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

Abstract

The purpose of this invention is to provide a photosensitive resin composition that exhibits high copper adhesion during high-temperature curing, minimal copper migration in the b-HAST test (i.e., no short circuit after prolonged use), and high resolution; as well as a method for forming a hardened embossed pattern using this photosensitive resin composition, and a method for manufacturing a hardened film and a polyimide film. This invention provides a photosensitive resin composition containing a polyimide precursor and / or polyimide resin, a compound having a specific heterocyclic structure, and a photopolymerization initiator; and a method for forming a hardened embossed pattern using this photosensitive resin composition, and a method for manufacturing a hardened film and a polyimide film.

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 hardened film and a polyimide film. [Previous 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 by coating, exposing, developing, and performing thermoimidization treatment using the composition for curing. Such photosensitive resin compositions have 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 (packaging structure) for mounting semiconductor devices onto printed wiring substrates is also changing. The previous mounting method using metal leads and lead-tin eutectic bonding has been replaced by a structure using polyimide coatings and solder bumps in direct contact, such as BGA (Ball Grid Array) and CSP (Chip Scale Package), which allow for higher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, where the surface of the semiconductor chip has multiple rewiring layers 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. For example, Patent Document 2 describes the use of purine derivatives to suppress copper discoloration and improve adhesion. [Prior Art Documents] [Patent Documents]

[0005] [Patent Document 1] US Patent No. 10658199 Specification [Patent Document 2] Japanese Patent Application Publication No. 2012-194520 [Summary of the Invention]

[0006] [Problem to be Solved by the Invention] In recent years, due to the increasing performance, multifunctionality, low power consumption, and low cost of semiconductor devices, there is a demand for miniaturization of the wiring width of semiconductor components or circuits. With the progress of miniaturization, higher resolution is also emphasized for interlayer insulating films. Furthermore, because the wiring width becomes smaller due to miniaturization, copper sometimes migrates to the resin layer (interlayer insulating film) (hereinafter also referred to as "copper migration" in this invention), causing short circuits between wirings.

[0007] Furthermore, semiconductor devices are emerging in automotive or mobile phone applications. These semiconductor devices require high reliability and undergo reliability testing under high temperature and humidity conditions.

[0008] In previous reliability tests of interlayer insulating films under high temperature and humidity (b-HAST: Biased Highly Accelerated Stress Test), copper migration sometimes occurred as described above. If copper migration occurs, it can cause short circuits between wirings, especially in micro-wired semiconductor devices, thus preventing the film from fully performing its insulating properties. If copper migration progresses, voids (hereinafter also referred to as "copper voids" in this invention) may form at the interface between the copper wiring and the resin layer. If copper voids form at the interface between the copper wiring and the resin layer, the adhesion between the two decreases, and sometimes the resin peels off from the copper, resulting in impaired insulation. On the other hand, to improve copper migration suppression capabilities or film properties, the resin is sometimes cured at high temperatures; however, if the previous interlayer insulating film is cured at high temperatures, the copper adhesion may decrease.

[0009] In view of the above-mentioned problems, one object of the present invention is to provide a photosensitive resin composition that achieves high copper adhesion even during high-temperature curing, exhibits less copper migration in the b-HAST test (i.e., does not short-circuit after a long period of time), and has high resolution. Another object is to provide a method for forming a hardened embossed pattern using the photosensitive resin composition of the present invention, and a method for manufacturing a hardened film and a polyimide film. [Technical Means for Solving the Problems]

[0010] The inventors have discovered that the above-mentioned problems can be solved by adding specific heterocyclic compounds to the photosensitive resin composition. Examples of embodiments of the present invention are listed in items <1> to <14> below. <1> A photosensitive resin composition comprising the following components: (A) a polyimide precursor and / or a polyimide resin, (B) a heterocyclic compound, and (C) a photopolymerization initiator, wherein the heterocyclic compound (B) is a compound represented by the following general formula (1): [Chemical 1] {wherein, X1 is a nitrogen atom or a carbon atom substituted by R4, and R1, R2, R3 and R4 are each independently selected from hydrogen atoms or from the group consisting of hydroxyl, amino, amide, nitro, halogen and organic groups}, and a compound represented by the following general formula (2): [Chemical 2] {wherein, R5, R6 and R7 are each independently hydrogen atoms or from the group consisting of hydroxyl, amino, amide, nitro, halogen and organic groups}, and a compound represented by the following general formula (3): [Chemical 3] {wherein R8 and R9 are each independently hydrogen atoms or groups selected from the group consisting of hydroxyl, amino, amide, nitro, halogen and organic groups}, or compounds represented by the following general formula (4): [Chemical 4] {wherein X3 is a nitrogen atom or a carbon atom substituted by R11, and R10, R11 and R12 are each independently hydrogen atoms or groups selected from the group consisting of hydroxyl, amino, amide, nitro, halogen and organic groups}, or compounds represented by the following general formula (5): [Chemical 5] {wherein X4 is a nitrogen atom or a carbon atom substituted by R13, and R13 and R14 are each independently hydrogen atoms or groups selected from the group consisting of hydroxyl, amino, amide, nitro, halogen and organic groups}.<2> The photosensitive resin composition of Project 1, wherein the heterocyclic compound (B) is a compound represented by the following general formula (6): [Chemical 6] {wherein, X5 is a nitrogen atom or a carbon atom substituted by R18, and R15, R16, R17 and R18 are each independently hydrogen atoms or groups selected from hydroxyl, amino, amide, and organic groups having at least one of hydroxyl, amino, amide, carbonyl and carboxyl groups, having 1 to 10 carbon atoms}, and a compound represented by the following general formula (7): [Chemical 7] {wherein, R19, R20 and R21 are each independently hydrogen atoms or groups selected from hydroxyl, amino, amide, and organic groups having at least one of hydroxyl, amino, amide, carbonyl and carboxyl groups, having 1 to 10 carbon atoms}, and a compound represented by the following general formula (8): [Chemical 8] {wherein R22 and R23 are each independently a hydrogen atom or a group consisting of an organic group having 1 to 10 carbon atoms selected from hydroxyl, amino, amide, carbonyl, and carboxyl groups}, or a compound represented by the following general formula (9): [Chemical 9] {wherein X7 is a nitrogen atom or a carbon atom substituted by R25, and R24, R25, and R26 are each independently a hydrogen atom or a group consisting of an organic group having 1 to 10 carbon atoms selected from hydroxyl, amino, amide, carbonyl, and carboxyl groups}, or a compound represented by the following general formula (10): [Chem. 10] {where X8 is a nitrogen atom or a carbon atom substituted by R27, and R27 and R28 are each independently a hydrogen atom or a group selected from hydroxyl, amino, amide, and organic groups having at least one of hydroxyl, amino, amide, carbonyl and carboxyl groups with 1 to 10 carbon atoms}. <3> The photosensitive resin composition of item 1 or 2, wherein the photosensitive resin composition contains the polyimide precursor, the polyimide precursor having a structural unit represented by the following general formula (11): [Chemical 11] {wherein, X9 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer from 2 to 150, and R29 and R30 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 (12): [Chemical 12] {wherein, X10 is a tetravalent organic group, Y2 is a divalent organic group, n2 is an integer from 2 to 150}. <4> The photosensitive resin composition of Project 3, wherein in the above general formula (11), at least one of R29 and R30 has the structural unit represented by the following general formula (13): [Formula 13] {wherein, L1, L2 and L3 are each independently hydrogen atoms or organic groups with a carbon number of 1 to 3, and m1 is an integer from 2 to 10}.<5> The photosensitive resin composition of any one of items 1 to 4, wherein the content of component (B) is 0.01 to 10 parts by weight relative to 100 parts by weight of component (A). <6> The photosensitive resin composition of any one of items 1 to 5 further contains (D) a solvent. <7> The photosensitive resin composition of any one of items 1 to 6 further contains (E) a photopolymerizable monomer. <8> The photosensitive resin composition of any one of items 1 to 7 further contains (F) a thermal crosslinking agent. <9> The photosensitive resin composition of any one of items 1 to 8 further contains (G) a silane coupling agent. <10> The photosensitive resin composition of any one of items 1 to 9 contains (H) an acid component. <11> A photosensitive resin composition as described in any one of items 1 to 10, 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. <12> A method for manufacturing a hardened embossed pattern, comprising the following steps: (1) coating a photosensitive resin composition as described in any one of items 1 to 11 onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer; (3) developing the exposed photosensitive resin layer to form an embossed pattern; and (4) heat-treating the embossed pattern to form a hardened embossed pattern. <13> The method for manufacturing a hardened embossed pattern as described in item 12, wherein the temperature of the heat treatment in step (4) is 170°C or higher and 350°C or lower. <14> A hardened film comprising a hardened form of a photosensitive resin composition as described in any one of items 1 to 11. <15> A method of manufacturing a polyimide film comprising curing a photosensitive resin composition as described in any one of items 1 to 11. [Effects of the Invention].

[0011] According to the present invention, a photosensitive resin composition that exhibits high copper adhesion under high-temperature curing, less copper migration in the b-HAST test, and high resolution can be provided. Furthermore, according to the present invention, a method for manufacturing a hardened embossed pattern using the photosensitive resin composition, a method for manufacturing a hardened film, and a polyimide film can be provided.

Implementation Method

[0012] Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the embodiments described below, and various changes can be made within its scope. Furthermore, throughout the present invention, when multiple structures represented by the same symbol in the general formula exist in the molecule, they may be the same or different from each other. 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 heterocyclic compound, and (C) a photopolymerization initiator.

[0014] (A) Polyimide Precursor (A) The polyimide precursor is a resin component contained in the photosensitive resin composition, which is converted into polyimide by a heat cyclization treatment. 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; it is preferably non-alkali-soluble. By making the polyimide precursor non-alkali-soluble, higher chemical resistance can be obtained. Furthermore, it is also preferable that the polyimide precursor does not contain fluorine atoms. This further inhibits copper migration of the polyimide.

[0015] The polyimide precursor is preferably a polyimide having the structure represented by the following general formula (11): [Chemical 14] {wherein, X9 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer from 2 to 150, and R29 and R30 are each independently a hydrogen atom or a monovalent organic group}. As a polyimide precursor, it is also preferable that Y1 does not have an acidic group such as a carboxylic acid group or a phenolic hydroxyl group.

[0016] In general formula (11), it is preferred that at least one of R29 and R30 has the structural unit represented by the following general formula (13): [Chemical 15] {wherein, L1, L2 and L3 are each independently hydrogen atoms or monovalent organic groups with carbon number 1 to 3, and m1 is an integer from 2 to 10}.

[0017] The ratio of hydrogen atoms R29 and R30 in general formula (11) is preferably 10% or less, more preferably 5% or less, and even more preferably 1% or less, based on the total mole number of R29 and R30. Furthermore, the ratio of monovalent organic groups R29 and R30 in general formula (11) to the total mole number of R29 and R30 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 (13) are within the above ranges, it is preferable from the viewpoint of photosensitivity and storage stability.

[0018] In general formula (11), n1 is not limited as long as it is 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 (11), the tetravalent organic group represented by X9 is preferably an organic group with 6 to 40 carbon atoms, from the viewpoint of balancing heat resistance and photosensitivity. More preferably, it is an aromatic group or an alicyclic aliphatic group in which the -COOR29 group and the -COOR30 group are adjacent to the -CONH- group. Specifically, the tetravalent organic group represented by X9 can be exemplified as an organic group with 6 to 40 carbon atoms containing an aromatic ring, such as a group having the structure represented by the following general formula (14): [Chemical 16] {wherein, R31 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 them. Furthermore, the structure of X9 can be one or a combination of two or more. From the viewpoint of balancing heat resistance and photosensitivity, X9 with the structure represented by the above formula (14) is particularly good.

[0020] As the X9 base, the structure represented by the above formula (14) is particularly the tetravalent organic group represented by the following general formula (15): [Chemical 17] {wherein, R31 is selected from at least one of the group consisting of fluorine atoms, a hydrocarbon group with one valence of carbon number 1 to 10, and a fluorinated hydrocarbon group with one valence of carbon number 1 to 10, and m is an integer selected from 0 to 3} It is better from the viewpoints of aceimidization rate, degassing, copper adhesion, chemical resistance, etc. when heated at low temperature.

[0021] In the above general formula (11), the divalent organic group represented by Y1 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 (16) can be cited as an example: [Chemical 18] {wherein, R32 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 l, m and n are each independently selected from integers of 0 to 4}, but is not limited to them. Furthermore, the structure of Y1 can be one or a combination of two or more. The Y1 group having the structure represented by the above formula (16) is particularly preferred from the viewpoint of balancing heat resistance and photosensitivity.

[0022] As Y1 base, the structure represented by the above formula (16) is particularly the divalent base represented by the following general formula (17): [Chemical 19] {wherein, R32 is selected from at least one of the group consisting of fluorine atoms, a hydrocarbon group with one valence of carbon number 1 to 10, and a fluorinated hydrocarbon group with one valence of carbon number 1 to 10, and l and m are each independently selected from integers from 0 to 4} It is better from the viewpoints of aceimidization rate, degassing, copper adhesion, chemical resistance, etc. when heated at low temperature.

[0023] The organic groups with one to three carbon atoms in L1, L2 and L3 of the above general formula (13) are, for example, hydrocarbon groups with one to three carbon atoms, preferably alkyl groups. L1 is preferably a hydrogen atom or a methyl group, and L2 and L3 are preferably hydrogen atoms from the viewpoint of photosensitivity. Also, m1 is an integer of 2 to 10 from the viewpoint of photosensitivity, preferably an integer of 2 to 4.

[0024] In one embodiment, (A) the polyimide precursor is preferably a polyimide precursor having the structural unit represented by the following general formula (18):

[0020] {wherein, R33, R34 and n3 can be defined as R29, R30 and n1 in the above general formula (11)}.

[0025] In general formula (18), it is more preferable that at least one of R33 and R34 is a monovalent organic group represented by the above general formula (13). Furthermore, by making (A) a polyimide precursor preferably a polyimide precursor having a tetravalent structure represented by the following general formula (19): [Chemical 21], chemical resistance is particularly improved.

[0026] In one embodiment, it is preferable from the viewpoint of thermophysical properties that (A) the polyimide precursor is a polyimide precursor having the structural unit represented by the following general formula (20):

[22] {wherein, R35, R36 and n4 can be defined as R29, R30 and n1 in the above general formula (11) respectively}.

[0027] In general formula (20), it is more preferable that at least one of R35 and R36 is a monovalent organic group represented by the above general formula (13).

[0028] (A) Polyimide precursors tend to have particularly high resolution by containing both structural units represented by general formula (18) and structural units represented by general formula (20). For example, (A) polyimide precursors may contain copolymers of structural units represented by general formula (18) and structural units represented by general formula (20), or mixtures of polyimide precursors represented by general formula (18) and polyimide precursors represented by general formula (20).

[0029] (A) The polyimide precursor is preferably a polyimide precursor having the structural unit represented by the following general formula (21): [Chemical 23] {wherein, R37, R38 and n5 can be defined as R29, R30 and n1 in the above general formula (11)}.

[0030] (A) The polyimide precursor is preferably a polyimide precursor having the structural unit represented by the following general formula (22): [Chemical 24]{wherein, R39, R40 and n6 can be defined as R29, R30 and n1 in the above general formula (11), respectively}. (A) The polyimide precursor containing the polyimide precursor represented by general formula (22) has particularly high chemical resistance.

[0031] (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.

[0032] (A) Method for preparing polyimide precursor (A) The polyimide precursor is prepared by first reacting a tetracarboxylic acid dianhydride containing the above-mentioned tetravalent organic group X9 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 acid / ester body). Subsequently, it is obtained by amide polycondensation of the partially esterified tetracarboxylic acid with a diamine containing the above-mentioned divalent organic group Y1.

[0033] (Preparation of acid / ester body) As a preferred tetracarboxylic dianhydride containing a tetravalent organic group X9 for preparing (A) polyimide precursor, the tetracarboxylic dianhydride represented by the above general formula (14) is preferred. Examples include: 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.

[0034] Alcohols having photopolymerizable unsaturated double bonds, preferably used for preparing (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-tri-butoxypropyl acrylate, acrylic acid 2-Hydroxy-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-tributoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, etc.

[0035] Alternatively, a portion of alcohols without unsaturated double bonds, such as methanol, ethanol, 1-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., may be mixed into the above-mentioned alcohols with photopolymerizable unsaturated double bonds.

[0036] Furthermore, as a polyimide precursor, a non-photosensitive polyimide precursor prepared solely from the aforementioned alcohols without unsaturated double bonds can be mixed with a photosensitive polyimide precursor for use. From the viewpoint of resolution, 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 stirred, dissolved, and mixed in a solvent as described below in the presence of an alkaline catalyst such as pyridine, at a temperature of 20–50°C for 4–24 hours, thereby carrying out an esterification reaction of the anhydride to obtain the desired acid / ester body.

[0037] (Preparation of polyimide precursor) In the above-mentioned acid / ester body (typically a solution in the solvent 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 form a polyanhydride. Then, a diamine containing a divalent organic group Y1 is added dropwise to the acid / ester body to undergo amide polycondensation, thereby obtaining the target polyimide precursor. Alternatively, the acid / ester body can be partially chlorinated with thionyl chloride, and then reacted with a diamine compound in the presence of a base such as pyridine to obtain the target polyimide precursor.

[0038] As diamines containing a divalent organic group Y1, diamines having the structure represented by the following general formula (23) are preferred: [Chemical 25], 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'-diaminodiphenyl biphenyl, 3,4'-diaminodiphenyl biphenyl, 3,3'-diaminodiphenyl biphenyl, 4,4'-diaminodibenzophenone, 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] benzoyl, bis[4-(3-aminophenoxy)phenyl] benzoyl, 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-toluidine sulfonate, 9 9-Bis(4-aminophenyl)benzene (BAFL) and others, wherein a portion of the hydrogen atom on the benzene ring is replaced by methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen, etc., for example, 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.

[0039] 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. The polymer is then vacuum dried 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.

[0040] When determining the molecular weight of the polyimide precursor (A) by converting it to the weight-average molecular weight of polystyrene using gel permeation chromatography, it 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 150,000 or lower, 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.

[0041] (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.

[0042] (A) Polyimide resin does 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.

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

[0044] The amide ratio of the polyimide resin can be determined by known methods, but in this invention it is calculated by the following method. First, the infrared absorption spectrum of the polyimide resin is measured to confirm the presence of absorption peaks of the amide structure (around 1780 cm⁻¹ and around 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 ratio of the polyimide resin.

[0045] (A) From the viewpoint of solvent solubility and coating flatness, the polyimide resin preferably contains the structure represented by the following general formula (12). Furthermore, it is a structure suitable for solvent-developable photosensitive resin compositions. The polyimide resin (A) is preferably non-alkali-soluble, and it is also preferable that X10 and / or Y2 in general formula (12) do not have acidic groups such as carboxylic acids or phenolic hydroxyl groups. Furthermore, it is also preferable that the polyimide resin (A) does not have fluorine atoms. This further suppresses copper migration in the polyimide. [Chemical 26] {wherein, X10 is a tetravalent organic group, Y2 is a divalent organic group, and n2 is an integer from 2 to 150}

[0046] X10 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 superior copper adhesion of the hardened film, suppression of copper voids after high-temperature storage test, suppression of copper migration in b-HAST test, excellent elongation, excellent chemical resistance, and solvent solubility, it is preferable to have at least one structure represented by the following formulas (24) to (32). [Chemical 27][Chemical 28][Chemical 29][Chemical 30][Chemical 31][Chemical 32][Chemical 33][Chemical 34][Chemical 35]

[0047] Furthermore, from the viewpoint of the inhibition of copper voids, the inhibition of copper migration in the b-HAST test, the elongation, and the chemical resistance of the hardened film obtained from the photosensitive resin composition of the present invention, X10 in general formula (12) is preferably having at least one structure represented by formula (24) to (31). Furthermore, from the viewpoint of the heat resistance of the hardened film obtained from the photosensitive resin composition of the present invention, X10 is even more preferably having at least one structure represented by formula (24) to (26) and (28) to (31). In addition, from the viewpoint of the coating uniformity and the elongation of the hardened film of the photosensitive resin composition of the present invention being particularly excellent, X10 is especially preferably having at least one structure represented by formula (24) and (29) to (31).

[0048] Y2 in general formula (12) is a divalent organic group. There are no particular limitations as long as it is derived from a known diamine structure. From the viewpoint of superior copper adhesion of the hardened film, excellent copper migration inhibition, elongation, and chemical resistance in the b-HAST test, and good solvent solubility, it is preferable to have at least one structure represented by the following formulas (33) to (41). [Chemical 36][Chemical 37][Chemical 38][Chemical 39][Chemical 40][Chemical 41][Chemical 42][Chemical 43][Chemical 44]

[0049] 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, Y2 preferably has at least one structure represented by formulas (33) to (39). Furthermore, from the viewpoint of the mechanical properties of the hardened film obtained from the photosensitive resin composition of the present invention, Y2 preferably has at least one structure represented by formulas (33) to (38). 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, Y2 particularly preferably has at least one structure represented by formulas (35) to (38). The reason why the structures represented by formulas (35) to (38) have excellent solvent solubility is that these structures have side-chain phenyl structures.

[0050] In formula (12), n2 is an integer from 2 to 150, preferably from 3 to 100, and even more preferably from 5 to 70. n2 is preferably an integer that satisfies the following (A) of the weight average molecular weight of the polyimide resin.

[0051] From the viewpoint of solubility in 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 (42) to (44). [Chem. 45] {In the formula, R41 and R42 are independently selected from hydrogen atoms and monovalent organic groups with 1 to 3 carbon atoms, respectively; R43 is a divalent organic group with 1 to 20 carbon atoms that may contain heteroatoms; k is an integer from 1 to 2; R44 is a hydrogen atom and an organic group with 1 to 4 carbon atoms; * indicates the bonding site with the end of (A) polyimide resin} [Chem. 46] {In the formula, R45 and R46 are independently selected from hydrogen atoms and monovalent organic groups with 1 to 3 carbon atoms, respectively; and * indicates the bonding site with the end of (A) polyimide resin} [Chem. 47] {In the formula, R47, R48, and R49 are independently selected from hydrogen atoms or monovalent organic groups with 1 to 3 carbon atoms, respectively; j is an integer from 2 to 10; and * indicates the bonding site with the end of (A) polyimide resin}

[0052] 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 (42), the structures represented by the following formulas (45) to (48) can be cited. [Chemical 48][Chemical 49][Chemical 50][Chemical 51] {where * indicates the bonding site with the end of (A) polyimide resin}

[0053] As a more detailed specific example of the structure represented by general formula (43), the structures represented by the following formulas (49) and (50) can be cited. [Chemical 52][Chemical 53] {where * indicates the bonding site at the end of (A) polyimide resin}

[0054] As a more detailed specific example of the structure represented by general formula (44), the following structures represented by formulas (51) to (54) can be cited. [Chemical 54][Chemical 55][Chemical 56][Chemical 57] {where * indicates the bonding site at the end of (A) polyimide resin}

[0055] From the viewpoints of the higher 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 X10 of general formula (12) is any structure represented by general formula (24) to (32), and Y2 is any structure represented by general formula (33) to (41).

[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 solubility in the solvent. 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 or more and 100,000 or less. 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 solvent, preferably containing 10% to 70% by mass, more preferably containing 20% ​​to 65% by mass.

[0059] (A) Method for preparing polyimide resin (A) Polyimide resin is obtained by amide-imidizing polyamide obtained by reacting tetracarboxylic dianhydride with diamine.

[0060] There is no limitation on the method of dehydrating and closing the ring of polyacrylic acid. For example, the heating acetylation method can be used to dehydrate and close the ring of polyacrylic acid by heating it at high temperature, or the chemical acetylation method can be used to dehydrate and close the ring by adding acetic anhydride as a dehydrating reducing agent and a tertiary amine.

[0061] There is no particular limitation on the temperature in the heating amide process. From the viewpoint of promoting the ring-closing reaction, the lower limit is preferably 150°C or higher, and more preferably 160°C or higher. On the other hand, from the viewpoint of suppressing side reactions, the upper limit is preferably 200°C or lower, and more preferably 180°C.

[0062] There is no particular limitation on the tetracarboxylic acid 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), 9,9-bis(3, Examples of tetracarboxyphenyl dianhydrides include 4-dicarboxyphenyl 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). 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) are preferred as tetracarboxylic dianhydrides.

[0063] As a diamine, there is no particular limitation. 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 Examples of diamines include '-diphenyl-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). Among these, 6-(4-aminophenoxy)biphenyl-3-amine (PDPE) and 9,9'-bis(4-aminophenyl)benzoyl (BAFL) are preferred as diamines.

[0064] When the terminal of (A) polyimide resin is an anhydride group, a carboxyl group, and an amine group, (A) polyimide resin is obtained by amide imidization of polyamide obtained by reacting tetracarboxylic dianhydride with diamine. The anhydride group, carboxyl group, and amine group at the terminal of (A) polyimide resin can be reacted with a specified compound to make the terminal structure represented by the above general formulas (42) to (44).

[0065] The polyimide resin (A) with the structure represented by general formula (42) at the end is obtained, for example, by reacting the amino group at the end of the polyimide with an isocyanate compound. 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 the isocyanate compound is not particularly limited, and the reaction with the amino group of the dehydrated ring-closed polyimide can be achieved by adding the isocyanate compound to a solution of dehydrated ring-closed polyimide and stirring at room temperature.

[0066] The (A) polyimide resin with the structure represented by general formula (43) at the end is obtained, for example, by reacting the amino group at the end of the polyimide with a chloride-based compound. Examples of chloride-based compounds include acrylonitrile chloride and methacrylonitrile chloride. There is no particular limitation 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 group of the dehydrated ring-closed polyimide.

[0067] The polyimide resin (A) with the structure represented by general formula (44) at the end is 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. A condensing agent such as N,N'-dicyclohexylcarbodiimide (DCC) or an esterification catalyst 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 manner. 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-dimethylmethoxyamine, 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) The polyimide resin can be purified by the 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) Heterocyclic compounds (B) Heterocyclic compounds are represented by the following general formulas (1), (2), (3), (4) or (5). [Chem. 58] {In the formula, X1 is a nitrogen atom or a carbon atom substituted by R4, and R1, R2, R3, and R4 are each independently a hydrogen atom or a group selected from the group consisting of hydroxyl, amino, amide, nitro, halogen, and organic groups.} [Chem. 59] {In the formula, R5, R6, and R7 are each independently a hydrogen atom or a group selected from the group consisting of hydroxyl, amino, amide, nitro, halogen, and organic groups.} [Chem. 60] {In the formula, R8 and R9 are each independently a hydrogen atom or a group selected from the group consisting of hydroxyl, amino, amide, nitro, halogen, and organic groups.} [Chem. 61] {In the formula, X3 is a nitrogen atom or a carbon atom substituted by R11, and R10, R11, and R12 are each independently a hydrogen atom or a group selected from the group consisting of hydroxyl, amino, amide, nitro, halogen, and organic groups.} [Chem. 62] {In the formula, X4 is a nitrogen atom or a carbon atom substituted by R13, and R13 and R14 are each independently a hydrogen atom or a group selected from the group consisting of hydroxyl, amino, amide, nitro, halogen, and organic groups}

[0072] R1 to R14 in general formulas (1) to (5) are not particularly limited as long as they are hydrogen atoms, hydroxyl groups, amino groups, amide groups, nitro groups, halogen groups, or organic groups. As organic groups, they can be branched or straight-chain alkyl groups, aromatic groups, or carboxyl groups, and the alkyl or aromatic groups can have substituents. The number of carbon atoms in the alkyl group is not particularly limited, for example, it can be 1 to 10, or it can be 1 to 5.

[0073] By including the heterocyclic compound represented by formulas (1), (2), (3), (4), or (5) above in (B), excellent copper adhesion can be obtained not only under low-temperature curing but also under high-temperature curing. Furthermore, high-temperature curing goes without saying, but even low-temperature curing can achieve copper migration inhibition and copper void inhibition effects. The reasons are uncertain and not limited to theory, but the following considerations are made: the unshared electron pairs attached to the nitrogen atoms in the heterocyclic skeleton act on copper and are segregated at the copper interface. Furthermore, the secondary amine formed by the presence of ketones in the skeleton forms hydrogen bonds with the polyimide precursor or polyimide, thereby the resin interacts with copper, which can improve the copper adhesion. In addition, it is believed that by making the heterocyclic compound segregated at the copper interface, the oxidation reaction of the copper interface can be strongly inhibited, thereby inhibiting copper migration and copper voids.

[0074] Specifically, examples of (B) heterocyclic compounds represented by general formula (1) include, for example, pyrido[2,3-d]pyrimidin-4-ol, pteridine-4-ol, 7-phenyl-pteridine-4-ol, purine-6-carboxylic acid, and 6-nitro-3H-pyrido[2,3-d]pyrimidin-4-one, but are not limited thereto. Among these, purine-6-carboxylic acid is preferred from the viewpoint of copper adhesion and copper migration inhibition.

[0075] Furthermore, from the point of view of solubility, X1 in formula (1) is preferably a carbon atom substituted with R4.

[0076] Specifically, examples of heterocyclic compounds represented by formula (2) (B) include, for example: 7-methyl-2,4-dioxy-1,2,3,4-tetrahydropyrido[2,3-d]pyrimidine-5-carboxylic acid, 1H,2H,3H,4H-pyrido[2,3-d]pyrimidine-2,4-dione, 7-chloropyrido[2,3-d]pyrimidine-2,4(1H,3H)-dione, but are not limited to them.

[0077] Specifically, examples of heterocyclic compounds represented by formula (3) (B) include, for example, xanthophenine and 2-amino-3,4a,5,8a-tetrahydropteridine-4,6-dione, but are not limited to them. Among them, xanthophenine is preferred from the viewpoint of copper adhesion and copper migration inhibition.

[0078] Specifically, examples of heterocyclic compounds represented by formula (4) (B) include, for example: allopurinol, 4-[2-(2-amino-4,7-dihydro-4-sideoxy-3H-pyrrolo[2,3-d]pyrimidin-5-yl)ethyl]benzoic acid, 6-amino-1H-pyrazolo[3,4-d]pyrimidin-4(7H)-one, 7-deazoxinine, 2-amino-4-sideoxy-4,7-dihydro-1H-pyrrolo[2,3-d]pyrimidin-5-carboxylic acid, 6-(trifluoromethyl)-1H-pyrazolo[3,4-d]pyrimidin-4-ol, but are not limited to them. Among these, from the viewpoint of copper adhesion and copper migration inhibition, 4-[2-(2-amino-4,7-dihydro-4-sideoxy-3H-pyrrolo[2,3-d]pyrimidin-5-yl)ethyl]benzoic acid, 6-amino-1H-pyrazolo[3,4-d]pyrimidin-4(7H)-one, and 2-amino-4-sideoxy-4,7-dihydro-1H-pyrrolo[2,3-d]pyrimidin-5-carboxylic acid are preferred.

[0079] Furthermore, from the point of view of solubility, when X3 in formula (4) is C-R11, it is preferable that at least one of R10, R11 or R12 is a hydroxyl group, an amino group, a amide group, a nitro group, a halogen group or an organic group.

[0080] Specifically, examples of heterocyclic compounds represented by formula (5) (B) include, for example, 1H-pyrazolo[3,4-d]pyrimidine-4,6(2H,5H)-dione, 7-denitroxanthine, and 5-(4-iodophenyl)-1H-pyrrolo[2,3-d]pyrimidine-2,4(3H,7H)-dione, but are not limited to these. Furthermore, when these compounds are added to a resin composition, they may be in the form of hydrates.

[0081] Especially from the viewpoint of copper closeness, (B) heterocyclic compounds are preferably compounds represented by formulas (6), (7), (8), (9) or (10) below. [Chemical 63] {wherein, X5 is a nitrogen atom or a carbon atom substituted by R18, and R15, R16, R17 and R18 are each independently a hydrogen atom or a group consisting of organic groups having 1 to 10 carbon atoms selected from hydroxyl, amino, amide, and at least one of hydroxyl, amino, amide, carbonyl and carboxyl groups} [Chemical 64] {wherein, R19, R20 and R21 are each independently a hydrogen atom or a group consisting of organic groups having 1 to 10 carbon atoms selected from hydroxyl, amino, amide, and at least one of hydroxyl, amino, amide, carbonyl and carboxyl groups} [Chem. 65] {In the formula, R22 and R23 are each independently a hydrogen atom or a group consisting of an organic group having 1 to 10 carbon atoms selected from hydroxyl, amino, amide, and carbonyl or carboxyl groups.} [Chem. 66] {In the formula, X7 is a nitrogen atom or a carbon atom substituted by R25, and R24, R25 and R26 are each independently a hydrogen atom or a group consisting of an organic group having 1 to 10 carbon atoms selected from hydroxyl, amino, amide, and carbonyl or carboxyl groups.} [Chem. 67] {In the formula, X8 is a nitrogen atom or a carbon atom substituted by R27, and R27 and R28 are each independently a hydrogen atom or a group selected from hydroxyl, amino, amide, and organic groups having at least one of hydroxyl, amino, amide, carbonyl, and carboxyl groups with 1 to 10 carbon atoms.}

[0082] R15 to R28 in general formulas (6) to (10) are not particularly limited as long as they are hydrogen atoms, hydroxyl groups, amino groups, acetamino groups, or organic groups with 1 to 10 carbon atoms. They can be carboxyl groups, branched or linear alkyl groups or aromatic groups with the above-mentioned functional groups. Examples include: hydroxymethyl, hydroxyethyl, acetyl, acetoxy, and p-carboxyphenyl.

[0083] Specifically, examples of (B) heterocyclic compounds represented by general formula (6) include, for example, pyrido[2,3-d]pyrimidin-4-ol, pteridine-4-ol, 7-phenyl-pteridine-4-ol, and purine-6-carboxylic acid, but are not limited to these. Among these, purine-6-carboxylic acid is preferred from the viewpoint of copper adhesion and copper migration inhibition.

[0084] Furthermore, from the point of view of solubility, X5 in formula (6) is preferably a carbon atom that has been substituted by R18.

[0085] As a heterocyclic compound represented by general formula (7), examples include, for example, 7-methyl-2,4-dioxy-1,2,3,4-tetrahydropyrido[2,3-d]pyrimidine-5-carboxylic acid, 1H,2H,3H,4H-pyrido[2,3-d]pyrimidine-2,4-dione, but are not limited to them.

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

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

[0088] Furthermore, from the point of view of solubility, when X7 in formula (9) is C-R25, it is preferable that at least one of R24, R25 or R26 is a hydroxyl group, an amino group, a amide group, or an organic group with 1 to 10 carbon atoms.

[0089] Specifically, examples of heterocyclic compounds represented by general formula (10) include, for example, 1H-pyrazolo[3,4-d]pyrimidine-4,6(2H,5H)-dione and 7-denitroxanthine, but are not limited to them. Furthermore, when these compounds are added to a resin composition, they may be in the form of hydrates.

[0090] (B) The content of the heterocyclic compound relative to 100 parts by weight of (A) polyimide precursor or polyimide resin is preferably 0.001 parts by weight or more and 20 parts by weight, more preferably 0.005 parts by weight or more and 15 parts by weight, and even more preferably 0.01 parts by weight or more and 10 parts by weight. As for the above content, considering the need to achieve sufficient effect from the viewpoint 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 it is less likely to form a weak layer between the copper layer and the resin layer, thus improving copper adhesion, and preventing the ionic content in the resin layer from increasing to the required level, while also improving copper migration.

[0091] (C) Photopolymerization Initiator The photopolymerization initiator (C) is described below. As a photopolymerization initiator, preferably a photoradical polymerization initiator, preferred examples include: benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fentanyl ketone and other benzophenone derivatives; 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylphenylacetone, 1-hydroxycyclohexylphenyl ketone and other acetophenone derivatives; 9-oxosulfuron-methyl, 2-methyl-9-oxosulfuron-methyl, 2-isopropyl-9-oxosulfuron-methyl, diethyl-9-oxosulfuron-methyl and other 9-oxosulfuron-methyl derivatives; benzoin, benzoin dimethyl ketal, benzoin-β-methoxyethyl acetal and other benzoin derivatives; benzoin, benzoin methyl ether and other benzoin derivatives. Oximes such as 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, 1,3-diphenyltrione-2-(O-ethoxycarbonyl)oxime, and 1-phenyl-3-ethoxytrione-2-(O-benzoyl)oxime; N-aryl glycine acids such as N-phenylglycine; aromatic biimidazoles; titanium dioxide; and photoacid generating agents such as α-(n-octylsulfoxyimino)-4-methoxyphenylacetonitrile, but not limited to these. Of the aforementioned photopolymerization initiators, oximes are preferred, especially in terms of photosensitivity.

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

[0093] (D) The photosensitive resin composition may further contain solvent (D). Solvent (D) will be described. Examples of solvents include: amines, sulfides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, alcohols, etc. 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, diethyl oxalate, etc. 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.

[0094] 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, 3-butoxy-N,N-dimethylpropionic acid, etc. In particular, from the viewpoint of in-plane uniformity when the photosensitive resin composition is coated on the substrate, γ-butyrolactone and 3-methoxy-N,N-dimethylpropionic acid are preferred.

[0095] The solvent may be one type 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. In the case of containing two or more solvents, 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.

[0096] 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.

[0097] The (E) photopolymerizable monomer photosensitive resin composition may further contain the (E) photopolymerizable monomer. If the (E) photopolymerizable monomer is used, the photosensitive resin composition undergoes cross-linking, thereby improving resolution and reducing the moisture permeability of the hardened film, thus also achieving a copper migration inhibition effect. Preferably, the photosensitive resin composition contains 5 to 150 parts by mass of the photopolymerizable monomer relative to 100 parts by mass of the (A) polyimide precursor or polyimide resin. To obtain good resolution, the photosensitive resin composition preferably contains 5 or more parts by mass of the photopolymerizable monomer, more preferably 10 or more parts by mass, and even more preferably 20 or more parts by mass. On the other hand, if too much photopolymerizable monomer is contained, the copper adhesion may sometimes decrease. The reason is uncertain and not limited to theory, but it is speculated that due to a higher content of photopolymerizable monomer, a weak layer is formed between the copper layer and the resin layer, resulting in decreased copper adhesion. From the perspective of copper adhesion, the upper limit that can be combined with the above lower limit is preferably 150 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 50 parts by mass or less.

[0098] The term photopolymerizable monomer is not particularly limited as long as it is a compound that undergoes free radical polymerization reaction by means of photopolymerization initiator and thermal polymerization initiator. It is preferably a (meth)acrylic acid compound, for example represented by the following general formula (55): [Chemical 68] {In formula (55), X11 is an organic group, L4, L5 and L6 are each independently a hydrogen atom or an organic group with a carbon number of 1 to 3; n7 is an integer from 1 to 10}.

[0099] The photopolymerizable monomers 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 polyethylene glycol; mono-, di-, or triacrylates and methacrylates of glycerol; cyclohexane diacrylate and dimethacrylates; diacrylates and dimethacrylates of 1,4-butanediol; and diacrylates and dimethacrylates of 1,6-hexanediol. Compounds such as 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 neopentyl tertrol, and ethylene oxide or propylene oxide adducts of such compounds. More specifically, compounds represented by the following formulas (56) and (57) can be cited as examples: [Chem. 69][Chem. 70], but are not limited to the above.

[0100] In this invention, when the number of free radical polymerizable groups in a photopolymerizable monomer 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 are collectively referred to as multifunctional. The photopolymerizable monomer can be monofunctional or difunctional or above. From the viewpoint of inhibiting copper migration, the free radical polymerizable compound is preferably trifunctional or above, more preferably tetrafunctional or above, and even more preferably hexafunctional or above. On the other hand, from the viewpoint of copper adhesion, it is preferably decafunctional or below.

[0101] The molecular weight of the photopolymerizable monomer is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more. As an upper limit, it is preferably 1000 or less, and more preferably 800 or less. By setting the molecular weight of the photopolymerizable monomer within the above range, the resolution is improved.

[0102] Also, photopolymerizable monomers may contain hydroxyl or urea groups.

[0103] As a photopolymerizable monomer having hydroxyl groups in the molecule, an example can be given by the structure represented by the following general formula (58): [Chemical 71] {In formula (58), X12 is an organic group, L7, L8 and L9 are each independently a hydrogen atom or an organic group with one to three carbon atoms; n8 is an integer from 1 to 10, and n9 is an integer from 1 to 10}. In the above formula (58), it is better from the point of view of free radical reactivity when L7 is a hydrogen atom or a methyl group, and L8 and L9 are hydrogen atoms. More specifically, a compound represented by the following formula (59) can be given as an example: [Chemical 72], but is not limited to the above. Due to the presence of hydroxyl groups in the molecular structure, the copper adhesion becomes good. The number of hydroxyl groups in the molecular structure is preferably 1 or more, more preferably 2 or more. As an upper limit, it is preferably 10 or less, more preferably 6 or less, and even more preferably 3 or less. By setting the number of hydroxyl groups in the molecular structure to the above range, the copper adhesion to the substrate becomes good.

[0104] A photopolymerizable monomer having a urea group in its molecule can be represented by the following general formula (60): [Chemistry 73] {In formula (60), X13, X14, X15, and X16 are each independently hydrogen atoms, an organic group having a monovalent group represented by the following general formula (61), or an organic group having a monovalent group containing heteroatoms with 1 to 20 carbon atoms, and at least one of X13, X14, X15, and X16 is an organic group having a monovalent group represented by the following general formula (61)} [Chemistry 74] {In formula (61), L10, L11, and L12 are each independently hydrogen atoms or an organic group having a monovalent group with 1 to 3 carbon atoms}. In the above formula (61), it is better from the viewpoint of free radical reactivity when L10 is a hydrogen atom or a methyl group, and L11 and L12 are hydrogen atoms.

[0105] Examples of heteroatoms that are photopolymerizable monomers include: oxygen atoms, nitrogen atoms, phosphorus atoms, and sulfur atoms.

[0106] In formula (60), when X13, X14, X15, and X16 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. X13, X14, X15, and X16 in formula (60) 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 X13, X14, X15, and X16 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 X13, X14, X15, and X16 is a hydrogen atom. On the other hand, from the point of view of solubility, it is preferable that the number of hydrogen atoms in X13, X14, X15, and X16 is two or less. Specifically, the compound represented by the following formula (62) can be exemplified: [Chem. 75].

[0107] Furthermore, 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 (63): [Chemical 76] {In formula (63), X17, X18, X19, and X20 are each independently hydrogen atoms, an organic group having a monovalent group represented by the following general formula (64), and an organic group having a monovalent group containing heteroatoms with 1 to 20 carbon atoms, at least one of X17, X18, X19, and X20 is an organic group having a monovalent group represented by the following general formula (64), and at least one is a hydroxyl group} [Chemical 77] {In formula (64), L13, L14, and L15 are each independently hydrogen atoms or organic groups having a monovalent group with 1 to 3 carbon atoms}. In the above formula (64), it is preferable from the viewpoint of free radical reactivity when L13 is a hydrogen atom or a methyl group, and L14 and L15 are hydrogen atoms.

[0108] In formula (63), when X17, X18, X19, and X20 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. X17, X18, X19, and X20 in formula (63) 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 X17, X18, X19, and X20 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 X17, X18, X19, and X20 is a hydrogen atom. On the other hand, from the point of view of solubility, it is preferable that the number of hydrogen atoms in X17, X18, X19, and X20 is two or less. Specifically, the following compound represented by formula (65) can be cited as an example: [Chem. 78].

[0109] The method for manufacturing photopolymerizable monomers having urea groups is not particularly limited. For example, they can be obtained by reacting an isocyanate compound having a free radical polymerizable group 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.

[0110] A single photopolymerizable monomer may be used, but it is preferable to use a mixture of two or more. When using a mixture of two or more photopolymerizable monomers, from the viewpoint of controlling the crosslinking density, it is preferable to use six or fewer, and more preferably four or fewer.

[0111] When using a mixture of multiple photopolymerizable monomers, it is preferable that at least one of the photopolymerizable monomers has a different functional group. When using three or more photopolymerizable monomers, it is acceptable as long as at least one of them has a different functional group, but it is preferable that all photopolymerizable monomers have different functional groups. When using a mixture of multiple photopolymerizable monomers, from the viewpoint of elongation at break, it is preferable to include at least one monofunctional photopolymerizable monomer.

[0112] (F) The thermal crosslinking agent is used to inhibit copper migration in the hardened film. The photosensitive resin composition may contain (F) thermal crosslinking agent in any way.

[0113] The thermal crosslinking agent is not particularly limited as long as it is one that forms a crosslink when the embossed pattern formed using the photosensitive resin composition of the present invention is heated and hardened. (A) The polyimide precursor and / or polyimide resin can react with (F) the thermal crosslinking agent, (F) the thermal crosslinking agent with each other, and (F) the thermal crosslinking agent with other components to form a crosslinked body. The reaction temperature is preferably 150°C or higher.

[0114] Examples of thermal crosslinking agents include: alkoxymethyl compounds, epoxy compounds, oxetane compounds, bismaleimide compounds, allyl compounds, and capped isocyanate compounds. From the viewpoint of inhibiting hardening shrinkage, (F) thermal crosslinking agents are preferably those containing nitrogen atoms.

[0115] As examples of alkoxymethyl compounds, compounds of the following formula (66) can be cited, but are not limited to them. [Chemistry 79]

[0116] Also, examples of commercially available alkoxymethyl compounds include: alkyl urea resin (product name NIKALAC MX290 (stock) Sanwa Chemical Manufacturing) or 1,3,4,6-tetra(methoxymethyl) glycourea (product name NIKALAC MX270 (stock) Sanwa Chemical Manufacturing), etc.

[0117] 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.) can be used more preferably.

[0118] 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. Oxymethyl ether, bis(3-ethyl-3-oxetane)methyl bisphenol A, trimethylolpropane tri(3-ethyl-3-oxetane)methyl ether, neopentyl tetroxide tetra(3-ethyl-3-oxetane)methyl ether, poly[[3-[(3-ethyl-3-oxetane)methoxy]propyl]sesquioxane] derivatives, oxetane silicate oxycyclobutane, phenolic varnish-type oxetane, and 1,3-bis[(3-ethyloxetane-3-yl)methoxy]benzene, etc. For example, OXT121 (product name, manufactured by Dong-A Synthetic (Stock)) and OXT221 (product name, manufactured by Dong-A Synthetic (Stock)) are preferred.

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

[0120] 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, etc.

[0121] 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.); 4,4'-diphenylmethane diisocyanate-based terminal isocyanates (e.g., manufactured by Mitsui Chemicals, trade name: Takenate B-815N; manufactured by Daiei Sangyo, trade name: Blonate PMD-OA01 and PMD-MA01, etc.); 1,3-bis(isocyanatomethyl)cyclohexane-based terminal isocyanates (e.g., manufactured by Mitsui Chemicals, trade name: Takenate B-846N; manufactured by Tosoh, trade name: Coronate BI-301, 2507 and 2554, etc.); and isophorone diisocyanate-based terminal isocyanates (e.g., manufactured by Baxenden, trade name: 7950, 7951 and 7990, etc.).

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

[0123] 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 inhibiting copper migration, the lower limit of the thermal crosslinking agent is more preferably 0.5 parts by weight or more, and more preferably 1 part by weight or more. From the viewpoint of the copper adhesion of the photosensitive resin composition of the present invention, the upper limit of the thermal crosslinking agent is more preferably 20 parts by weight or less, and more preferably 10 parts by weight or less.

[0124] (G)Silane coupling agent: To improve the copper adhesion of the hardened film, the photosensitive resin composition may contain (G)silane coupling agent in any way.

[0125] Examples of silane coupling agents 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), mercaptopropyltri ... 3-Mercaptomethyltrimethoxysilane (manufactured by Azmax (stock): trade name SIM6473.5C), 3-mercaptomethylmethyldimethoxysilane (manufactured by Azmax (stock): trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane 3-Mercaptopropyldimethoxypropoxysilane, 3-Mercaptopropylmethoxypropoxysilane, 2-Mercaptoethyltrimethoxysilane, 2-Mercaptoethyldiethoxymethoxysilane, 2-Mercaptoethylethoxydimethoxysilane, 2-Mercaptoethyltripropoxysilane, 2-Mercaptoethyltripropoxysilane, 2-Mercaptoethylethoxydipropoxysilane, 2-Mercaptoethyldimethoxypropoxysilane, 2-Mercaptoethylmethoxydipropoxysilane 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., but not limited to them.

[0126] Also, as silane coupling agents, other 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), 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)propyl Trimethoxysilane (manufactured by Azmax (stock): trade name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax (stock): trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax (stock): trade name SLA0599.1), aminophenyltrimethoxysilane (manufactured by Azmax (stock): trade name SLA0599.2), etc., but not limited to them.

[0127] Furthermore, examples include: 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax (stock): trade name SIT8396.0), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylmethylethyl)pyridine, aminocarboxylic acid (3-triethoxysilylpropyl)-tert-butyl ester, (3-glycidoxypropyl)triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane. Alkane, tetraisobutoxysilane, tetra-tertiary 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.

[0128] The silane coupling agents listed above can be used alone or in combination. Among the silane coupling agents listed above, from the viewpoint of copper adhesion, N-phenyl-3-aminopropyltrimethoxysilane, tributyl carbamate (3-triethoxysilylpropyl) and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane are preferred.

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

[0130] The (H) acid component is used to improve the copper adhesion of the hardened film or inhibit copper migration. The photosensitive resin composition may contain the (H) acid component in any way. By using the (H) component in combination with, for example, a (F) thermal crosslinking agent, the thermal crosslinking reaction of the (F) thermal crosslinking agent can be promoted, thereby improving the inhibition of copper migration.

[0131] As an (H) acid component, examples include: (±) mandelic acid, benzoic acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, p-aminobenzoic acid, m-trifluoromethylbenzoic acid, 4-biphenylcarboxylic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc., but are not limited to them.

[0132] When using the (H) acid component, its content is preferably 0.001 to 5 parts by weight relative to 100 parts by weight of the (A) polyimide precursor or polyimide resin. From the viewpoint of inhibiting copper migration in the photosensitive resin composition of the present invention, the lower limit of the (H) acid component is preferably 0.005 parts by weight or more, and more preferably 0.01 parts by weight or more. From the viewpoint of adhesion, the upper limit of the (H) acid component is preferably 3 parts by weight or less, and more preferably 2 parts by weight or less.

[0133] The photosensitive resin composition may further contain components other than those in (A) to (H) above. There are no limitations on the components other than those in (A) to (H), and examples include: (I) a thermal alkali generating agent, (J) a hindered phenolic compound, (K) an organotitanium compound, (L) a sensitizer, and (M) a polymerization inhibitor.

[0134] (I) The photosensitive resin composition may contain (I) an alkali-generating agent. An alkali-generating agent refers to a compound that generates alkali by heating. By containing a heat-alkali-generating agent, the amide formation of the photosensitive resin composition can be further promoted.

[0135] No particular type is specified as a heat-generating agent, but examples include amine compounds protected by a tertiary butoxycarbonyl 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.

[0136] Examples of amine compounds protected by a tertiary 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 alcohol, 3-amino-1,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valine alcohol, and 3-amino-1,2-dimethyl-1-propanol. -Propylene glycol, 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 alcohol, 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 an amino acid and its derivatives is protected by a tertiary butoxycarbonyl group, but not limited thereto.

[0137] The content 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 less, more preferably 1 part by weight or more and 20 parts by weight or less. From the viewpoint of promoting amide formation, the above content 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 30 parts by weight or less.

[0138] (J) Hindered phenolic compounds are used to suppress discoloration on copper surfaces. The photosensitive resin composition may contain hindered phenolic compounds in any way.

[0139] The hindered phenolic compound is not limited, but examples include: 2,6-di-tri-butyl-4-methylphenol, 2,5-di-tri-butyl-hydroquinone, octadecyl 3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate, isooctyl 3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-tri-butylphenol), 4,4'-thio-bis(3-methyl-6-tri-butylphenol), 4,4'-butylene-bis(3-methyl-6-tri-butylphenol), triethylene glycol-bis[3-(3-tri-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5- [3,5-Di-tert-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylbis[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), neopentyltetramethyltetra[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.

[0140] Furthermore, examples of hindered phenolic compounds include, for instance: 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tertiary-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-secondary-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3- [Hydroxy-2,6-dimethylbenzyl]-1,3,5-tris(2,4,6)-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-tris(2,4,6)-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-tris(2,4,6)-(1H,3H,5H)-trione, 1,3,5-tris(4-tributyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-tris(2,4,6)-(1H,3H,5H)-trione 1,3,5-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-2,6-dimethylbenzyl)-1,3,5-tris(4-tert-butyl-5,6-di ... The following are examples of triones, but are not limited to: (methylbenzyl)-1,3,5-tris(4-tributyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tributyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tributyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris(4-tributyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris(4-tributyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tributyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris(4-tributyl-2,4,6-(1H,3H,5H)-trione.

[0141] Among them, 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.

[0142] The content of the 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 content is 0.1 parts by weight or more, for example, when a photosensitizing resin composition is formed 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.

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

[0144] Examples of usable organotitanium compounds include organic chemical substances that are bonded to titanium atoms via covalent or ionic bonds.

[0145] Specific examples of organotitanium compounds are shown in I) to VII) below: I) Titanium chelate compounds: Among them, titanium chelates having two or more alkoxy groups are more preferably used in terms of obtaining the storage stability and good pattern of the photosensitive resin composition. Specific examples are: 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.

[0146] 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.

[0147] III) Titanium diacetic compounds: such as pentamethylcyclopentadienyltrimethyltitanium, bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, etc.

[0148] IV) Monoalkoxy titanium compounds: such as titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonic acid) isopropoxide, etc.

[0149] V) Titanium oxide compounds: such as bis(glutaric acid) titanium oxide, bis(tetramethylpimelic acid) titanium oxide, phthalocyanine titanium oxide, etc.

[0150] VI) Titanium tetraacetate compounds: such as titanium tetraacetate, etc.

[0151] VII) Titanate coupling agents: such as tris(dodecylbenzenesulfonyl)titanate isopropyl ester, etc.

[0152] Wherein, when the organotitanium compound is selected from at least one compound of the group consisting of I) titanium chelate compounds, II) tetraalkoxy titanium compounds, and III) diacetic titanium compounds, it is preferable from the viewpoint of exhibiting 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.

[0153] When the organic titanium compound is formulated, its content relative to 100 parts by weight of (A) polyimide precursor or polyimide is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 2 parts by weight. When the content is 0.05 parts by weight or more, it exhibits good heat resistance and chemical resistance; on the other hand, when it is 10 parts by weight or less, it exhibits excellent storage stability.

[0154] (L) The sensitizer photosensitive resin composition may contain sensitizers in any way to improve photosensitivity.

[0155] Examples of 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-di... Methylaminocinnamoyl 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-diethylamino) 3-ethoxy-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-hydroxy-2-phenanthone, di- Isoamyl methylaminobenzoate, 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 in combination, for example, of 2 to 5 types.

[0156] When the photosensitive resin composition contains a sensitizer, the content 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.

[0157] (M) Polymerization inhibitor To improve the stability of viscosity and photosensitivity of the photosensitive resin composition, especially when stored in a solution containing solvent, the photosensitive resin composition may contain polymerization inhibitors in any way.

[0158] As polymerization inhibitors, the following can 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.

[0159] <Method for manufacturing hardened embossed patterns and semiconductor device> The method for manufacturing hardened embossed patterns of the present invention includes the following steps: (1) coating the above-mentioned photosensitive resin composition of the present invention onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the above-mentioned photosensitive resin layer; (3) developing the exposed photosensitive resin layer to form an embossed pattern; (4) heat-treating the above-mentioned embossed pattern to form a hardened embossed pattern.

[0160] (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 by a spin coater, bar coater, doctor blade coater, curtain coater, screen printing machine, etc., or spray coating methods performed by a spray coater, etc.

[0161] (2) Exposure Step 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 above-formed photosensitive resin layer through a patterned photomask or reticle or directly through an ultraviolet light source.

[0162] (3) Embossed Pattern Forming Step In this step, the unexposed portions of the exposed photosensitive resin layer are removed by development. As for the development method for developing the exposed (irradiated) photosensitive resin layer, any method can be selected from previously known photoresist development methods, 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 after development can be performed as needed using any combination of temperature and time.

[0163] The developing solution used in the developing process is preferably a good solvent for the photosensitive resin composition, or a combination of such a good solvent and a poor solvent. A good solvent is preferably N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. A poor solvent is preferably toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate, and water, etc. When a good solvent and a poor solvent are used in combination, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the photosensitive resin composition. Furthermore, two or more solvents may be used, for example, in combination.

[0164] (4) Hardening Embossed Pattern Forming Step In this step, the embossed 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 embossed pattern (hardened film) containing polyimide. As a method of heat treatment, various methods can be selected, such as the method of using a heating plate, the method of using an oven, and the method of 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. In order to further improve the copper adhesion, the heat treatment temperature is preferably below 350°C, more preferably below 230°C, and even more preferably below 200°C, and even more preferably below 180°C. Furthermore, in order to further suppress copper migration, the heat treatment temperature is preferably above 170°C, and even more preferably above 250°C. To balance copper adhesion and copper migration inhibition, the heat treatment temperature is preferably 170℃~350℃, and more preferably 200℃~280℃. Air, or inert gases such as nitrogen or argon, can be used as the ambient gas during heat hardening.

[0165] <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 (A) polyimide resin of the present invention 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 (A) 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, a polyimide film can also 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 (68). [Chemistry 80]

[0166] For the same reason, the preferred X9 and Y1 in general formula (11) and the preferred X10 and Y2 in general formula (12) are also preferred in the polyimide with X21 and Y3 represented by the above general formula (68). In the above general formula (68), the number of repeating units n9 is not particularly limited and can be an integer from 2 to 150.

[0167] <Semiconductor Device> A semiconductor device preferably has a hardened raised pattern obtained by the above-described method for manufacturing a hardened raised pattern. A 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. A semiconductor device can be manufactured using a semiconductor element as a substrate, with the method for manufacturing a hardened raised pattern of the present invention as part of the manufacturing process. More specifically, a semiconductor device can be manufactured by a semiconductor device manufacturing method including forming a 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.

[0168] <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 with the display element, or it can be deposited with other layers in between. Examples of such hardened films include: surface protective films, insulating films, and planarization films for TFT liquid crystal display elements and color filter elements, protrusions for MVA type liquid crystal display devices, and spacers for organic EL element cathodes.

[0169] 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 applications 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, and liquid crystal alignment films, etc. [Examples]

[0170] Hereinafter, embodiments of the present invention will be specifically described, but the implementation methods are 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.

[0171] <Determination and Evaluation Methods> (1) Weight-average molecular weight The weight-average molecular weight (Mw) of each resin was determined by gel permeation chromatography (conversion to standard polystyrene) under the following conditions. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Column: 2 Shodex KD-806M manufactured by Showa Denko (Stock) in series, or Shodex 805M / 806M manufactured by Showa Denko (Stock) in series Standard monodisperse polystyrene: Shodex STANDARD SM-105 manufactured by Showa Denko (Stock) Mobile phase: 0.1 mol / L LiBr / N-methyl-2-pyrrolidone (NMP) Flow rate: 1 mL / min.

[0172] (2) Evaluation of copper adhesion: On a 6-inch silicon wafer (manufactured by Fujimi Electronic Industry, 625±25 μm thick), a sputtering apparatus (SME-200E type, manufactured by ULVAC) 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 hardened film thickness of approximately 8 μm using a coating and developing machine (D-Spin60A type, manufactured by SOKUDO). The wafer was then pre-baked at 110°C for 240 seconds using a heated plate to form a coating on the copper wafer. Afterward, the entire surface was exposed to 800 mJ / cm2 using a parallel light mask aligned with an exposure machine (PLA-501FA type, manufactured by Canon). Subsequently, a temperature-programmed curing oven (VF-2000 type, manufactured by Koyo Lindberg) was used to heat the material for 2 hours in a nitrogen atmosphere at the temperatures recorded in Tables 1 to 4 to obtain a hardened embossed pattern (a thermosetting polyimide coating).

[0173] An Evercel OPP Tape (No. 830NEV, manufactured by Sekisui Chemicals Co., Ltd.) was bonded to the sample, and the tape and polyimide coating were cut into 5 mm wide pieces using a cutting machine. Subsequently, using a Tensilon universal testing machine (RTG-1210, manufactured by A&D Co., Ltd.), the tape and polyimide coating were peeled between copper and polyimide, stretched for 60 mm at a speed of 50 mm / min at 180 degrees. The load at this point was calculated by integral averaging, and this value was evaluated as the adhesion strength. If the evaluation is C or above, it can be better used as a hardened embossed pattern for semiconductors. A: Bond strength is 0.4 N / mm or higher. B: Bond strength is 0.3 N / mm or higher but less than 0.4 N / mm. C: Bond strength is 0.2 N / mm or higher but less than 0.3 N / mm. D: Bond strength is less than 0.2 N / mm.

[0174] (3) b-HAST test preparation: A TEG wafer with comb-shaped Cu wiring of 10 μm / 10 μm and 5 μm height was formed on a silicon wafer with SiOx layer on the surface. The TEG wafer was immersed in 1% acetic acid aqueous solution and ion-exchange water for 1 minute respectively, then rinsed with ion-exchange water and dried with an air gun. Then, oxygen plasma was subjected to 25°C for 120 seconds at an oxygen flow rate of 1500 mL / min, 50 Pa, MW 1500 W, RF 200 W. Subsequently, a photosensitive resin composition was spin-coated onto the TEG wafer using a coating and developing machine (D-Spin60A type, manufactured by SOKUDO). The hardened film thickness was approximately 8 μm. A pre-baking process was performed at 110°C for 240 seconds using a heated plate to form the coating. Then, the wafer was exposed to 800 mJ / cm² using a parallel light mask aligned with an exposure machine (PLA-501FA type, manufactured by Canon). To ensure conductivity during the b-HAST test, the Cu electrode area was exposed while being shielded from light, and the unexposed areas were removed by subsequent development. After exposure, and after a period of more than 30 minutes, a spin-spray development was performed at 23°C using cyclopentanone as the developer in a coating developer (D-Spin60A model, manufactured by SOKUDO). The development time was 1.4 times the time required for the unexposed areas to completely dissolve and disappear. This was 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) was used under a nitrogen atmosphere and heated for 2 hours at the temperatures recorded in Tables 1-4 to obtain a hardened embossed pattern.

[0175] Using an ion migration evaluation system (AMI-025-U-5, manufactured by ESPEC) and a high-acceleration life testing apparatus (HAST CHAMBER, EHS-222M, manufactured by ESPEC), the sample was subjected to a b-HAST test at 130°C and 85%RH with an applied voltage of 50 V. The insulation resistance between copper wirings was measured every 30 minutes. If it was less than 1 × 10⁴ Ω, it was considered as insulation failure. The time from the start of the test to insulation failure was calculated and evaluated based on the following criteria. If the evaluation is C or higher, it can be better used as a hardened relief pattern for semiconductors. A: More than 500 hours until insulation failure B: More than 300 hours but less than 500 hours until insulation failure C: More than 100 hours but less than 300 hours until insulation failure D: Less than 100 hours until insulation failure

[0176] (4) Resolution evaluation: On a 6-inch silicon wafer (manufactured by Fujimi Electronic Industry, 625±25 μm thick), a sputtering apparatus (SME-200E type, manufactured by ULVAC) was used to sequentially sputter a 200 nm thick titanium (Ti) and a 400 nm thick copper (Cu) layer. Subsequently, a photosensitive resin composition was spin-coated onto the wafer using a coating and developing machine (D-Spin60A type, manufactured by SOKUDO) to achieve a hardened film thickness of approximately 8 μm. The wafer was then pre-baked at 110°C for 240 seconds using a heating plate to form a coating on the copper wafer. The coating was exposed to i-rays using a lithography system (Ultratech AP-200, Veeco) with circular masks of 9 μm, 10 μm, and 11 μm in diameter, at a focal length of 0 μm and in steps of 25 mJ / cm² from 50 mJ / cm² to 300 mJ / cm². After at least 30 minutes, it was developed using a coating developer (D-Spin 60A, SOKUDO) at 23°C with cyclopentanone as the developer for 1.4 times the time required for the unexposed areas to completely dissolve. This was followed by a 10-second spin wash with propylene glycol monomethyl ether acetate. Finally, a temperature-programmed curing oven (VF-2000, Koyo Lindberg) was used under nitrogen atmosphere at the temperatures listed in Tables 1-4 for 2 hours to obtain a hardened embossed pattern.

[0177] The circular hole pattern obtained for this sample was observed using a field emission scanning electron microscope S-4800 (manufactured by Hitachi High-Technologies). If the bottom of the circular hole is not raised and the opening is in a positive cone manner, and the area of ​​the obtained circular hole opening is more than 1 / 2 of the opening area of ​​the corresponding pattern mask, it is considered to be resolved. The minimum diameter of the exposure mask in the resolved opening is shown as the evaluation result.

[0178] <Manufacturing Example> Manufacturing Example 1: (A) Synthesis of polyimide precursor A1 147.1 g of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) was placed in a 2 L separable flask, along with 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone (hereinafter 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 completed, the reaction mixture was cooled to room temperature and left to stand for 16 hours.

[0179] 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.

[0180] The obtained reaction solution was added to 3 L of ethanol to generate 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 dried under vacuum 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.

[0181] Manufacturing Example 2: (A) The synthesis of polyimide precursor A2 was carried out in the same manner as described in Manufacturing Example 1 above, except that 155.1 g of 4,4'-oxophthalic dianhydride (ODPA) was used instead of 147.1 g of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) 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 21,000.

[0182] Manufacturing Example 3: (A) The synthesis of polyimide precursor A3 was carried out in the same manner as described in Manufacturing Example 1 above, except that 124.0 g of 4,4'-oxophthalic dianhydride (ODPA) and 29.4 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) were used in place of 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 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 24,000.

[0183] Manufacturing Example 4: (A) The synthesis of polyimide precursor A4 was carried out in the same manner as described in Manufacturing Example 1 above, except that 155.1 g of 4,4'-oxophthalic dianhydride (ODPA) was used instead of 147.1 g of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), and 49.2 g of 1,4-phenylenediamine (pPD) was used instead of 93.0 g of 4,4'-oxodiphenylamine (ODA), to obtain the polymer (polyimide precursor A4). The molecular weight of polyimide precursor A4 was determined by gel permeation chromatography (converted to standard polystyrene), and the weight average molecular weight (Mw) was 21,000.

[0184] Manufacturing Example 5: (A) The synthesis of polyimide precursor A5 was carried out in the same manner as described in Manufacturing Example 1 above, except that 62 g of 4,4'-oxophthalic dianhydride (ODPA) and 88.3 g of pyromellitic dianhydride (PMDA) were used instead of 147.1 g of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), and 98.6 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) was used instead of 93.0 g of 4,4'-oxodiphenylamine (ODA), to obtain polymer (A5). The molecular weight of polymer (A5) was determined by gel permeation chromatography (converted to standard polystyrene), and the weight average molecular weight (Mw) was 28,000.

[0185] Manufacturing Example 6: (A) Synthesis of Polyimide Resin A6 200 g of N-methyl-2-pyrrolidone (hereinafter NMP) and 33.1 g (0.012 mol) of 6-(4-aminophenoxy)biphenyl-3-amine (PDPE) were added to a 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 acid dianhydride (BCD) and 50.0 g of toluene were added, and the mixture was heated to 180°C. After confirming that the theoretical amount of water and the added toluene in the Dean-Stark extraction apparatus had been extracted, heating was stopped, and the mixture was cooled to room temperature. The obtained reaction solution was added dropwise to 2000 g of ion-exchanged water to precipitate the polymer. After filtration and separation, the polymer was dried under vacuum at 40°C to obtain a powdered polymer (polyimide resin A6). The weight-average molecular weight of polyimide resin A6 was determined by gel permeation chromatography (conversion to standard polystyrene), and the result was Mw = 14,300.

[0186] Manufacturing Example 7: (A) Synthesis of Polyimide Resin A7 (MOI Modified BCD-PDPE) 200 g of GBL and 33.1 g (0.12 mol) of PDPE were added to a three-necked flask equipped with a Dean-Stark extraction apparatus and purged with nitrogen, and dissolved. 24.8 g (0.1 mol) of 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.

[0187] Next, 6.2 g of ethyl 2-isocyanate methacrylate (hereinafter 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 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 = 15,200.

[0188] Manufacturing Example 8: (A) Synthesis of Polyimide Resin A8 Except for changing NMP to GBL in Manufacturing Example 6, changing the amount of PDPE added to 23.0 g (0.083 mol), and changing BCD to 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 6. 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.

[0189] 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 6. 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.

[0190] <Example 1> A photosensitive resin composition was prepared using polyimide precursors A1 and A2 by the following method, and the prepared composition was evaluated. The following were prepared: (A) Polyimide precursors A1 and A2: 40 g of the polyimide precursor described in Manufacturing Example 1 and 60 g of the polyimide precursor described in Manufacturing Example 2; (B) 0.5 g of 7-methyl-2,4-dioxane-1,2,3,4-tetrahydropyrido[2,3-d]pyrimidine-5-carboxylic acid (manufactured by BLDpharm); (C) Photopolymerization initiator C1: 5 g of 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.); (E) Photopolymerizable monomer E1: 5 g of NK Ester 4G (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.); and (F) Thermal crosslinking agent F1: 1 g of NIKALAC MX-290 (manufactured by Sanhe Chemical Co., Ltd.). (G) Silane coupling agent G1: KBM573 (manufactured by Shin-Etsu Chemical Co., Ltd.) 1 g, (K) Organotitanium compound K1: ORGATIX TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.) 0.5 g, (L) Sensitizer L1: 2,2'-(phenylimino)diethanol (manufactured by Kanto Chemical Co., Ltd.) 10 g, dissolved in a mixed solvent of (D) solvent D1: γ-butyrolactone (hereinafter referred to as GBL, manufactured by Mitsubishi Chemical Co., Ltd.) 80 g and solvent D2: dimethyl sulfoxide (hereinafter referred to as DMSO, manufactured by Toray Fine Chemical Co., Ltd.) 20 g. By adding the required amount of GBL:DMSO = 80:20 (mass ratio) solution, the viscosity of the obtained solution was adjusted to about 40 poise, thus preparing a photosensitive resin composition. The composition was evaluated according to the above method. The results are shown in Table 1.

[0191] <Examples 2-53, Comparative Examples 1-8> Except for the solvent, the formulations were adjusted according to the proportions shown in Tables 1-4. The solvents were dissolved in the same manner as in Example 1, and the viscosity was adjusted to prepare photosensitive resin compositions. Furthermore, the copper adhesion and copper migration properties of the photosensitive resin compositions shown in Tables 1-3 were evaluated. In addition to evaluating the copper adhesion and copper migration properties, the resolution of the photosensitive resin compositions shown in Table 4 was also evaluated. The results of the examples and comparative examples are shown in Tables 1-4. The compounds described in Tables 1-4 are as follows.

[0192] (A) Polyimide precursor or polymer used as a comparison: A1: Polyimide precursor described in Manufacturing Example 1; A2: Polyimide precursor described in Manufacturing Example 2; A3: Polyimide precursor described in Manufacturing Example 3; A4: Polyimide precursor described in Manufacturing Example 4; A5: Polyimide precursor described in Manufacturing Example 5; A6: Polyimide resin described in Manufacturing 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; A1': ZCR-1797H (acid-modified epoxy acrylate with a biphenyl backbone, manufactured by Nippon Kayaku Co., Ltd.)

[0193] (B) Heterocyclic compounds B1: 7-Methyl-2,4-dioxy-1,2,3,4-tetrahydropyrido[2,3-d]pyrimidin-5-carboxylic acid (manufactured by BLDpharm) B2: Xanthopterin (manufactured by Tokyo Chemical Industry Co., Ltd.) B3: Allopurinol (manufactured by Tokyo Chemical Industry Co., Ltd.) B4: 4-[2-(2-amino-4,7-dihydro-4-dioxy-3H-pyrrolo[2,3-d]pyrimidin-5-yl)ethyl]benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) B5: Pyrido[2,3-d]pyrimidin-4-ol (manufactured by Fujifilm and Hikari Pure Chemical Co., Ltd.) B6: 1H,2H,3H,4H-pyrido[2,3-d]pyrimidin-2,4-dione (manufactured by Fujifilm and Hikari Pure Chemical Co., Ltd.) B7: Pterin-4-ol (manufactured by Fujifilm and Hikari Pure Chemical Industries, Ltd.) B8: 7-Phenyl-pterin-4-ol (manufactured by Sigma-Aldrich) B9: Purine-6-carboxylic acid (manufactured by Sigma-Aldrich) B10: 6-amino-1H-pyrazolo[3,4-d]pyrimidin-4(7H)-one (manufactured by Combi-Blocks) B11: 1H-pyrazolo[3,4-d]pyrimidin-4,6(2H,5H)-dione (manufactured by Combi-Blocks) B12: 7-Denitroxanthine (manufactured by Tokyo Chemical Industry Co., Ltd.) B13: 7-Denitroxanthine (manufactured by BLDpharm) B14: 2-amino-4-sideoxy-4,7-dihydro-1H-pyrrolo[2,3-d]pyrimidin-5-carboxylic acid (manufactured by BLDpharm) B15: 6-Nitro-3H-pyrido[2,3-d]pyrimidin-4-one (manufactured by Combi-Blocks) B16: 7-Chloropyrido[2,3-d]pyrimidin-2,4(1H,3H)-dione (manufactured by Fujifilm and Hikari Pure Chemical Industries, Ltd.) B17: 6-(trifluoromethyl)-1H-pyrazolo[3,4-d]pyrimidin-4-ol (manufactured by Fujifilm and Hikari Pure Chemical Industries, Ltd.) B18: 5-(4-iodophenyl)-1H-pyrrolo[2,3-d]pyrimidin-2,4(3H,7H)-dione (manufactured by BLDpharm) B1': 8-azaadenine (manufactured by Tokyo Chemical Industry Co., Ltd.) B2': 5-amino-1H-tetrazole (manufactured by Chiyoda Chemical Co., Ltd.) B3': 1,2,3-Benztriazole (manufactured by Tokyo Chemical Industry Co., Ltd.) B4': Hypoxanthine (manufactured by Tokyo Chemical Industry Co., Ltd.) B5': 2,4-Dihydroxypteridine (manufactured by Tokyo Chemical Industry Co., Ltd.)

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

[0195] (D) Solvent D1: GBL (manufactured by Mitsubishi Chemical) D2: DMSO (manufactured by TORAY Fine Chemicals)

[0196] (E) Photopolymerizable monomers E1: Tetraethylene glycol dimethacrylate (trade name NK ESTER 4G, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) E2: Tris(2-acryloxyethyl) isocyanurate (product name NK ESTER A-9300, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) E3: Neopentyl terephthalol tetraacrylate (product name NK ESTER A-TMMT, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) E4: Tricyclodecanediethanol dimethacrylate (product name NK ESTER DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0197] (F) Thermal crosslinking agent F1: Alkyl urea resin (product name NIKALAC MX-290 manufactured by Sanhe Chemical Co., Ltd.) F2: 1,3,4,6-Tetra(methoxymethyl)glycourea (product name NIKALAC MX-270 manufactured by Sanhe Chemical Co., Ltd.)

[0198] (G)Silane Coupling Agent G1: N-Phenyl-3-aminopropyltrimethoxysilane (Product name KBM573, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) G2: Carbamate (3-triethoxysilylpropyl)-tertiary butyl ester (manufactured by Gelest Corporation) G3: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0199] (H) Acid components H1: (±)-Mandelic acid (manufactured by Fujifilm and Kohden Chemical Co., Ltd.) H2: p-Toluenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0200] (K) Organotitanium compound K1: Bis(ethyl acetate) diisopropoxide titanium (product name ORGATIX TC-750, manufactured by Matsumoto Fine Chemical Co., Ltd.)

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

[0202] [Table 1] polymer Heterocyclic compounds Photopolymerization initiator Photopolymerizable monomers thermal crosslinking agent Silane coupling agent organotitanium compounds sensitizer Curing temperature [°C] Evaluation results A1 A2 B1 B2 B3 B4 B5 B6 B7 B8 B9 B10 B11 B12 B13 B14 B15 B16 B17 B18 C1 E1 F1 G1 K1 L1 b-HAST Copper tightness Example 1 40 60 0.5 5 5 1 1 0.5 10 250 A B Example 2 40 60 0.5 5 5 1 1 0.5 10 250 A A Example 3 40 60 0.5 5 5 1 1 0.5 10 250 A B Example 4 40 60 0.5 5 5 1 1 0.5 10 250 A A Example 5 40 60 0.5 5 5 1 1 0.5 10 250 A B Example 6 40 60 0.5 5 5 1 1 0.5 10 250 A B Example 7 40 60 0.5 5 5 1 1 0.5 10 250 A B Example 8 40 60 0.5 5 5 1 1 0.5 10 250 A B Example 9 40 60 0.5 5 5 1 1 0.5 10 250 A A Example 10 40 60 0.5 5 5 1 1 0.5 10 250 A A Example 11 40 60 0.5 5 5 1 1 0.5 10 250 A B Example 12 40 60 0.5 5 5 1 1 0.5 10 250 A B Example 13 40 60 0.5 5 5 1 1 0.5 10 250 A B Example 14 40 60 0.5 5 5 1 1 0.5 10 250 A A Example 15 40 60 0.5 5 5 1 1 0.5 10 250 A C Example 16 40 60 0.5 5 5 1 1 0.5 10 250 A C Example 17 40 60 0.5 5 5 1 1 0.5 10 250 A C Example 18 40 60 0.5 5 5 1 1 0.5 10 250 A C

[0203] [Table 2] polymer Heterocyclic compounds Photopolymerization initiator Photopolymerizable monomers thermal crosslinking agent Silane coupling agent organotitanium compounds sensitizer Curing temperature [℃] Evaluation results A1 A2 A3 A4 A5 A6 A7 A8 A9 B1 B2 B3 B4 C1 E1 F1 G1 K1 L1 b-HAST Copper tightness Example 19 40 60 0.005 5 5 1 1 0.5 10 250 A C Example 20 40 60 0.05 5 5 1 1 0.5 10 250 A A Example 21 40 60 15 5 1 1 0.5 10 250 B B Example 22 40 60 0.5 5 5 1 1 0.5 10 200 C A Example 23 40 60 0.5 5 5 1 1 0.5 10 200 C A Example 24 40 60 0.5 5 5 1 1 0.5 10 200 C A Example 25 40 60 0.5 5 5 1 1 0.5 10 200 C A Example 26 40 60 0.5 5 5 1 1 0.5 10 230 B A Example 27 40 60 0.5 5 5 1 1 0.5 10 230 A A Example 28 40 60 0.5 5 5 1 1 0.5 10 230 A A Example 29 40 60 0.5 5 5 1 1 0.5 10 230 A A Example 30 40 60 0.5 5 5 1 1 0.5 10 150 C C Example 31 40 60 0.5 5 5 1 1 0.5 10 170 C B Example 32 40 60 0.5 5 5 1 1 0.5 10 280 A B Example 33 40 60 0.5 5 5 1 1 0.5 10 350 A C Example 34 100 0.5 5 5 1 1 0.5 10 200 C A Example 35 100 0.5 5 5 1 1 0.5 10 250 B B Example 36 100 0.5 5 5 1 1 0.5 10 250 B B Example 37 100 0.5 5 5 1 1 0.5 10 250 B C Example 38 100 0.5 5 5 1 1 0.5 10 250 A B Example 39 100 0.5 5 5 1 1 0.5 10 250 A B Example 40 100 0.5 5 5 1 1 0.5 10 250 B B Example 41 100 0.5 5 5 1 1 0.5 10 250 A B

[0204] [Table 3] polymer Heterocyclic compounds Photopolymerization initiator Photopolymerizable monomers thermal crosslinking agent Silane coupling agent organotitanium compounds Acid components other than (B) sensitizer Curing temperature [°C] Evaluation results A1 A2 A1' B1 B4 B1' B2' B3' B4' B5' C1 E1 E2 E3 E4 F1 F2 G1 G2 G3 K1 H1 H2 L1 b-HAST Copper tightness Example 42 40 60 0.5 5 30 1 1 0.5 10 250 B C Example 43 40 60 0.5 5 5 1 1 0.5 10 250 A C Example 44 100 0.5 5 5 1 1 0.5 10 250 A B Example 45 40 60 0.5 5 5 1 1 0.5 10 250 A A Example 46 40 60 0.5 5 5 1 0.5 10 250 A B Example 47 40 60 0.5 5 5 1 1 0.5 10 250 A A Example 48 40 60 0.5 5 5 1 1 0.5 10 250 B A Example 49 40 60 0.5 5 5 1 1 0.5 0.5 10 250 A A Example 50 40 60 0.5 5 5 1 1 0.5 0.05 10 250 A A Example 51 40 60 0.5 5 5 1 0.5 10 250 B B Comparative Example 1 40 60 0.5 5 5 1 1 0.5 10 200 D B Comparative Example 2 40 60 0.5 5 5 1 1 0.5 10 250 A D Comparative Example 3 40 60 0.5 5 5 1 1 0.5 10 250 A D Comparative Example 4 40 60 0.5 5 5 1 1 0.5 10 250 B D Comparative Example 5 40 60 0.5 5 30 1 1 0.5 10 250 B D Comparative Example 6 40 60 5 5 1 1 0.5 10 250 B D Comparative Example 7 100 0.5 0.5 5 5 1 1 0.5 10 250 C D Comparative Example 8 40 60 0.5 5 5 1 1 0.5 10 250 A D

[0205] [Table 4] polymer Heterocyclic compounds Photopolymerization initiator Photopolymerizable monomers thermal crosslinking agent Silane coupling agent organotitanium compounds sensitizer Curing temperature [℃] Evaluation results A1 A2 B4 C1 E1 F1 G1 K1 L1 bHAST Copper tightness resolution Example 52 40 60 0.2 5 10 1 1 0.5 10 250 A A 9 μm Example 53 40 60 0.2 5 1 1 0.5 10 250 A A 11 μm

[0206] Observing the results in Tables 1 to 3, Comparative Examples 1 to 8, which do not meet the necessary conditions of the present invention, cannot achieve good results in both copper adhesion and copper migration performance (b-HAST test results). On the other hand, Examples 1 to 53, which meet the necessary conditions of the present invention, show excellent performance in both adhesion and copper migration performance. From the comparison of Comparative Examples 2 to 4 and 6 with Examples 1 to 18, Comparative Examples 5 with Example 42, and Comparative Examples 8 with Example 44, it can be seen that by using the (B) heterocyclic compound of the present invention, copper adhesion is improved, and good adhesion is also shown at a high curing temperature of 250°C. Furthermore, from the comparison of Comparative Examples 1 with Examples 22 to 25, it can be seen that by using the (B) heterocyclic compound of the present invention, copper migration performance and adhesion can also be improved at a curing temperature of 200°C. Furthermore, a comparison between Comparative Example 7 and Example 43 shows that by using the polyimide precursor (A) and / or polyimide resin of the present invention, both copper adhesion and copper migration properties can be improved.

[0207] Furthermore, if we observe the examples, it can be seen from the comparison between Examples 1-14 and Examples 15-18 that the structure having the general formula (6)-(10) of the present invention is better than the structure having the general formula (1)-(5) in terms of copper adhesion. Examples 4 and 19-21 are compositions with different contents of (B) heterocyclic compound, but Examples 4 and 20, with contents in the range of 0.01-10 parts by mass, have better copper adhesion or copper migration performance. By adjusting the content of (B) heterocyclic compound to less than 10 parts by mass, the reason is uncertain and not limited to theory, it is speculated that the ionic component in the resin layer will not increase to the required level, and copper migration also becomes good.

[0208] It is known that Examples 38 to 41 used polyimide resin, but since Examples 38, 39 and 41 do not contain fluorine, their migration performance is better than that of Example 40.

[0209] Comparing Examples 52 and 53 in Table 4, the minimum pore size is reduced and the resolution is improved by using (E) photopolymerizable monomers. It is speculated that if (E) photopolymerizable monomers are used, the photosensitive resin composition will be crosslinked, thereby improving the resolution.

[0210] A comparison of Examples 4 and 51 shows that the presence of a (F) thermal crosslinking agent improves copper adhesion and copper migration properties. Furthermore, a comparison of Examples 4 and Examples 45-47 shows that the presence of a (G) silane coupling agent improves copper adhesion. Moreover, a comparison of Examples 48-50 shows that the presence of an (H) acid component results in good copper migration. [Industrial Applicability]

[0211] By using the photosensitive resin composition of the present invention, a hardened embossed pattern with excellent copper adhesion during high-temperature curing and minimal 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 heterocyclic compound, and (C) a photopolymerization initiator, wherein the heterocyclic compound (B) is a compound represented by the following general formula (1): [Chemical 1] {wherein, X1 is a nitrogen atom or a carbon atom substituted by R4, and R1, R2, R3 and R4 are each independently a hydrogen atom or a group selected from the group consisting of hydroxyl, amino, amide, nitro, halogen and organic groups}, a compound represented by the following general formula (2): [Chemical 2] {wherein, R5, R6 and R7 are each independently a hydrogen atom or a group selected from the group consisting of hydroxyl, amino, amide, nitro, halogen and organic groups}, a compound represented by the following general formula (3): [Chemical 3] {wherein, R8 and R9 are each independently a hydrogen atom or a group selected from the group consisting of hydroxyl, amino, amide, nitro, halogen and organic groups}, or the compound represented by the following general formula (4): [Chemical 4] {wherein, X3 is a nitrogen atom or a carbon atom substituted by R11, and R10, R11 and R12 are each independently a hydrogen atom or a group selected from the group consisting of hydroxyl, amino, amide, nitro, halogen and organic groups}, or the compound represented by the following general formula (5): [Chemical 5] {wherein, X4 is a nitrogen atom or a carbon atom substituted by R13, and R13 and R14 are each independently a hydrogen atom or a group selected from the group consisting of hydroxyl, amino, amide, nitro, halogen and organic groups}.

2. The photosensitive resin composition of claim 1, wherein the heterocyclic compound (B) is a compound represented by the following general formula (6): [Chemical 6] {wherein, X5 is a nitrogen atom or a carbon atom substituted by R18, and R15, R16, R17 and R18 are each independently a hydrogen atom or a group selected from hydroxyl, amino, amide, and an organic group having at least one of hydroxyl, amino, amide, carbonyl and carboxyl groups, having 1 to 10 carbon atoms}, and a compound represented by the following general formula (7): [Chemical 7] {wherein, R19, R20 and R21 are each independently a hydrogen atom or a group selected from hydroxyl, amino, amide, and an organic group having at least one of hydroxyl, amino, amide, carbonyl and carboxyl groups, having 1 to 10 carbon atoms}, and a compound represented by the following general formula (8): [Chemical 8] {wherein, R22 and R23 are each independently a hydrogen atom or a group selected from hydroxyl, amino, amide, and an organic group having at least one of hydroxyl, amino, amide, carbonyl, and carboxyl groups, having 1 to 10 carbon atoms}, or a compound represented by the following general formula (9): [Chemistry 9] {wherein, X7 is a nitrogen atom or a carbon atom substituted by R25, and R24, R25, and R26 are each independently a hydrogen atom or a group selected from hydroxyl, amino, amide, and an organic group having at least one of hydroxyl, amino, amide, carbonyl, and carboxyl groups, having 1 to 10 carbon atoms}, or a compound represented by the following general formula (10): [Chemistry 10] {In the formula, X8 is a nitrogen atom or a carbon atom substituted by R27, and R27 and R28 are each independently a hydrogen atom or a group selected from hydroxyl, amino, amide, and organic groups having at least one of hydroxyl, amino, amide, carbonyl, and carboxyl groups with 1 to 10 carbon atoms}.

3. The photosensitive resin composition of claim 1 or 2, wherein the photosensitive resin composition contains the polyimide precursor, the polyimide precursor having a structural unit represented by the following general formula (11): [Chemistry 11] {wherein, X9 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer from 2 to 150, and R29 and R30 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 (12): [Chemistry 12] {wherein, X10 is a tetravalent organic group, Y2 is a divalent organic group, n2 is an integer from 2 to 150}.

4. The photosensitive resin composition of claim 3, wherein in the above general formula (11), at least one of R29 and R30 has a structural unit represented by the following general formula (13): [Chemical 13] {wherein, 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}.

5. 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).

6. The photosensitive resin composition of claim 1 or 2 further contains (D) solvent.

7. The photosensitive resin composition of claim 1 or 2 further contains (E) a photopolymerizable monomer.

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

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

10. The photosensitive resin composition of claim 1 or 2, which contains (H) acid.

11. 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.

12. 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.

13. The method for manufacturing a hardened embossed pattern as claimed in claim 12, wherein the temperature of the heat treatment in step (4) above is 170°C or higher and 350°C or lower.

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

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