it is speculated that a weak layer is less likely to form between the copper layer and the resin layer, thus improving copper adhesion, preventing the ionic content in the resin layer from increasing to the required level, and also improving copper migration.

[0083] (C) Photopolymerization initiator (C) Photopolymerization initiators will be described. Preferably, photoradical polymerization initiators are photoinitiators, and examples include: benzophenone, methyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, benzophenone derivatives such as benzophenone, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylphenylacetone, 1-hydroxycyclohexylphenyl ketone, and other acetophenone derivatives; 9-oxosulfuron-methyl... 2-Methyl-9-oxosulfur 2-Isopropyl-9-oxosulfur Diethyl-9-oxosulfur 9-Oxysulfur Derivatives, benzoin, benzoin dimethyl ketal, benzoin-β-methoxyethyl acetal and other benzoin derivatives, benzoin, benzoin methyl ether and other benzoin derivatives, 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2 Oximes such as -(O-benzoyl)oxime, 1,3-diphenyltrione-2-(O-ethoxycarbonyl)oxime, and 1-phenyl-3-ethoxytrione-2-(O-benzoyl)oxime; N-aryl glycine acids such as N-phenylglycine; peroxides such as benzoyl perchlorate; aromatic biimidazoles; titanium dioxide; and photoacid generating agents such as α-(n-octylsulfoxyimino)-4-methoxyphenylacetonitrile, but not limited to these. Among the above-mentioned photopolymerization initiators, oximes are particularly preferred in terms of photosensitivity.

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

[0085] (D) Solvent The solvent (D) is described below. Examples of solvents include: amines, sulfides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and alcohols. For example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylmethamide, dimethyl sulfide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, and diethyl oxalate. Esters, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenylethylene glycol, tetrahydrofuran methanol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, α-porphyrin, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, 1,3,5-trimethylbenzene, etc. From the viewpoints of resin solubility, resin composition stability, and adhesion to the substrate, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenylethylene glycol, 3-methoxy-N,N-dimethylpropionic acid, 3-butoxy-N,N-dimethylpropionic acid, and tetrahydrofuran methanol are preferred.

[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-dimethylpropionic acid, and 3-butoxy-N,N-dimethylpropionic acid. Especially from the viewpoint of in-plane uniformity when coating the photosensitive resin composition onto a substrate, γ-butyrolactone and 3-methoxy-N,N-dimethylpropionic acid are preferred.

[0087] The solvent may be one or a mixture of two or more solvents. From the viewpoint of suitably adjusting the stability of the resin composition, two or more solvents are preferred. When two or more solvents are contained, from the viewpoint of in-plane uniformity, 50% by weight or more of the solvent is preferably either γ-butyrolactone or 3-methoxy-N,N-dimethylpropionic acid, and more preferably γ-butyrolactone.

[0088] In the photosensitive resin composition, the amount of solvent used is preferably 100 to 1000 parts by weight relative to 100 parts by weight of (A) polyimide precursor or polyimide resin, more preferably 120 to 700 parts by weight, and even more preferably 125 to 500 parts by weight.

[0089] (E) Free radical polymers The photosensitive resin composition may further contain an (E) radical polymerizable compound. When an (E) radical polymerizable compound is used, the photosensitive resin composition undergoes cross-linking, reducing the moisture permeability of the hardened film, thereby achieving a copper migration inhibition effect. Preferably, the photosensitive resin composition contains 5 to 150 parts by mass of the radical polymerizable compound relative to 100 parts by mass of the (A) polyimide precursor or polyimide resin. To obtain good chemical resistance, the photosensitive resin composition preferably contains 5 or more parts by mass of the radical polymerizable compound, more preferably 10 or more parts by mass, and even more preferably 20 or more parts by mass. If too much radical polymerizable compound is contained, copper adhesion may sometimes decrease. However, it is known that the photosensitive resin composition of the present invention, by containing the aforementioned specific tetrazolium compound, can obtain higher copper adhesion even when containing a larger amount of the radical polymerizable compound. From the viewpoint of patterning characteristics, the upper limit value, which can be arbitrarily combined with the above lower limit value, 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.

[0090] The term "free radical polymerizable compound" is not particularly limited to any compound that undergoes free radical polymerization reaction by means of photopolymerization initiators and thermal polymerization initiators. It is preferably a (meth)acrylic acid compound, for example, represented by the following general formula (43): [Chemistry 72] {In formula (43), X 11 is an organic group, L 11, L 12 and L 13 are each an independent hydrogen atom or an organic group with one to three carbon atoms; n 11 is an integer from 1 to 10}.

[0091] Free radical polymerizable compounds are not particularly limited to the following, but examples include: 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; diacrylates and dimethacrylates of 1,4-butanediol; and diacrylates and dimethacrylates of 1,6-hexanediol. Compounds including acrylates, diacrylates and dimethacrylates of neopentyl glycol, mono- or diacrylates and methacrylates of bisphenol A, trimethacrylates, isoacrylates and isomethacrylates, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylates, di- or triacrylates and methacrylates of glycerol, di, tri- or tetraacrylates and methacrylates of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds. More specifically, compounds represented by the following formulas (44) and (45) can be exemplified: [Chemistry 73] [Chemistry 74] , However, it is not limited to the above.

[0092] In this invention, when the number of free radical polymerizable compounds is one, it is called monofunctional; when there are two or more, it is called x-functional group according to the number x of free radical polymerizable groups. However, sometimes, difunctional and above compounds are collectively referred to as polyfunctional. Free radical polymerizable compounds can be monofunctional or difunctional or above. From the viewpoint of chemical resistance, free radical polymerizable compounds are preferably trifunctional or above, more preferably tetrafunctional or above, and even more preferably hexafunctional or above. On the other hand, from the viewpoint of elongation at break, decafunctionality or below is preferred.

[0093] The molecular weight of the free radical polymerizable compound is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more. As an upper limit, it is preferably 1000 or less, and more preferably 800 or less. By setting it within the above range, chemical resistance and patterning properties are improved.

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

[0095] As a free radical polymerizable compound having hydroxyl groups in its molecule, the structure represented by the following general formula (46) can be cited as an example: [Chemistry 75] {In formula (46), X 11 is an organic group, L 11, L 12, and L 13 are each independently a hydrogen atom or an organic group with one to three carbon atoms; n 11 is an integer from 1 to 10, and n 12 is an integer from 1 to 10}. From the perspective of free radical reactivity, it is better if L 11 is a hydrogen atom or a methyl group, and L 12 and L 13 are hydrogen atoms in the above formula (46). More specifically, the following compound represented by formula (47) can be cited as an example: [Chemistry 76] , However, it is not limited to the above. Due to the presence of hydroxyl groups in the molecular structure, chemical resistance becomes particularly good. The number of hydroxyl groups in the molecular structure is preferably one or more, and more preferably two or more. As an upper limit, it is preferably 10 or less, more preferably 6 or less, and more preferably 3 or less. By setting it within the above range, chemical resistance and adhesion to the substrate become good.

[0096] Radical polymerizable compounds containing urea groups in their molecules can be represented by the following general formula (48): [Chemistry 77] {In formula (48), X20, X21, X22, and X23 are respectively a hydrogen atom, an organogroup with a monovalent charge of the group represented by the following general formula (49), and an organogroup with a monovalent charge of 1 to 20 carbon atoms that may contain heteroatoms; at least one of X20, X21, X22, and X23 is an organogroup with a monovalent charge of the group represented by the following general formula (49)} [Chemistry 78] {In formula (49), L11, L12, and L13 are each independently a hydrogen atom or an organogroup with one to three carbon atoms in a single valence}. From the perspective of free radical reactivity, it is better if L11 is a hydrogen atom or a methyl group, and L12 and L13 are hydrogen atoms in the above formula (49).

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

[0098] In formula (48), when X20, X21, X22, and X23 are monovalent organic groups with 1 to 20 carbon atoms and heteroatoms, it is preferable that they contain oxygen atoms from the viewpoint of reproducibility. There is no limitation as long as the number of carbon atoms is 1 to 20, but from the viewpoint of heat resistance, the number of carbon atoms is preferably 1 to 10, and more preferably 3 to 10. X20, X21, X22, and X23 in formula (48) can bond with each other to form a cyclic structure, but from the viewpoint of chemical resistance, it is preferable that they do not have a cyclic structure. By making X20, X21, X22, and X23 bond with each other to form a cyclic structure, the degree of freedom of the bonding angle of the urea group is lost, and the formation of strong hydrogen bonds becomes difficult. From the viewpoint of forming hydrogen bonds with other molecules, it is preferable that at least one of X20, X21, X22, and X23 is a hydrogen atom. On the other hand, from the viewpoint of solubility, it is preferable that X20, X21, X22, and X23 have two or fewer hydrogen atoms. Examples of compounds represented by the following formulas can be specifically illustrated: [Chemistry 79] .

[0099] Free radical polymerizable compounds preferably have at least one hydroxyl group and at least one urea group in their molecule. A free radical polymerizable compound having at least one hydroxyl group and at least one urea group in its molecule can be represented, for example, by the following general formula (50): [Chemistry 80] {In formula (50), X30, X31, X32, and X33 are respectively a hydrogen atom, an organogroup with a monovalent group having a group represented by the following general formula (51), and an organogroup with a monovalent group having 1 to 20 carbon atoms that may contain heteroatoms; at least one of X30, X31, X32, and X33 is an organogroup with a monovalent group having a group represented by the following general formula (51), and at least one is a hydroxyl group} [Chemistry 81] {In formula (51), L11, L12, and L13 are each independently a hydrogen atom or an organogroup with one to three carbon atoms in a single valence}. In the case of L11 being a hydrogen atom or a methyl group, and L12 and L13 being hydrogen atoms in the above formula (51), it is better from the viewpoint of free radical reactivity.

[0100] In formula (50), when X30, X31, X32, and X33 are monovalent organic groups with 1 to 20 carbon atoms and heteroatoms, it is preferable that they contain oxygen atoms from the viewpoint of developability. There is no limitation as long as the number of carbon atoms is 1 to 20, but from the viewpoint of heat resistance, the number of carbon atoms is preferably 1 to 10, and more preferably 3 to 10. In formula (51), X30, X31, X32, and X33 can be bonded to each other to form a cyclic structure, but from the viewpoint of chemical resistance, it is preferable that they do not have a cyclic structure. By making X30, X31, X32, and X33 bonded to each other to form a cyclic structure, the degree of freedom of the bonding angle of the urea group is lost, and the formation of strong hydrogen bonds becomes difficult. From the viewpoint of forming hydrogen bonds with other molecules, it is preferable that at least one of X 30, X 31, X 32, and X 33 is a hydrogen atom. On the other hand, from the viewpoint of solubility, it is preferable that X 30, X 31, X 32, and X 33 contain two or fewer hydrogen atoms. Examples of compounds represented by the following formulas can be specifically illustrated: [Chemistry 82] .

[0101] There is no particular limitation on the method for manufacturing free radical polymerizable compounds, especially those containing urea groups. For example, they can be obtained by reacting an isocyanate compound with an amine-containing compound. When the amine-containing compound contains functional groups such as hydroxyl groups that can react with isocyanates, a portion of the isocyanate compound may contain compounds that react with functional groups such as hydroxyl groups.

[0102] The free radical polymerizable compound can be used alone, but 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 improved in-plane uniformity is speculative, but it is believed that when a large amount of a single free radical polymerizable compound is added, microphase separation occurs between it and the polyimide precursor component in the varnish. For the above reasons, when using the free radical polymerizable compound alone, the amount is preferably 60 parts by mass or less, and more preferably 40 parts by mass or less, relative to 100 parts by mass of the polyimide precursor.

[0103] When two or more free radical polymerizable compounds are used in combination, from the viewpoint of controlling the crosslinking density, it is preferable to use six or fewer, and more preferably four or fewer.

[0104] When using a mixture of multiple free radical polymerizable compounds, it is preferable that at least one of the free radical polymerizable compounds has a different number of functional groups. When using three or more free radical polymerizable compounds, it is acceptable as long as at least one of them has a different number of functional groups, but it is preferable that all the free radical polymerizable compounds have a different number of functional groups. When using a mixture of multiple free radical polymerizable compounds, from the viewpoint of elongation at break, it is preferable to include at least one monofunctional free radical polymerizable compound.

[0105] When using two or more free radical polymerizable compounds in combination, it is preferable to use at least one free radical polymerizable compound containing a nitrogen atom and one free radical polymerizable compound without a nitrogen atom. The aforementioned free radical polymerizable compound containing a nitrogen atom is preferably a free radical polymerizable compound containing a urea group. Free radical polymerizable compounds containing nitrogen atoms can form stronger hydrogen bonds, thus exhibiting excellent chemical resistance. However, if multiple free radical polymerizable compounds containing nitrogen atoms are added, a complex hydrogen bond network structure is formed, resulting in insufficient solubility.

[0106] The photosensitive resin composition may further contain components other than those listed in (A) to (E). There are no limitations on the components other than (A) to (E), but examples include: (F) thermal crosslinking agents, (G) heterocyclic compounds, (H) thermal alkali generating agents, (I) hindered phenolic compounds, (J) organotitanium compounds, (K) adhesive aids, (L) sensitizers, and (M) polymerization inhibitors.

[0107] (F) Thermal crosslinking agent To suppress copper adhesion or copper migration in polyimide films, the photosensitive resin composition may contain a thermal crosslinking agent.

[0108] The term "thermal crosslinking agent" refers to a compound that undergoes an addition reaction or a condensation reaction by means of heat. These reactions are produced by a combination of (A) polyimide resin and (F) thermal crosslinking agent, (F) thermal crosslinking agent with itself, and (F) thermal crosslinking agent with other components described below, with the reaction temperature preferably being 150°C or higher.

[0109] Examples of thermal crosslinking agents include: alkoxymethyl compounds, epoxy compounds, oxetane compounds, bismaleimide compounds, allyl compounds, and terminal isocyanate compounds. From the viewpoint of inhibiting hardening shrinkage, (F) thermal crosslinking agents are preferably those containing nitrogen atoms.

[0110] Examples of alkoxymethyl compounds include compounds with the following formulas, but are not limited to these. [Chemistry 83]

[0111] Furthermore, examples of commercially available alkoxymethyl compounds include: alkyl urea resin (product name MX290, manufactured by NIKALAC) or 1,3,4,6-tetra(methoxymethyl)glycourea (product name MX270, manufactured by NIKALAC), etc.

[0112] Examples of epoxy compounds include: 4-hydroxybutyl acrylate glycidyl ether, epoxy compounds containing bisphenol A groups, and hydrogenated bisphenol A diglycidyl ether. For example, Epolight 4000 (product name, manufactured by Kyoei Chemical Co., Ltd.) is preferred.

[0113] Examples of oxetane compounds include: 1,4-bis{[(3-ethyl-3-oxetane)methoxy]methyl}benzene, bis[1-ethyl(3-oxetane)]methyl ether, 4,4'-bis[(3-ethyl-3-oxetane)methyl]biphenyl, 4,4'-bis(3-ethyl-3-oxetane)methoxy)biphenyl, ethylene glycol bis(3-ethyl-3-oxetane)methyl ether, and diethylene glycol bis(3-ethyl-3-oxetane)methyl ether. Ethers, bis(3-ethyl-3-oxetanebutylmethyl) bisphenol A, trimethylolpropane tri(3-ethyl-3-oxetanebutylmethyl) ether, pentaerythritol tetra(3-ethyl-3-oxetanebutylmethyl) ether, poly[[3-[(3-ethyl-3-oxetanebutyl)methoxy]propyl]sesquioxane] derivatives, oxetane silicate butyl ester, phenolic varnish-type oxetane, and 1,3-bis[(3-ethyloxetane-3-yl)methoxy]benzene, etc. For example, OXT121 (product name, Toa Synthetic Manufacturing Co., Ltd.) and OXT221 (product name, Toa Synthetic Manufacturing Co., Ltd.) are preferred.

[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-epenylphenylbis(maleimide), 4-methyl-N,N'- 1,3-Phenylbenzylbis(maleimide), N,N'-1,4-Phenylbenzylbis(maleimide), 3-methyl-N,N'-1,4-Phenylbenzylbis(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, etc.

[0115] Examples of allyl compounds include: allyl alcohol, allyl anisole, allyl benzoate, allyl cinnamate, N-allyloxyphthalimide, allyl phenol, allyl phenyl ether, allyl urea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl isocyanate, triallylamine, triallyl isocyanate, triallyl cyanurate, triallylamine, 1,3,5-tristylacetate, triallyl trimellitate, triallyl phosphate, triallyl phosphite, and triallyl citrate.

[0116] Examples of end-capped isocyanate compounds include: hexamethylene diisocyanate-based end-capped 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 Corporation, trade name: Takenate B-882N; and manufactured by Baxenden Corporation, trade names: 7960, 7961, 7982, 7991, and 7992, etc.); toluene diisocyanate-based end-capped isocyanates (e.g., manufactured by Mitsui Chemicals Corporation, trade name: Takenate B-830, etc.); and 4,4'-diphenylmethane diisocyanate-based end-capped isocyanates (e.g., manufactured by Mitsui Chemicals Corporation, trade name: Takenate). B-815N, manufactured by Daiei Sangyo (stock), trade names: Blonate PMD-OA01 and PMD-MA01, etc.; 1,3-bis(isocyanomethyl)cyclohexane-terminated isocyanates (e.g., manufactured by Mitsui Chemicals (stock), trade name: Takenate); B-846N, manufactured by Tosoh (stock), trade names: Coronate BI-301, 2507 and 2554, etc.); and isophorone diisocyanate-terminated isocyanates (e.g., manufactured by Baxenden, trade names: 7950, 7951 and 7990, etc.).

[0117] Of these, from the viewpoint of preserving stability, end-capped isocyanate compounds or bismaleimide compounds are preferred. (F) Thermal crosslinking agents can be used alone or in combination of two or more.

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

[0119] (G) Heterocyclic compounds In addition to the tetrazolium compound (B), the photosensitive resin composition of the present invention may also contain heterocyclic compounds for the purpose of improving copper adhesion or development properties, copper migration inhibition ability, etc. Examples of heterocyclic compounds include imidazole derivatives, triazole derivatives, tetrazolium 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-amino Adenine, 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. One of these heterocyclic compounds may be used, or a mixture of two or more may be used.

[0121] When the photosensitive resin composition contains heterocyclic compounds, the amount of these compounds relative to 100 parts by weight of (A) polyimide precursor or polyimide resin is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight from the viewpoint of copper adhesion. When the above-mentioned amount is 0.1 parts by weight or more, copper discoloration is suppressed when the photosensitive resin composition is formed on copper; on the other hand, when it is 10 parts by weight or less, copper adhesion is excellent.

[0122] (H) Thermal alkali generating agent The photosensitive resin composition may contain an alkali-generating agent. An alkali-generating agent is a compound that produces an alkali upon heating. The presence of a thermal alkali-generating agent can further promote the acetylation of the photosensitive resin composition.

[0123] No particular type is specified as a heat-generating agent, but examples include amine compounds protected by a tributoxycarbonyl group, or heat-generating agents disclosed in International Publication No. 2017 / 038598. However, it is not limited to these, and other known heat-generating agents may also be used.

[0124] Examples of amine compounds protected by the third 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, valine, and 3-amino-1,2-propanediol. 2-Amino-1,3-propanediol, tyramine, demethylephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, Diethanolamine, diisopropanolamine, 3-pyrrolidone, 2-pyrrolidone methanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidine methanol, 3-piperidine methanol, 2-piperidine methanol, 4-piperidine ethanol, 2-piperidine ethanol, 2-(4-piperidinyl)-2-propanol, 1,4-butanol bis(3-aminopropyl) ether, 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 amino acids and their derivatives is protected by a tert-butoxycarbonyl group, but are not limited to these.

[0125] The amount of the heat-alkali generating agent relative to 100 parts by weight of (A) polyimide precursor or polyimide resin is preferably 0.1 parts by weight or more and 30 parts by weight or more, more preferably 1 part by weight or more and 20 parts by weight or less. As for the above-mentioned amount, from the viewpoint of promoting amide formation, it is 0.1 parts by weight or more, and from the viewpoint of the physical properties of the photosensitive resin layer after curing the photosensitive resin composition, it is preferably 20 parts by weight or less.

[0126] (I) Hindered phenolic compounds To suppress discoloration on the copper surface, the photosensitive resin composition may optionally contain a hindered phenolic compound. There are no limitations on the hindered phenolic compound; examples include: 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, 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'-butylene-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], and 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. Tributyl-4-hydroxyphenyl)propionate, 2,2-thiodiethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyphenylpropionamide), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), pentaerythritol-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, etc.

[0127] Furthermore, examples of hindered phenolic compounds include: 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-tris(2,6-dimethyl-4-isopropylbenzyl)-1,3,5-tris(2,6-dimethyl-3-hydroxy-2,6-dimethyl ...[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1, [6-Dimethylbenzyl]-1,3,5-tris(2,6-dimethylbenzyl)-1,3,5-tris(2,6-dimethylbenzyl)-1,3,5-tris(2,6-dimethylbenzyl)-1,3,5-tris(2,6-dimethylbenzyl)-1,3,5-tris(2,6-dimethylbenzyl)-1,3,5-tris(2,6-dimethylbenzyl)-1,3,5-tris(2,6-dimethylbenzyl)-2,4,6-(1,3,5-dimethylbenzyl)-1,3,5-tris(2,6 ... 3,5-Tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris(4-tert-butyl-5,6-diethyl-3-hydroxy-2,6 ... Tris(4-tert-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tert-butyl-2,4,6-(1H,3H,5H)-trione), etc., but not limited to them.

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

[0129] The amount of hindered phenolic compound is preferably 0.1 to 20 parts by weight relative to 100 parts by weight of (A) polyimide precursor or polyimide resin, and more preferably 0.5 to 10 parts by weight from the viewpoint of photosensitivity characteristics. When the above-mentioned amount is 0.1 parts by weight or more, for example, when forming a photosensitive resin composition on copper or copper alloy, discoloration and corrosion of copper or copper alloy are prevented; on the other hand, when it is 20 parts by weight or less, the photosensitivity is excellent.

[0130] (J) Organotitanium Compounds The photosensitive resin composition may contain organotitanium compounds. By containing organotitanium compounds, a photosensitive resin layer with excellent chemical resistance can be formed even when curing at low temperatures.

[0131] Examples of usable organotitanium compounds include organic chemical substances that are bonded to titanium atoms via covalent or ionic bonds.

[0132] Specific examples of organotitanium compounds are shown in sections I) to VII) below. I) Titanium chelate compounds: Among these, titanium chelates having two or more alkoxy groups are more preferably preferred in terms of obtaining the storage stability and good patterning of the photosensitive resin composition. Specific examples include: titanium bis(triethanolamine)diisopropoxide, titanium bis(2,4-glutaric acid)di-n-butoxide, titanium bis(2,4-glutaric acid)diisopropoxide, titanium bis(tetramethylheptanoic acid)diisopropoxide, titanium bis(ethylacetic acid)diisopropoxide, etc.

[0133] II) Tetraalkoxy titanium compounds: such as tetra(n-butanol)titanium, tetraethanol titanium, tetra(2-ethylhexanol)titanium, tetraisobutanol titanium, tetraisopropanol titanium, tetramethanol titanium, tetramethoxypropanol titanium, tetramethylphenol titanium, tetra(n-nonanol)titanium, tetra(n-propanol)titanium, tetrastearyl titanium, tetra[bis{2,2-(allyloxymethyl)butanol}]titanium, etc.

[0134] III) Titanium decene compounds: such as pentamethylcyclopentadienyltrimethyltitanium, 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: such as titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonic acid) isopropoxide, etc.

[0136] V) Titanium oxide compounds: such as bis(glutaric acid) titanium oxide, bis(tetramethylpimelic acid) titanium oxide, phthalocyanine titanium oxide, etc.

[0137] VI) Tetraacetylpyruvate titanium compounds: such as tetraacetylpyruvate titanium, etc.

[0138] VII) Titanate coupling agents: such as tris(dodecylbenzenesulfonyl)titanate isopropyl ester, etc.

[0139] When the organotitanium compound is selected from at least one compound in the group consisting of I) titanium chelates, II) tetraalkoxy titanium compounds, and III) diacetic titanium compounds, it is preferable to exhibit better chemical resistance. Particularly preferred are bis(ethylacetic acid)diisopropoxide titanium, tetra(n-butanol) titanium, and bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl) titanium.

[0140] When the organic titanium compound is incorporated, the amount incorporated is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 2 parts by weight, relative to 100 parts by weight of (A) polyimide precursor or polyimide. When the amount incorporated is 0.05 parts by weight or more, good heat resistance and chemical resistance are observed; on the other hand, when the amount is less than 10 parts by weight, excellent storage stability is observed.

[0141] (K) Next, the additives To improve the adhesion between the film formed using the photosensitive resin composition and the substrate, the photosensitive resin composition may optionally contain an adhesive aid. Examples of adhesive aids include: γ-aminopropyl dimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyl dimethoxysilane, γ-glycidoxypropylmethyl dimethoxysilane, γ-mercaptopropylmethyl dimethoxysilane, 3-methacryloxypropyl dimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinylpropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)butadieneimide, and N-[3-(triethoxysilyl)propyl]phthalimide. Silicon coupling agents such as methacin, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylacetamide)-4,4'-dicarboxylic acid, phenyl-1,4-bis(N-[3-triethoxysilyl]propylacetamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureopropyltrimethoxysilane, 3-ureopropyltriethoxysilane, 3-(trialkoxysilyl)propylsuccinic anhydride, and aluminum-based adhesives such as tris(ethylacetate)aluminum, tris(acetylacetonate)aluminum, and ethylaluminum diisopropylacetate.

[0142] Of these adhesive aids, silane coupling agents are preferred in terms of adhesion strength. When the photosensitive resin composition contains adhesive aids, the amount of adhesive aid prepared relative to 100 parts by weight of (A) polyimide precursor is preferably in the range of 0.5 to 25 parts by weight.

[0143] As a silane coupling agent, there are no limitations; examples include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd.: trade name KBM803, manufactured by Chisso Co., Ltd.: trade name Sila-Ace). S810), N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd.: trade name KBM573), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd.: trade name LS1375, manufactured by Azmax Co., Ltd.: trade name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropyltripropoxysilane 2-Mercaptoethyltrimethoxysilane, 2-Mercaptoethyldiethoxymethoxysilane, 2-Mercaptoethylethoxydimethoxysilane, 2-Mercaptoethylethoxydimethoxysilane, 2-Mercaptoethyltripropoxysilane, 2-Mercaptoethyltripropoxysilane, 2-Mercaptoethylethoxydipropoxysilane, 2-Mercaptoethylethoxydipropoxysilane, 2-Mercaptoethyldimethoxypropoxysilane, 2-Mercaptoethyltripropoxysilane Oxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, aminocarboxylic acid (3-triethoxysilylpropyl)-tertiary butyl ester, 4,4-carbonylbis(2-(((3-triethoxysilyl)propyl)amino)carbonyl)benzoic acid, 2-(3-triethoxysilylpropylaminomethyl)benzoic acid, etc.

[0144] Furthermore, there are no limitations on the silane coupling agent used; examples include: N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Industry Co., Ltd.: trade name LS3610, manufactured by Azmax Co., Ltd.: trade name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Co., Ltd.: trade name SIU9058.0), and N-(3-diethoxymethoxysilylpropyl)urea. N-(3-ethoxydimethoxysilylpropyl)urea, N-(3-tripropoxysilylpropyl)urea, N-(3-diethoxypropoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-dimethoxypropoxysilylpropyl)urea, N-(3-methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea, N-(3-ethoxydimethoxysilylethyl)urea, N -(3-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)propoxysilylethyl)urea M-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.1), and aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.2), etc.

[0145] Furthermore, examples of silane coupling agents include: 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax Inc.: trade name SIT8396.0), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylmethylethyl)pyridine, carbamate (3-triethoxysilylpropyl)-tert-butyl ester, (3-glycidoxypropyl)triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, and tetra-n-butoxysilane. Tetraisobutoxysilane, tetratert-butoxysilane, tetra(methoxyethoxysilane), tetra(methoxy-n-propoxysilane), tetra(ethoxyethoxysilane), tetra(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-tert-butoxydiethoxysilane, di-isobutoxyaluminoxytriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butyldiphenylsilanediol, isobutylphenylsilanediol, tri-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilane, n-propylmethylphenylsilane. Isopropyl methylphenylsilane, n-butyl methylphenylsilane, isobutyl methylphenylsilane, tributyl methylphenylsilane, ethyl n-propylphenylsilane, ethyl isopropylphenylsilane, n-butyl ethylphenylsilane, isobutyl ethylphenylsilane, tributyl ethylphenylsilane, methyl diphenylsilane, ethyl diphenylsilane, n-propyl diphenylsilane, isopropyl diphenylsilane, n-butyl diphenylsilane, isobutyl diphenylsilane, tributyl diphenylsilane, triphenylsilane, etc., but not limited to these.

[0146] The silane coupling agents listed above can be used alone or in combination. From the viewpoint of preserving stability, the preferred silane coupling agents are phenylsilane triol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenylsilane diol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-tolylsilane, triphenylsilane alcohol, and silane coupling agents having the structures represented by the following formulas: [Chemistry 84] .

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

[0148] (L) sensitizer To improve photosensitivity, the photosensitive resin composition may optionally contain a sensitizer. Examples of such sensitizers include: milchnerone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzyl)cyclopentane, 2,6-bis(4'-diethylaminobenzyl)cyclohexanone, 2,6-bis(4'-diethylaminobenzyl)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylamino... Cinnamyl dihydroindone, p-dimethylaminobenzyl dihydroindone, 2-(p-dimethylaminophenylbenzyl)-benzothiazole, 2-(p-dimethylaminophenylvinyl)benzothiazole, 2-(p-dimethylaminophenylvinyl)isonaphthothiazole, 1,3-bis(4'-dimethylaminophenylmethylene)acetone, 1,3-bis(4'-diethylaminophenylmethylene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarone) ), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-phospholinylbenzophenone, dimethyl... Isoamyl aminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, 2,2'-(phenylimino)diethanol, etc. These can be used alone or, for example, in combination of 2 to 5.

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

[0150] (M) Polymerization Inhibitor To improve the stability of viscosity and photosensitivity of photosensitive resin compositions, especially when stored in solutions containing solvents, the photosensitive resin compositions may optionally contain polymerization inhibitors. As polymerization inhibitors, the following may be used: hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenanthrene, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, etc.

[0151] <Manufacturing Method and Semiconductor Device for Hardened Embossed Patterns> The method for manufacturing a hardened embossed pattern according to the present invention includes the following steps: (1) coating the photosensitive resin composition of the present invention onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the resin layer; (3) developing the exposed resin layer to form an embossed pattern; and (4) heat-treating the embossed pattern to form a hardened embossed pattern.

[0152] (1) Resin layer formation step In this step, the photosensitive resin composition is coated onto the substrate and then dried as needed to form a photosensitive resin layer. As a coating method, methods previously used for coating photosensitive resin compositions can be used, such as coating methods performed using a spin coater, bar coater, doctor blade coater, curtain coater, screen printing machine, or spray coating method using a spray coater.

[0153] (2) Exposure steps In this step, an exposure device such as a contact exposure machine, a mirror projection exposure machine, or a stepper is used to expose the resin layer formed above through a patterned photomask or reticle, or directly through an ultraviolet light source.

[0154] (3) Steps for forming raised patterns In this step, the unexposed portions of the exposed photosensitive resin layer are removed by development. As for the development method for the exposed (irradiated) photosensitive resin layer, any previously known photoresist development method can be selected, such as spin spraying, immersion, or immersion with ultrasonic treatment. Furthermore, after development, for the purpose of adjusting the shape of the embossed pattern, baking with any combination of temperature and time can be performed as needed.

[0155] The developing solution used in development is preferably a good solvent for the photosensitive resin composition, or a combination of such a good solvent and a poor solvent. Preferred good solvents include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Preferred poor solvents include toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate, and water. When a good solvent and a poor solvent are used in combination, the ratio of the poor solvent to the good solvent is preferably adjusted according to the solubility of the polymer in the photosensitive resin composition. Furthermore, two or more solvents may be used, for example, in combination.

[0156] (4) Steps for hardening and forming raised patterns In this step, the raised pattern obtained by the above development is subjected to heat treatment to dilute the photosensitive components and amide-imide the (A) polyimide precursor, thereby converting it into a hardened raised pattern (hardened film) containing polyimide. Various methods can be selected for the heat treatment, such as using a heating plate, using an oven, or using a temperature-controlled oven. The heat treatment can be performed, for example, at 160°C to 350°C for 30 minutes to 5 hours. For further improving copper adhesion, the heat treatment temperature is preferably below 350°C, more preferably below 230°C, further preferably below 200°C, and even more preferably below 180°C. Furthermore, to further suppress copper migration, the temperature is preferably above 200°C, more preferably above 230°C. Air, or inert gases such as nitrogen or argon, can be used as the ambient gas during heat curing.

[0157] Polyimide film The polyimide film (cured film) of the present invention can be manufactured by curing the photosensitive resin composition of the present invention. The present invention also provides a cured film formed from a cured product of the photosensitive resin composition of the present invention. For example, a photosensitive resin composition containing the polyimide resin of the present invention (A) can be used to manufacture a polyimide film based on the above-described method for manufacturing a cured embossed pattern. Alternatively, for example, a photosensitive resin composition containing the polyimide precursor of the present invention can be amided to form a cured polyimide with an amide content of 80-100%, thereby manufacturing a polyimide film. In this case, the polyimide film can be manufactured based on the above-described method for manufacturing a cured embossed pattern. The structure of the polyimide contained in the cured embossed pattern formed from the above-described polyimide precursor composition is represented by the following general formula. [Chemistry 85]

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

[0159] Semiconductor Devices The semiconductor device preferably has a hardened raised pattern obtained by the above-described method for manufacturing a hardened raised pattern. The semiconductor device preferably has a substrate serving as a semiconductor element, and a hardened raised pattern of polyimide formed on the substrate by the above-described method for manufacturing a hardened raised pattern. The semiconductor device can use a semiconductor element as a substrate and is manufactured by incorporating the method for manufacturing a hardened raised pattern of the present invention as part of the manufacturing process. More specifically, the semiconductor device can be manufactured by a semiconductor device manufacturing method that includes forming the hardened raised pattern formed by the method for manufacturing a hardened raised pattern of the present invention into a surface protective film, an interlayer insulating film, a rewiring insulating film, a protective film for flip-chip devices, or a protective film for a semiconductor device having a bump structure.

[0160] <Display Device> The display device is preferably a display device comprising a display element and a hardened film disposed on the upper part of the display element, wherein the hardened film is the aforementioned hardened raised pattern. Here, the hardened raised pattern can be directly deposited onto the display element, or it can be deposited with other layers in between. Examples of such hardened films include: surface protective films, insulating films, planarization films for TFT (thin-film transistor) liquid crystal display elements and color filter elements, protrusions for MVA (Multi-Domain Vertical Alignment) type liquid crystal display devices, and spacers for cathodes of organic EL (Electroluminescence) elements.

[0161] The photosensitive resin composition of the present invention is preferably a photosensitive resin composition for forming insulating components or for forming interlayer insulating films. Furthermore, the photosensitive resin composition can be used to form surface protective films, interlayer insulating films, reinforcing films, protective films for flip-chip devices, or protective films for semiconductor devices with bump structures. In addition to its application in semiconductor devices as described above, the photosensitive resin composition of the present invention can also be used for interlayer insulating films in multilayer circuits, cover coatings for flexible copper foils, solder resist films, liquid crystal alignment films, and other applications. [Example]

[0162] The following describes specific embodiments of the present invention, but the implementation is not limited thereto. In the embodiments, 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 determined using gel permeation chromatography (converted to standard polystyrene) under the following conditions. Pump: JASCO PU-980 Detector: JASCO RI-930 Column Oven: JASCO CO-965 40℃ Tube column: Two Shodex KD-806M tubes manufactured by Showa Denko Co., Ltd., connected in series, or Shodex 805M / 806M series-connected power supplies manufactured by Showa Denko Co., Ltd. Standard monodisperse polystyrene: Shodex STANDARD SM-105 manufactured by Showa Denko (Co., Ltd.) Mobile phase: 0.1 mol / L LiBr / N-methyl-2-pyrrolidone (NMP) Flow rate: 1 mL / min.

[0164] (2) Creation of hardened embossed patterns for evaluating copper porosity On a 6-inch silicon wafer (manufactured by Fujimi Electronic Industry Co., Ltd., 625±25 μm thick), a 200 nm thick layer of titanium (Ti) and a 400 nm thick layer of copper (Cu) were sequentially sputtered using a sputtering apparatus (L-440S-FHL type, manufactured by CANON ANELVA). Subsequently, a photosensitive resin composition prepared by the following method was spin-coated onto the wafer using a coating and developing machine (D-Spin60A type, manufactured by SOKUDO). Pre-baking was performed at 110°C for 180 seconds using a heated plate to form a coating film approximately 10 μm thick. A mask with a test pattern was then used to irradiate the coating film with i-rays at an energy of 650 mJ / cm² using a Prisma GHI (manufactured by Ultratech). Subsequently, using cyclopentanone as the developer, after a time of 1.4 times the time until the unexposed areas are completely dissolved and disappeared, the coating was spray-developed using a coating developer (D-Spin60A type, manufactured by SOKUDO). The coating was then washed with propylene glycol methyl ether acetate in a rotating spray for 10 seconds to obtain the raised pattern on Cu.

[0165] Using a temperature-programmed curing oven (VF-2000, manufactured by Koyo Lindberg), the wafer with the raised pattern formed on Cu was heated at 230°C for 2 hours in a nitrogen atmosphere to obtain a resin-containing hardened raised pattern of about 6-9 μm thickness on Cu.

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

[0167] The wafer with the hardened raised pattern formed on Cu was heated in air at 150°C for 168 hours using a temperature-programmed curing oven (VF-2000 type, manufactured by Koyo Lindberg). Subsequently, the resin layer on Cu was completely removed by plasma etching using a plasma surface treatment apparatus (EXAM type, manufactured by Shinko Seiki Co., Ltd.). The areas where resin was originally present were observed under the conditions described below to evaluate copper porosity. The plasma etching conditions are as follows. Output: 133 W Gas type and flow rate: O2: 40 mL / min + CF4: 1 mL / min Atmospheric pressure: 50 Pa Mode: Hard mode Etching time: 4200 seconds

[0168] The surface of Cu with all resin layers removed was observed under the following conditions using FE-SEM (S-4800 type, manufactured by Hitachi High Technology Co., Ltd.). The area occupied by voids on the surface of Cu layer was calculated using image analysis software (A-Image, manufactured by Asahi Kasei Corporation). <Observation Conditions> Accelerating voltage: 20 kV • SE detector: hybrid, BSE-L (LA5) • Probe current: High • Working distance: 8 mm Tilt angle: 0° • Observation magnification: 1000x

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

[0170] (4) Evaluation of copper tightness On a 6-inch silicon wafer (manufactured by Fujimi Electronic Industry Co., Ltd., thickness 625±25 μm), a sputtering apparatus (L-440S-FHL type, manufactured by CANON ANELVA) was used to sequentially sputter a 200 nm thick titanium (Ti) layer and a 400 nm thick copper (Cu) layer. Subsequently, a photosensitive resin composition was spin-coated onto the wafer to a cured film thickness of approximately 9 μm. After drying, the entire surface was exposed to 800 mJ / cm² using a parallel photomask aligned with an exposure machine (PLA-501FA type, manufactured by Canon). A temperature-programmable curing oven (VF-2000 type, manufactured by Koyo Lindberg) was used under a nitrogen atmosphere and heated for 2 hours at the temperatures described in Tables 1-4 to obtain a cured embossed pattern (thermally cured polyimide coating). For the heat-treated film, the adhesion characteristics between the copper substrate and the cured resin coating are evaluated based on the following criteria using the cross-cutting method according to JIS K 5600-5-6 standard. If the evaluation is B or higher, it can be better used as a cured relief pattern suitable for semiconductors. A: The grid number of the hardened resin coating bonded to the substrate is 100. B: The grid number of the hardened resin coating bonded to the substrate is 80 or more but less than 100. C: The grid number of the hardened resin coating bonded to the substrate is 40 or more but less than 80. D: The number of grids in the hardened resin coating bonded to the substrate is less than 40.

[0171] (5) b-Hast test A TEG (Test Element Group) wafer with comb-shaped Cu wiring of 10 μm / 10 μm and 5 μm height was prepared on a silicon wafer. The TEG wafer was immersed in a 1% acetic acid aqueous solution for 1 minute, then rinsed with deionized water and dried with an air gun. A low-pressure plasma (manufactured by Shinko Seiki Co., Ltd., EXAM) was applied for 20 seconds at 40 mL / min, 133 W, and 50 Pa. Subsequently, a photosensitive resin composition was spin-coated to a thickness of 10 μm using a coating and developing machine (D-Spin60A type, manufactured by Sokudo Co., Ltd.), and pre-baked at 110°C for 180 seconds using a heated plate to form a coating on the TEG wafer. Finally, the wafer was exposed to 800 mJ / cm² using a parallel light mask aligned with an exposure machine (PLA-501FA type, manufactured by Canon Co., Ltd.). At this point, to ensure conductivity during the b-HAST test, the Cu electrode area is exposed while being shielded from light, and the unexposed areas are removed by subsequent development. After exposure, after more than 30 minutes, a spin-spray development is performed at 23°C using cyclopentanone as the developer in a coating developer (D-Spin60A model, manufactured by SOKUDO), for a time 1.4 times longer than the time required for the unexposed areas to completely dissolve and disappear. This is followed by a 10-second spin-spray wash with propylene glycol monomethyl ether acetate. Subsequently, a temperature-programmed curing oven (VF-2000 model, manufactured by Koyo Lindberg) is used under nitrogen atmosphere and heated for 2 hours at the temperatures listed in Tables 2-4 to obtain a hardened embossed pattern.

[0172] Using a HAST Chamber (EHS-222M, ESPEC Inc.) and a highly accelerated life testing apparatus, the b-HAST test was conducted at 130°C and 85%RH with an applied voltage of 50 V. The insulation resistance between copper wirings was measured at 30-minute intervals; a resistance below 1 × 10⁴ Ω indicated insulation failure. The time from the start of the test to insulation failure was calculated and evaluated based on the following criteria. A rating of D or higher indicates that the pattern is suitable for use as a hardened raised pattern for semiconductors. A: More than 250 hours until insulation failure. B: The insulation failure occurs within 200 hours to less than 250 hours. C: The insulation failure occurs within 150 hours to less than 200 hours. D: The insulation failure occurs within 100 hours to less than 150 hours. E: Less than 100 hours have elapsed until insulation failure.

[0173] <Manufacturing Example> Manufacturing Example 1: (A) Synthesis of polyimide precursor A1 124.0 g of 4,4'-oxophthalic dianhydride (ODPA) and 29.4 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) were placed in a 2 L separable flask, followed by 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone (GBL). The mixture was stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain the reaction mixture. After the exothermic reaction was complete, the reaction mixture was cooled to room temperature and allowed to stand for 16 hours.

[0174] Next, under ice bath cooling, while stirring, a solution obtained by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 200 mL of γ-butyrolactone was added to the reaction mixture over 20 minutes. Then, while stirring, a solution obtained by suspending 93.0 g of 4,4'-oxodiphenylamine (ODA) in 350 mL of γ-butyrolactone was added over 30 minutes. After stirring at room temperature for 4 hours, 30 mL of ethanol was added and stirring for 1 hour, followed by the addition of 400 mL of γ-butyrolactone. The precipitate formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0175] The obtained reaction solution was added to 3 L of ethanol, generating a precipitate containing crude polymer. The crude polymer was separated by filtration 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. The precipitate was separated by filtration and then vacuum dried to obtain a powdered polymer (polyimide precursor A1). The molecular weight of polyimide precursor A1 was determined by gel permeation chromatography (converted to standard polystyrene), and the weight-average molecular weight (Mw) was 24,000.

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

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

[0178] Manufacturing Example 4: (A) Synthesis of polyimide precursor A4 Except for replacing 124.0 g of 4,4'-oxophthalic dianhydride (ODPA) and 29.4 g of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) with 155.1 g of ODPA and 93.0 g of 4,4'-oxodiphenylamine (ODA) with 98.6 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB), the reaction was carried out in the same manner as described in Manufacturing Example 1 above to obtain polymer (A4). The molecular weight of polymer (A4) was determined by gel permeation chromatography (converted to standard polystyrene), and the weight-average molecular weight (Mw) was 21,000.

[0179] Manufacturing Example 5: (A) Synthesis of polyimide precursor A5 Except for replacing 124.0 g of 4,4'-oxophthalic dianhydride (ODPA) and 29.4 g of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) with 155.1 g of ODPA and 49.2 g of 1,4-phenylenediamine (pPD) with 93.0 g of 4,4'-oxodiphenylamine (ODA), the reaction was carried out in the same manner as described in Manufacturing Example 1 above to obtain the polymer (polyimide precursor A5). The molecular weight of polyimide precursor A5 was determined by gel permeation chromatography (converted to standard polystyrene), and the weight-average molecular weight (Mw) was 21,000.

[0180] Manufacturing Example 6: (A) Synthesis of polyimide precursor A6 Except that 62 g of 4,4'-oxophthalic dianhydride (ODPA) and 88.3 g of pyromellitic dianhydride (PMDA) were used instead of 155.1 g of 4,4'-oxophthalic dianhydride (ODPA) in Manufacturing Example 4, the reaction was carried out in the same manner as described in Manufacturing Example 1 above to obtain a polymer (polyimide precursor A6). The molecular weight of polyimide precursor A6 was determined by gel permeation chromatography (converted to standard polystyrene), and the weight-average molecular weight (Mw) was 28,000.

[0181] Manufacturing Example 7: (A) Synthesis of Polyimide Resin A7 200 g of N-methyl-2-pyrrolidone (NMP) and 33.1 g (0.012 mol) of 6-(4-aminophenoxy)biphenyl-3-amine (PDPE) were added to a three-necked flask equipped with a Dean-Stark extraction apparatus and purged with nitrogen and dissolved. 24.8 g (0.1 mol) of bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BCD) and 50.0 g of toluene were then added, and the mixture was heated to 180°C. After confirming that the theoretical amount of water and added toluene in the Dean-Stark extraction apparatus had been extracted, heating was stopped, and the mixture was cooled to room temperature. The resulting reaction solution was added dropwise to 2000 g of ion-exchanged water to precipitate the polymer. After filtration and separation, the precipitate was dried under vacuum at 40°C to obtain a powdered polymer (polyimide resin A7). The weight-average molecular weight of polyimide resin A7 was determined by gel permeation chromatography (converted to standard polystyrene), and the result was Mw=14,300.

[0182] Manufacturing Example 8: (A) Synthesis of Polyimide Resin A8 Except for replacing NMP with GBL in Manufacturing Example 7, changing the amount of PDPE added to 23.0 g (0.083 mol), and replacing BCD with 4,4'-(hexafluoroisopropylidene)phthalic anhydride (6FDA) 44.4 g (0.1 mol), polyimide resin A8 was obtained in the same manner as in Manufacturing Example 7. The weight-average molecular weight of polyimide resin A8 was determined by gel permeation chromatography (converted to standard polystyrene), and the result was Mw = 14,000.

[0183] Manufacturing Example 9: (A) Synthesis of Polyimide Resin A9 Except for replacing NMP with GBL, PDPE with 30.1 g (0.088 mol) of 9,9'-bis(4-aminophenyl)furan (BAFL), and BCD with 19.6 g (0.1 mol) of 1,2,3,4-cyclobutanetetracarboxylic anhydride (CBDA), polyimide resin A9 was obtained in the same manner as in Manufacturing Example 7. The weight-average molecular weight of polyimide resin A9 was determined by gel permeation chromatography (converted to standard polystyrene), and the result was Mw = 29,000.

[0184] Manufacturing Example 10: (A) Synthesis of Polyimide Resin A10 (MOI Modified BCD-PDPE) 200 g of GBL and 33.1 g (0.12 mol) of PDPE were added to a three-necked flask equipped with a Dean-Stark extraction apparatus and purged with nitrogen 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 added toluene in the Dean-Stark extraction apparatus had been extracted, heating was stopped, and the mixture was cooled to room temperature.

[0185] Next, 6.2 g of ethyl 2-isocyanate methacrylate (MOI) was added at room temperature, and the reaction was allowed to proceed for 12 hours at room temperature. The resulting reaction solution was added dropwise to 2000 g of deionized water to precipitate the polymer. After filtration and separation, the polymer was vacuum dried at 40 °C to obtain a powdered polymer (polyimide resin A10). The weight-average molecular weight of polyimide resin A10 was determined by gel permeation chromatography (converted to 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. 100 g of (A) polyimide precursor A1: the polyimide precursor described in Manufacturing Example 1, 3 g of (B) tetrazolium compound B1: 1H-tetrazole-5-carboxylic acid (manufactured by Advanced ChemBlocks), 3 g of (C) photopolymerization initiator C1: TR-PBG-3057 (manufactured by TRONLY), and 10 g of (E) free radical polymerizable compound E1: NK Ester A-9300 (manufactured by Shin-Nakamura Chemical 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 Co., Ltd.) and solvent D2: dimethyl sulfoxide (hereinafter referred to as DMSO, manufactured by Toray Fine Chemical Co., Ltd.) 20 g. A photosensitive resin composition was prepared by adjusting the viscosity of the obtained solution to approximately 40 poise by adding the required amount of a GBL:DMSO solution in a ratio of 80:20 (mass ratio). The composition was evaluated according to the above method. The results are shown in Table 1.

[0187] <Examples 2-51, Comparative Examples 1-13> Except for the solvent, the formulation was adjusted according to the proportions shown in Tables 1-4. The solvent was dissolved in the same manner as in Example 1, and the viscosity was adjusted to prepare the photosensitive resin composition. Furthermore, copper adhesion and copper porosity were evaluated, or b-HAST tests were performed, to assess copper adhesion and copper migration properties. The results are shown in Tables 1-4. The compounds described in Tables 1-4 are as follows.

[0188] (A) Polyimide precursors or polymers that serve as comparisons. A1: Polyimide precursor described in Example 1 A2: Polyimide precursor described in Example 2 A3: Polyimide precursor described in Example 3 A4: Polyimide precursor described in Example 4 A5: Polyimide precursor described in Example 5 A6: Polyimide precursor described in Example 6 A7: Polyimide resin described in Manufacturing Example 7 A8: Polyimide resin described in Manufacturing Example 8 A9: Polyimide resin described in Manufacturing Example 9 A10: Polyimide resin described in Manufacturing Example 10 A1': ZCR-1797H (an acid-modified epoxy acrylate with a biphenyl backbone, manufactured by Nippon Kayaku Co., Ltd.)

[0189] (B) Tetrazol compounds B1: 1H-Tetrazol-5-carboxylic acid (manufactured by Advanced ChemBlocks) B2: 1H-Tetrazol-5-carboxylic acid ethyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.) B3: 1H-Tetrazol-5-acetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) B4: 1H-Tetrazol-5-ethyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) B5: 2-(2H-tetrazol-5-yl)succinic acid (manufactured by Enamine Building Blocks) B6: 2,2-Bis(2-2H-tetrazo-5-yl)ethyl)malonic acid (manufactured by Chemieliva Pharmaceuticals) B7: 4-(1H-tetrazole-5-yl)benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) B8: 1H-Tetrazol-5-propionic acid (manufactured by Enamine Building Blocks) B1': 5-Amino-1H-Tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.) B2':5-Phenyletetrazole (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 Qiangli Electronic New Materials Co., Ltd.) C2: 1-Phenylaceton-1,2-propanedione-2-(O-benzoyl)oxime (Product name KZ-941, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) C3: Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetylglucosime) (Product name: Irgacure OXE02, manufactured by BASF)

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

[0192] (E) Free 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 (trade name: NK Ester 4G, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) E3: Methoxyne(ethylene glycol) monomethacrylate (product name PME-400, manufactured by Nippon Oil Co., Ltd.) E4: Pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd. under product name A-TMMT) E5: Dipentaerythritol polyacrylate (product name A-DPH, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0193] (F) Thermal crosslinking agent F1: Alkyl urea resin (product name NIKALAC MX-290, manufactured by Sanwa Chemical Co., Ltd.) F2: 1,3,4,6-Tetra(methoxymethyl)glycourea (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) Organotitanium Compounds J1: Di(ethylacetic acid) diisopropoxide titanium (product name ORGATIX TC-750, manufactured by Matsumoto Fine Chemical Co., Ltd.)

[0196] (K) Next, the additives K1: N-Phenyl-3-aminopropyltrimethoxysilane (product name KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.) K2: Carbamate (3-triethoxysilylpropyl)-tert-butyl ester (manufactured by Gelest Corporation) 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 (manufactured by our company) K5: 2-(3-Triethoxysilylpropylaminomethyl)benzoic acid (manufactured by our company)

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

[0198] [Table 1] Table 1 polymer Tetraazole compounds Photopolymerization initiator free radical polymeric compounds Curing temperature [℃] Evaluation results A1 A2 A3 A4 A1' B1 B2 B3 B4 B1' B2' C1 E1 Copper porosity Copper tightness Example 1 100 3 3 10 230 B B Example 2 100 3 3 10 230 B B Example 3 100 3 3 10 230 A A Example 4 100 15 3 10 230 A B Example 5 100 3 3 10 230 B B Example 6 100 3 3 40 230 B B Example 7 100 3 3 40 230 B B Example 8 100 3 3 40 230 A A Example 9 100 15 3 40 230 A B Example 10 100 3 3 40 230 B B Example 11 100 0 3 40 230 A A Example 12 100 3 3 10 230 A A Example 13 100 3 3 10 230 A A Example 14 100 3 3 10 230 A A Comparative Example 1 100 3 3 10 230 C C Comparative Example 2 100 3 3 10 230 C C Comparative Example 3 100 3 3 40 230 D D Comparative Example 4 100 3 3 40 230 D D Comparative Example 5 100 3 3 10 230 D D Comparative Example 6 100 3 3 40 230 D D

[0199] [Table 2] Table 2 polymer Tetraazole compounds Photopolymerization initiator free radical polymeric compounds thermal crosslinking agent organotitanium compounds Adhesive agent sensitizer Curing temperature [℃] Evaluation results A2 A3 B3 C1 C2 C3 E2 E3 E4 E5 F1 J1 K1 L1 bHast Copper tightness pKa 3.4 tPSA 91.76 Example 15 100 1 4 10 1 0.5 1 10 200 C B Example 16 40 60 1 4 10 1 0.5 1 10 200 C A Example 17 40 60 0.005 4 10 1 0.5 1 10 200 D B Example 18 40 60 3 4 10 1 0.5 1 10 200 B A Example 19 40 60 10 4 10 1 0.5 1 10 200 C A Example 20 40 60 15 4 10 1 0.5 1 10 200 D B Example 21 40 60 1 4 10 1 0.5 1 200 C A Example 22 40 60 1 4 10 1 0.5 1 200 C A Example 23 40 60 1 4 10 1 0.5 1 10 230 A B Example 24 40 60 3 4 10 1 0.5 1 10 230 A A Example 25 40 60 3 4 10 1 0.5 1 10 250 A B Example 26 40 60 3 4 10 1 0.5 1 10 280 A B Example 27 40 60 3 4 10 1 0.5 1 10 350 A B Example 28 40 60 3 4 10 1 0.5 1 10 200 B B Example 29 40 60 1 4 10 1 0.5 1 10 200 C A Example 30 100 1 4 10 1 0.5 1 10 200 B A Example 31 100 1 4 1 0.5 1 10 200 C A

[0200] [Table 3] Table 3 polymer Tetraazole compounds Photopolymerization initiator free radical polymeric compounds thermal crosslinking agent organotitanium compounds Adhesive agent sensitizer Curing temperature [℃] Evaluation results A2 A3 B1 B3 B5 B6 B7 B8 C2 E1 E2 F1 F2 J1 K1 K2 K3 K4 K5 L1 bHast Copper tightness pKa 2.3 3.4 2.7 1.5 3.6 4 tPSA 91.76 91.76 129.1 183.5 91.76 91.76 Example 32 40 60 3 4 40 1 0.5 1 10 200 A B Example 33 40 60 3 4 15 1 0.5 1 10 200 B B Example 34 40 60 1 4 10 1 0.5 1 10 200 C B Example 35 40 60 1 4 10 0.5 1 10 200 D B Beauty Example 36 40 60 1 4 10 1 0.5 1 10 200 C A Implementation Example 37 40 60 1 4 10 1 0.5 1 10 200 C A Example 38 40 60 1 4 10 1 0.5 0.5 0.5 10 200 C A Example 39 40 60 1 4 10 1 0.5 10 200 C B Beauty example 40 40 60 1 4 10 1 0.5 1 10 200 C A Example 41 40 60 1 4 10 1 0.5 1 10 200 C A Example 42 40 60 1 4 10 1 0.5 1 10 200 C A Example 43 40 60 1 4 10 1 0.5 1 10 200 C A Example 44 40 60 1 4 10 1 0.5 1 10 200 C A

[0201] [Table 4] Table 4 polymer Tetraazole compounds Heterocyclic compounds Photopolymerization initiator free radical polymeric compounds thermal crosslinking agent organotitanium compounds Adhesive agent sensitizer Curing temperature [℃] Evaluation results A2 A3 A5 A6 A7 A8 A9 A10 B3 B1' B2' B3' G1 G2 G3 C2 E1 E2 F1 J1 K1 L1 bHast Copper tightness pKa 3.4 5.9 4.3 1.1 8.4 3.5 12.8 tPSA 91.8 80.5 54.5 43.6 41.6 78.9 93.4 Example 45 1 4 10 1 0.5 1 10 230 C B Example 46 100 3 4 10 1 0.5 1 10 230 C B Example 47 100 3 4 10 1 0.5 1 10 230 C B Example 48 100 1 4 40 1 0.5 1 10 230 A B Example 49 100 1 4 40 1 0.5 1 10 230 A B Example 50 100 1 4 40 1 0.5 1 10 230 B B Example 51 100 1 4 40 1 0.5 1 10 230 A B Comparative Example 7 40 60 1 4 10 1 0.5 1 10 200 E B Comparative Example 8 40 60 1 4 10 1 0.5 1 10 200 B D Comparative Example 9 40 60 1 4 10 1 0.5 1 10 200 C D Comparative Example 10 40 60 1 4 10 1 0.5 1 10 200 E D Comparative Example 11 40 60 0.5 4 10 1 0.5 1 10 200 E B Comparative Example 12 100 0.5 4 40 1 0.5 1 10 230 E B Comparative Example 13 40 60 1 4 10 1 0.5 1 10 200 E A

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

[0203] Observation of the results in Tables 2-4 reveals that Comparative Examples 7-13, which do not meet the necessary conditions of the present invention, failed to achieve good results in both copper adhesion and copper migration performance (b-HAST test results). On the other hand, Examples 15-51 showed excellent performance in both adhesion and copper migration performance. From the comparison of Comparative Examples 7-11 and Comparative Examples 13 with Example 16, and Comparative Examples 12 with Example 47, it can be seen that copper adhesion and copper migration performance can be improved by using the (B) tetrazolium compound of the present invention. Comparative Examples 7-10 contain tetrazolium compounds, but do not have the structure of general formula (1) or (2), and their pKa and tPSA do not meet the preferred scope of the present invention, so sufficient effects cannot be obtained. Comparative Examples 11-13 contain heterocyclic compounds whose pKa and / or tPSA meet the preferred scope of the present invention, but these heterocyclic compounds are not tetrazolium compounds, so sufficient effects cannot be obtained.

[0204] Further observation of the examples revealed that Examples 16-20 consisted of compositions with varying amounts of (B) tetrazolium compounds, and Examples 16, 18, and 19, with contents ranging from 0.01 to 10 parts by mass, exhibited superior copper adhesion and copper migration properties. Furthermore, comparing Examples 16 with Examples 23, or Examples 18 with Examples 24-28, it was found that increasing the curing temperature improved copper migration, but the optimal temperature for copper adhesion was below 230°C, and further below 200°C. Comparing Examples 31 with Examples 30, it was found that the presence of (E) free radical polymerizable compounds improved copper migration. Furthermore, comparing Examples 34 with Examples 33, it was found that the presence of (F) thermal crosslinking agents improved copper migration. Comparing Examples 38 with Examples 16, it was found that the presence of (G) adhesion promoters improved copper adhesion. Furthermore, comparing Example 33 with Example 32, it can be seen that Example 32, in which the content of (E) free radical polymerizable compound is in the range of 20 to 80 parts by mass, exhibits good copper migration. [Industrial Applicability]

[0205] By using the photosensitive resin composition of the present invention, a hardened embossed pattern with excellent copper adhesion and copper void suppression, and less copper migration in the b-HAST test, can be obtained. The photosensitive resin composition of the present invention is preferably used, for example, in the field of photosensitive materials useful in the manufacture of electrical and electronic materials such as semiconductor devices and multilayer wiring boards. More specifically, it can be used, for example, in the formation of embossed patterns in insulating materials for electronic components, and in passivation films, buffer coatings, and interlayer insulating films of semiconductor devices.

Claims

1. A photosensitive resin composition comprising: (A) a polyimide precursor and / or a polyimide resin, (B) a tetrazolium compound, (C) a photopolymerization initiator, and (D) a solvent, wherein the pKa of the tetrazolium compound is 1.3 to 4.1, the polar surface area (tPSA) of the tetrazolium compound is 81 to 200, and the ratio of the component (B) to 100 parts by mass of the component (A) is 0.001 parts by mass or more and 20 parts by mass or less.

2. A photosensitive resin composition comprising: (A) a polyimide precursor and / or a polyimide resin, (B) a tetrazolium compound, (C) a photopolymerization initiator, and (D) a solvent, wherein the (B) tetrazolium compound comprises the following general formula (1): [Chemical 1] {In formula (1), R1 is a hydrogen atom, or a monovalent organic group selected from the group consisting of alkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 10 carbon atoms; the hydrogen atoms of the alkyl group and the aryl group may be independently substituted by at least one substituent selected from the group consisting of halogen atoms, hydroxyl groups, alkoxysilyl groups, and amino groups, or may not be substituted} or the following general formula (2): [Chemical 2] {In formula (2), R2 is a hydrogen atom or a monovalent organic group selected from the group consisting of alkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 10 carbon atoms; R3 is an alkyl group having 1 to 10 carbon atoms; the hydrogen atoms of the above alkyl, aryl and alkyl groups may be independently substituted by at least one substituent selected from the group consisting of halogen atoms, hydroxyl groups, alkoxysilyl groups and amino groups, or may not be substituted} the compound represented by the above (B) component, and the ratio of the above component (A) component to 100 parts by mass is more than 0.001 parts by mass and less than 20 parts by mass.

3. The photosensitive resin composition of claim 1, wherein the (B) tetrazolium compound comprises a carboxylic acid or an ester.

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

5. The photosensitive resin composition of claim 1 or 2, wherein the above (B) tetrazolium compound contains a compound represented by the following general formula (3); [Chemical 3] {In formula (3), R4 is a hydrogen atom or a monovalent organic group selected from the group consisting of alkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 10 carbon atoms; the hydrogen atoms of the alkyl group and the aryl group may be independently substituted by at least one substituent selected from the group consisting of halogen atoms, hydroxyl groups, alkoxysilyl groups and amino groups, or may not be substituted}.

6. The photosensitive resin composition of claim 1 or 2, wherein the above-mentioned (B) tetrazolium compound contains a compound represented by the following formula; [Chemical 4].

7. The photosensitive resin composition of claim 1 or 2, further comprising (E) free radical polymerizable compound.

8. The photosensitive resin composition of claim 7, wherein the content of component (E) is 20 to 80 parts by mass relative to 100 parts by mass of component (A).

9. The photosensitive resin composition of claim 1 or 2, wherein the photosensitive resin composition contains the polyimide precursor, the polyimide precursor being represented by the following general formula (4): [Chemical 5] {In formula (4), X1 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer from 2 to 150, and R11 and R12 are each independently a hydrogen atom or a monovalent organic group} and / or the photosensitive resin composition contains the polyimide resin, the polyimide resin having a structural unit represented by the following general formula (4'): [Chemical 6] {In formula (4'), X1 is a tetravalent organic group, Y1 is a divalent organic group, n is an integer from 1 to 150}.

10. The photosensitive resin composition of claim 9, wherein in the above general formula (4), at least one of R11 and R12 has a structural unit represented by the following general formula (5): [Chemical 7] {In formula (5), L1, L2 and L3 are each independently a hydrogen atom or an organic group with a carbon number of 1 to 3, and m1 is an integer from 2 to 10}.

11. The photosensitive resin composition of claim 9, wherein X1 of the above general formula (4') is selected from at least one structure represented by general formulas (6) to (14) below, or Y1 of the above general formula (4') is selected from at least one structure represented by general formulas (15) to (23) below; [Chemical 8] [Chemical 9] [Chemical 10] [Chemical 11] [Chemical 12] [Chemical 13] [Chemical 14] [Chemical 15] [Chemical 16] [Chemical 17] [Chemical 18] [Chemical 19] [Chemical 20] [Chemical 21] [Chemical 22] [Chemical 23] [Chemical 24] [Chemical 25].

12. The photosensitive resin composition of claim 1 or 2 further contains (F) a thermal crosslinking agent.

13. The photosensitive resin composition of claim 1 or 2 further contains (K) adhesive additive.

14. The photosensitive resin composition of claim 1 or 2, wherein the photosensitive resin composition is a photosensitive resin composition used to form a surface protective film, an interlayer insulating film, a rewiring insulating film, a protective film for flip-chip devices, or a protective film for a semiconductor device having a bump structure.

15. A method for manufacturing a hardened embossed pattern, comprising the following steps: (1) A step of coating a photosensitive resin composition as claimed in 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 exposed photosensitive resin layer to form an embossed pattern; and (4) A step of heat-treating the embossed pattern to form a hardened embossed pattern.

16. The method for manufacturing a hardened embossed pattern as claimed in claim 15, wherein the heat treatment in step (4) above is a heat treatment at 350°C or below.

17. A hardened film comprising a hardened form of a photosensitive resin composition as claimed in claim 1 or 2.

18. A method for manufacturing a polyimide film, comprising curing a photosensitive resin composition as claimed in claim 1 or 2.