Photosensitive resin composition, method for producing cured relief pattern and semiconductor device

Abstract

To provide a photosensitive resin composition that gives a resin layer having high adhesion with no voids occurring at an interface of a Cu layer in contact with a cured photosensitive resin layer, after a high temperature storage test, and a method of forming a cured relief pattern using the photosensitive resin composition, and a semiconductor device having the cured relief pattern.SOLUTION: A photosensitive resin composition gives a cured film with the occurrence of voids prevented at an interface in contact with a Cu layer, after a high temperature storage test, by containing a cyclic compound having a carbonyl group in a photosensitive resin composition of a specific structure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition used for forming relief patterns of insulating materials for electronic components, passivation films, buffer coat films, interlayer insulating films, and the like in semiconductor devices, a method for forming a cured relief pattern using the same, and a semiconductor device. [Background technology]

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

[0003] Semiconductor devices (hereinafter also referred to as "elements") are mounted on printed circuit boards using various methods depending on the purpose. Conventional elements have generally been fabricated using wire bonding, which connects the external terminals (pads) of the element to the lead frame with thin wires. However, as elements have become faster and their operating frequencies have reached GHz, differences in the wiring length of each terminal during mounting have come to affect the operation of the element. As a result, when mounting elements for high-end applications, it has become necessary to accurately control the length of the mounting wiring, and wire bonding has become difficult to meet this requirement.

[0004] To address this issue, flip-chip mounting has been proposed, in which a rewiring layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed on the rewiring layer, and then the chip is flipped over and directly mounted on a printed circuit board (see, for example, Patent Document 1). Because flip-chip mounting allows for precise control of wiring distance, it has been adopted for high-end devices that handle high-speed signals, and for mobile phones and other devices due to its small mounting size, and demand for this technology is rapidly expanding. When materials such as polyimide, polybenzoxazole, and phenolic resin are used for flip-chip mounting, a metal wiring layer formation process is performed after the resin layer pattern is formed. The metal wiring layer is typically formed by plasma etching the surface of the resin layer to roughen it, then forming a metal layer that serves as a plating seed layer by sputtering to a thickness of 1 μm or less, and then electroplating the metal layer using the metal layer as an electrode. In this process, Ti is typically used as the metal for the seed layer, and Cu is used as the metal for the rewiring layer formed by electroplating.

[0005] For such a metal rewiring layer, high adhesion between the rewired metal layer and the resin layer is required after reliability testing. Examples of reliability tests performed here include a high-temperature storage test in which the device is stored in air at a high temperature of 125°C or higher for 100 hours or more, a high-temperature operation test in which the device is stored in air at a temperature of about 125°C for 100 hours or more while wiring and applying a voltage, a temperature cycle test in which the device is cycled between a low temperature state of about -65 to -40°C and a high temperature state of about 125 to 150°C in air, a high-temperature, high-humidity storage test in which the device is stored in a water vapor atmosphere at a temperature of 85°C or higher and a humidity of 85% or higher, a high-temperature, high-humidity bias test in which the same test is performed while wiring and applying a voltage, and a solder reflow test in which the device is passed through a solder reflow oven at 260°C multiple times in air or nitrogen.

[0006] However, in the past, there was a problem in the case of the high-temperature storage test among the reliability tests mentioned above, in that voids were generated at the interface where the rewired Cu layer contacted the resin layer after the test. When voids are generated at the interface between the Cu layer and the resin layer, the adhesion between the two layers is reduced. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2001-338947 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention has been devised in view of the above-described conventional circumstances, and aims to provide a photosensitive resin composition that, after a high-temperature storage test, produces a resin layer with high adhesion without generating voids at the interface where the Cu layer contacts the cured photosensitive resin layer, a method for forming a cured relief pattern using the photosensitive resin composition, and a semiconductor device having the cured relief pattern. [Means for solving the problem]

[0009] The present inventors have found that by incorporating a cyclic compound having a carbonyl group into a photosensitive resin composition, a photosensitive resin composition can be obtained that provides a cured film that is excellent in inhibiting discoloration even on copper or a copper alloy, and have thus completed the present invention.

[0010] [1] (A) 100 parts by mass of at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, novolak, polyhydroxystyrene, and phenolic resin, (B) at least one compound selected from the group consisting of cyclic compounds having two or more carbonyl groups, wherein the carbonyl groups are directly bonded to the cyclic structure, and in the case of a monocyclic compound, one-third or more of the atoms forming the cyclic structure are N atoms, and in the case of a fused cyclic compound, one-third or more of the atoms forming the cyclic structure having the carbonyl group are N atoms, in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the (A) resin; and (C) 1 to 50 parts by mass of a photosensitizer based on 100 parts by mass of the (A) resin, A photosensitive resin composition comprising: [2] The photosensitive resin composition according to [1], wherein the resin (A) is at least one selected from the group consisting of a polyimide precursor having the following general formula (1), a polyamide having the following general formula (4), a polyoxazole precursor having the following general formula (5), a polyimide having the following general formula (6), and a novolak, a polyhydroxystyrene, and a phenolic resin having the following general formula (7). The following general formula (1) is [ka] In the formula, X1 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer of 2 to 150, and R1 and R2 each independently represent a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, an aromatic group, or a group represented by the following general formula (2): [ka] (wherein R3, R4, and R5 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m1 is an integer of 2 to 10), or a saturated aliphatic group having 1 to 4 carbon atoms, or a monovalent organic group represented by the following general formula (3): [ka] (wherein R6, R7, and R8 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m2 is an integer of 2 to 10), and is a monovalent ammonium ion represented by the formula:}, and is a polyamic acid, polyamic acid ester, or polyamic acid salt, which is a precursor of a polyimide represented by the formula: The following general formula (4) [ka] {In the formula, X2 is a trivalent organic group having 6 to 15 carbon atoms, Y2 is a divalent organic group having 6 to 35 carbon atoms and may have the same structure or multiple structures, R9 is an organic group having 3 to 20 carbon atoms and having at least one radically polymerizable unsaturated bond group, and n2 is an integer of 1 to 1,000.} It is a polyamide having a structure represented by The following general formula (5) is [ka] {In the formula, Y3 is a tetravalent organic group having a carbon atom, Y4, X3, and X4 are each independently a divalent organic group having two or more carbon atoms, n3 is an integer of 1 to 1000, n4 is an integer of 0 to 500, n3 / (n3+n4)>0.5, and the arrangement order of the n3 dihydroxydiamide units including X3 and Y3 and the n4 diamide units including X4 and Y4 is not important.} and a polyhydroxyamide, which is a polyoxazole precursor, having a structure represented by the formula: The following general formula (6) is [ka] wherein X5 is a tetravalent to tetratetratetravalent organic group, Y5 is a divalent to ditetradodecavalent organic group, and R 10 and R 11 each independently represents an organic group having at least one group selected from a phenolic hydroxyl group, a sulfonic acid group, or a thiol group, n5 represents an integer of 3 to 200, and m3 and m4 represent integers of 0 to 10. and a polyimide having a structure represented by The following general formula (7) is [ka] wherein a is an integer of 1 to 3, b is an integer of 0 to 3, 1≦(a+b)≦4, and R 12 represents a monovalent substituent selected from the group consisting of a monovalent organic group having 1 to 20 carbon atoms, a halogen atom, a nitro group, and a cyano group, and when b is 2 or 3, a plurality of R 12 may be the same or different, and X represents a divalent aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic group having 3 to 20 carbon atoms, or a group represented by the following general formula (8): [ka] (wherein p is an integer of 1 to 10), and a divalent organic group selected from the group consisting of a divalent alkylene oxide group represented by the formula: [3] The photosensitive resin composition contains a phenolic resin having a repeating unit represented by the general formula (7), and X in the general formula (7) is a repeating unit represented by the following general formula (9): [ka] {where, R 13 , R 14 , R 15 and R 16 are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a monovalent aliphatic group having 1 to 10 carbon atoms in which some or all of the hydrogen atoms have been substituted with fluorine atoms, and n6 is an integer of 0 to 4. When n6 is an integer of 1 to 4, R 17 is a halogen atom, a hydroxyl group, or a monovalent organic group having 1 to 12 carbon atoms, and at least one R 17 is a hydroxyl group, and when n6 is an integer of 2 to 4, multiple R 17 may be the same or different from each other.} and a divalent group represented by the following general formula (10): [ka] {where, R 18 , R 19 , R 20 and R 21 each independently represents a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a monovalent aliphatic group having 1 to 10 carbon atoms in which some or all of the hydrogen atoms have been substituted with fluorine atoms; W represents a single bond, an aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, an alicyclic group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, or a group represented by the following general formula (8): [ka] (wherein p is an integer of 1 to 10), and a divalent alkylene oxide group represented by the following formula (11): [ka] The photosensitive resin composition according to [1] or [2], wherein the divalent organic group is selected from the group consisting of divalent groups represented by the following formula: [4] (1) A step of forming a photosensitive resin layer on a substrate by applying the photosensitive resin composition according to any one of [1] to [3] onto the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) forming a hardened relief pattern by heat treating the relief pattern; 1. A method for producing a cured relief pattern, comprising: [5] The method according to [4], wherein the substrate is made of copper or a copper alloy. [6] A semiconductor device comprising a cured relief pattern obtained by the manufacturing method according to [4] or [5]. [Effects of the Invention]

[0011] According to the present invention, by combining a specific photosensitive resin with a specific compound, it is possible to provide a photosensitive resin composition that produces a photosensitive resin with high adhesion and that does not generate voids at the interface between a Cu layer and a polyimide layer after a high-temperature storage test; a method for forming a cured relief pattern using the photosensitive resin composition; and a semiconductor device having the cured relief pattern. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention will be specifically described below. Throughout this specification, when a plurality of structures represented by the same symbol in a general formula are present in a molecule, they may be the same or different from each other.

[0013] <Photosensitive resin composition> (Aspect A) The present invention comprises, as essential components, 100 parts by mass of (A) at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, as well as novolak, polyhydroxystyrene, and phenolic resin; (B) a cyclic compound having a carbonyl group: 0.01 to 10 parts by mass based on 100 parts by mass of the (A) resin; and (C) a photosensitizer: 1 to 50 parts by mass based on 100 parts by mass of the (A) resin.

[0014] (A) Resin The resin (A) used in the present invention will now be described. The resin (A) of the present invention is primarily composed of at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, and novolak, polyhydroxystyrene, and phenolic resin. Here, "primary component" means that the resin comprises 60% by mass or more, preferably 80% by mass or more, of the total resin. Furthermore, the resin may contain other resins as needed.

[0015] From the viewpoints of heat resistance and mechanical properties after heat treatment, the weight-average molecular weight of these resins is preferably 200 or more, more preferably 5.00 or more, as calculated in terms of polystyrene by gel permeation chromatography. The upper limit is preferably 500,000 or less, and when used as a photosensitive resin composition, from the viewpoint of solubility in a developer, it is more preferably 20,000 or less.

[0016] In the present invention, the resin (A) is a photosensitive resin for forming a relief pattern. The photosensitive resin is used together with a photosensitizer (C) described below to form a photosensitive resin composition, and is a resin that causes a phenomenon of dissolution or insolubilization in the subsequent development step.

[0017] Among the photosensitive resins that can be used, polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, and phenolic resins including novolac and polyhydroxystyrene, polyamic acid, polyamic acid ester, polyamic acid salt, polyamide, polyhydroxyamide, polyimide, and phenolic resin are preferred because the resins obtained after heat treatment have excellent heat resistance and mechanical properties. Furthermore, these photosensitive resins can be selected according to the desired application, such as whether a negative or positive photosensitive resin composition is prepared together with the photosensitizer (C) described below.

[0018] [(A) Polyamic acid, polyamic acid ester, polyamic acid salt] In the photosensitive resin composition of the present invention, one example of the most preferable (A) resin from the viewpoint of heat resistance and photosensitive properties is a resin represented by the general formula (1): [ka] In the formula, X1 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer of 2 to 150, and R1 and R2 each independently represent a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, or a group represented by the general formula (2): [ka] (wherein R3, R4, and R5 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m1 is an integer of 2 to 10), or a saturated aliphatic group having 1 to 4 carbon atoms.}; or The following general formula (3): [ka] (wherein R6, R7, and R8 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m2 is an integer of 2 to 10.) The polyamic acid, polyamic acid ester, or polyamic acid salt is a precursor of a polyimide represented by the formula (I). The polyimide precursor is converted into a polyimide by heating (for example, at 200° C. or higher) for cyclization. The polyimide precursor is suitable for use in a negative-type photosensitive resin composition.

[0019] In the above general formula (1), the tetravalent organic group represented by X1 is preferably an organic group having 6 to 40 carbon atoms, from the viewpoint of achieving both heat resistance and photosensitive properties, and more preferably an aromatic group in which the -COOR1 group, the -COOR2 group, and the -CONH- group are in the ortho position relative to each other, or an alicyclic aliphatic group. The tetravalent organic group represented by X1 is preferably an organic group having 6 to 40 carbon atoms containing an aromatic ring, and more preferably a group represented by the following formula (30): [ka] {In the formula, R25 is a monovalent group selected from a hydrogen atom, a fluorine atom, a C1 to C10 hydrocarbon group, and a C1 to C10 fluorinated hydrocarbon group, l is an integer selected from 0 to 2, m is an integer selected from 0 to 3, and n is an integer selected from 0 to 4.} Examples of suitable X1 structures include, but are not limited to, the following: In addition, the structure of X1 may be one type or a combination of two or more types. X1 groups having the structure represented by the above formula are particularly preferred in that they achieve both heat resistance and photosensitive properties.

[0020] In the above general formula (1), the divalent organic group represented by Y1 is preferably an aromatic group having 6 to 40 carbon atoms, in order to achieve both heat resistance and photosensitive properties, and is, for example, a group represented by the following formula (31): [ka] {In the formula, R25 is a monovalent group selected from a hydrogen atom, a fluorine atom, a C1 to C10 hydrocarbon group, and a C1 to C10 fluorine-containing hydrocarbon group, and n is an integer selected from 0 to 4.} Examples of the structure represented by the formula (31) include, but are not limited to, the structure represented by the formula (31). The structure represented by the formula (31) may be one type or a combination of two or more types. The Y1 group having the structure represented by the formula (31) is particularly preferred in that it has both heat resistance and photosensitive properties.

[0021] In the general formula (2), R3 is preferably a hydrogen atom or a methyl group, and R4 and R5 are preferably hydrogen atoms from the viewpoint of photosensitivity. Also, m1 is an integer of 2 or more and 10 or less, preferably an integer of 2 or more and 4 or less, from the viewpoint of photosensitivity.

[0022] When a polyimide precursor is used as the (A) resin, methods for imparting photosensitivity to a photosensitive resin composition include an ester bond type and an ionic bond type. The former is a method in which a photopolymerizable group, i.e., a compound having an olefinic double bond, is introduced into the side chain of the polyimide precursor via an ester bond, while the latter is a method in which a carboxyl group of the polyimide precursor is bonded to an amino group of a (meth)acrylic compound having an amino group via an ionic bond to impart a photopolymerizable group.

[0023] The ester bond-type polyimide precursor can be obtained by first reacting a tetracarboxylic acid dianhydride containing the above-mentioned tetravalent organic group X1 with an alcohol having a photopolymerizable unsaturated double bond and, optionally, a saturated aliphatic alcohol having 1 to 4 carbon atoms to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester), and then subjecting this to amide polycondensation with a diamine containing the above-mentioned divalent organic group Y1.

[0024] (Preparation of Acid / Ester Forms) In the present invention, examples of the tetracarboxylic acid dianhydride containing a tetravalent organic group X1 that is suitably used for preparing an ester bond type polyimide precursor include the tetracarboxylic acid dianhydride represented by the above general formula (30), as well as, for example, pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic acid dianhydride, benzophenone-3,3',4,4'-tetracarboxylic acid dianhydride, biphenyl-3,3',4,4'-tetracarboxylic acid dianhydride, and diphenylsulfone-3,3',4,4'-tetracarboxylic acid dianhydride. Examples of suitable dianhydrides include diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, and preferably include pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, and biphenyl-3,3',4,4'-tetracarboxylic dianhydride, but are not limited to these. These may be used alone or in combination of two or more.

[0025] In the present invention, examples of alcohols having a photopolymerizable unsaturated double bond that are preferably used to prepare an ester bond type polyimide precursor include 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-hydroxy ... Examples of the hydroxypropyl acrylate include 1-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

[0026] The above alcohols may also be partially mixed with saturated aliphatic alcohols having 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol.

[0027] The tetracarboxylic dianhydride suitable for the present invention and the alcohol described above are dissolved and mixed with stirring in a solvent as described below at a temperature of 20 to 50°C for 4 to 10 hours in the presence of a basic catalyst such as pyridine, whereby the esterification reaction of the acid anhydride proceeds, and the desired acid / ester form can be obtained.

[0028] (Preparation of Polyimide Precursor) The acid / ester compound (typically a solution in a solvent described below) is mixed with a suitable dehydration condensation agent, such as dicyclocarbodiimide (e.g., dicyclohexylcarbodiimide), 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, or N,N'-disuccinimidyl carbonate, under ice cooling to convert the acid / ester compound into a polyanhydride. A diamine containing a divalent organic group Y1, as preferred in the present invention, dissolved or dispersed in a separate solvent is then added dropwise to the resulting mixture to carry out amide polycondensation, thereby obtaining the desired polyimide precursor. Alternatively, the acid moiety of the acid / ester compound can be converted into an acid chloride using thionyl chloride or the like, followed by reaction with a diamine compound in the presence of a base such as pyridine, thereby obtaining the desired polyimide precursor.

[0029] Diamines containing a divalent organic group Y1 that are preferably used in the present invention include diamines having a structure represented by the above general formula (31), as well as, for example, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4' -diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene,

[0030] 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl) 2,2-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, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, and those in which some of the hydrogen atoms on the benzene ring are replaced by methyl groups, ethyl groups, hydroxymethyl groups, or the like. those substituted with a methyl group, a hydroxyethyl group, a halogen, or the like, 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'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, Examples of the fluorinated aromatic hydrocarbon include, but are not limited to, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, and the like, preferably p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, and the like, and mixtures thereof.

[0031] Furthermore, in order to improve the adhesion between various substrates and the resin layer formed on a substrate by applying the photosensitive resin composition of the present invention to the substrate, diaminosiloxanes such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane can also be copolymerized when preparing the polyimide precursor.

[0032] After the amide polycondensation reaction is completed, the water-absorbing by-product of the dehydrating condensing agent coexisting in the reaction solution is filtered off as needed, and then a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is added to the resulting polymer component to precipitate the polymer component, and the polymer is purified by repeating redissolution and reprecipitation procedures, followed by vacuum drying to isolate the desired polyimide precursor. To improve the degree of purification, the polymer solution may be passed through a column packed with an anion and / or cation exchange resin swollen with an appropriate organic solvent to remove ionic impurities.

[0033] On the other hand, the ionic bond-type polyimide precursor is typically obtained by reacting a tetracarboxylic dianhydride with a diamine, in which at least one of R1 and R2 in the general formula (1) is a hydroxyl group.

[0034] The tetracarboxylic dianhydride is preferably a tetracarboxylic anhydride having the structure of the above formula (30), and the diamine is preferably a diamine having the structure of the above formula (31). By adding a (meth)acrylic compound having an amino group, which will be described later, to the obtained polyamide precursor, a photopolymerizable group is imparted by an ionic bond between the carboxyl group and the amino group.

[0035] Preferred examples of the (meth)acrylic compound having an amino group include dialkylaminoalkyl acrylates or methacrylates such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, diethylaminopropyl methacrylate, dimethylaminobutyl acrylate, dimethylaminobutyl methacrylate, diethylaminobutyl acrylate, and diethylaminobutyl methacrylate. Among these, from the viewpoint of photosensitive properties, dialkylaminoalkyl acrylates or methacrylates in which the alkyl group on the amino group has 1 to 10 carbon atoms and the alkyl chain has 1 to 10 carbon atoms are preferred.

[0036] The blending amount of these (meth)acrylic compounds having an amino group is 1 to 20 parts by mass per 100 parts by mass of the (A) resin, and from the viewpoint of photosensitivity characteristics, it is preferably 2 to 15 parts by mass. Blending 1 part by mass or more of the (meth)acrylic compound having an amino group as the (C) photosensitizer per 100 parts by mass of the (A) resin provides excellent photosensitivity, and blending 20 parts by mass or less provides excellent thick-film curing properties.

[0037] The molecular weight of the ester-bonded and ionic-bonded polyimide precursors is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, as measured by gel permeation chromatography (GPC) in terms of polystyrene equivalent weight average molecular weight. A weight average molecular weight of 8,000 or higher provides good mechanical properties, while a weight average molecular weight of 150,000 or lower provides good dispersibility in a developer and good relief pattern resolution. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for GPC. The weight average molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended that the standard monodisperse polystyrene be selected from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko K.K.

[0038] [(A) Polyamide] Another example of a preferable resin (A) in the photosensitive resin composition of the present invention is a resin represented by the following general formula (4): [ka] {In the formula, X2 is a trivalent organic group having 6 to 15 carbon atoms, Y2 is a divalent organic group having 6 to 35 carbon atoms and may have the same structure or multiple structures, R9 is an organic group having 3 to 20 carbon atoms and having at least one radically polymerizable unsaturated bond group, and n2 is an integer of 1 to 1,000.} The polyamide has a structure represented by the following formula: This polyamide is suitable for use in a negative-type photosensitive resin composition.

[0039] In the above general formula (4), the group represented by R9 is preferably a group represented by the following general formula (32): [ka] {where, R 32 is an organic group having at least one radically polymerizable unsaturated bond group having 2 to 19 carbon atoms.} It is preferable that the group is a group represented by the following formula:

[0040] In the above general formula (4), the trivalent organic group represented by X2 is preferably a trivalent organic group having 6 to 15 carbon atoms, for example, a trivalent organic group represented by the following formula (33): [ka] and more preferably an aromatic group obtained by removing the carboxyl group and the amino group from an amino-substituted isophthalic acid structure.

[0041] In the above general formula (4), the divalent organic group represented by Y2 is preferably an organic group having 6 to 35 carbon atoms, and more preferably a cyclic organic group having 1 to 4 aromatic or aliphatic rings which may be substituted, or an aliphatic group or siloxane group which does not have a cyclic structure. Examples of the divalent organic group represented by Y2 include those represented by the following general formula (I) and the following general formulas (34) and (35): [ka] [ka] {where, R 33 and R 34 are each independently one group selected from the group consisting of a hydroxyl group, a methyl group (-CH3), an ethyl group (-C2H5), a propyl group (-C3H7), or a butyl group (-C4H9), and the propyl group and the butyl group include various isomers. [ka] In the formula, m7 represents an integer of 0 to 8, m8 and m9 each independently represent an integer of 0 to 3, and m 10 and m 11 are each independently an integer from 0 to 10, and R 35 and R 36 is a methyl group (-CH3), an ethyl group (-C2H5), a propyl group (-C3H7), a butyl group (-C4H9), or an isomer thereof.

[0042] The aliphatic group or siloxane group having no cyclic structure includes a group represented by the following general formula (36): [ka] {in formula, m 12 is an integer between 2 and 12, and m 13 is an integer from 1 to 3, and m 14 is an integer from 1 to 20, and R 37 , R 38 , R 39 and R 40are each independently an alkyl group having 1 to 3 carbon atoms or an optionally substituted phenyl group.} is mentioned as a preferred example.

[0043] The polyamide resin of the present invention can be synthesized, for example, as follows. (Synthesis of phthalic acid compound-capped compounds) First, one mole of a compound having a trivalent aromatic group X2, such as at least one compound selected from the group consisting of phthalic acid substituted with an amino group, isophthalic acid substituted with an amino group, and terephthalic acid substituted with an amino group (hereinafter referred to as a "phthalic acid compound"), is reacted with one mole of a compound that reacts with an amino group to synthesize a compound in which the amino group of the phthalic acid compound is modified and capped with a group containing a radically polymerizable unsaturated bond (described below) (hereinafter referred to as a "capped phthalic acid compound"). These compounds may be used alone or in combination.

[0044] When a phthalic acid compound is capped with a group containing the radically polymerizable unsaturated bond, negative photosensitivity (photocurability) can be imparted to the polyamide resin.

[0045] The group containing a radically polymerizable unsaturated bond is preferably an organic group containing a radically polymerizable unsaturated bond group having 3 to 20 carbon atoms, and particularly preferably a group containing a methacryloyl group or an acryloyl group.

[0046] The above-mentioned phthalic acid compound-blocked product can be obtained by reacting the amino group of the phthalic acid compound with an acid chloride, isocyanate, epoxy compound, or the like having at least one radically polymerizable unsaturated bond group having 3 to 20 carbon atoms.

[0047] Suitable acid chlorides include (meth)acryloyl chloride, 2-[(meth)acryloyloxy]acetyl chloride, 3-[(meth)acryloyloxy]propionyl chloride, 2-[(meth)acryloyloxy]ethyl chloroformate, 3-[(meth)acryloyloxypropyl]chloroformate, etc. Suitable isocyanates include 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis[(meth)acryloyloxymethyl]ethyl isocyanate, 2-[2-(meth)acryloyloxyethoxy]ethyl isocyanate, etc. Suitable epoxy compounds include glycidyl (meth)acrylate, etc. These may be used alone or in combination, but it is particularly preferred to use methacryloyl chloride and / or 2-(methacryloyloxy)ethyl isocyanate.

[0048] Furthermore, among these phthalic acid compound-blocked products, those in which the phthalic acid compound is 5-aminoisophthalic acid are preferred, since they have excellent photosensitive properties and can provide polyamides with excellent film properties after heat curing.

[0049] The above-mentioned sealing reaction can be carried out by stirring, dissolving, and mixing the phthalic acid compound and the sealing agent in the presence of a basic catalyst such as pyridine or a tin-based catalyst such as di-n-butyltin dilaurate, if necessary, in a solvent as described below.

[0050] Some types of capping agents, such as acid chlorides, produce hydrogen chloride as a by-product during the capping reaction. In this case, in order to prevent contamination of subsequent steps, it is preferable to purify the product appropriately by, for example, reprecipitation with water, washing with water, and drying, or by passing the product through a column filled with an ion exchange resin to remove and reduce ionic components.

[0051] (Polyamide synthesis) The polyamide of the present invention can be obtained by mixing the above-mentioned phthalic acid compound-blocked product and a diamine compound having a divalent organic group Y2 in a solvent such as described below in the presence of a basic catalyst such as pyridine or triethylamine, and then performing amide polycondensation.

[0052] Examples of the amide polycondensation method include a method in which a phthalic acid compound-terminated product is converted into a symmetrical polyacid anhydride using a dehydrating condensing agent and then mixed with a diamine compound; a method in which a phthalic acid compound-terminated product is converted into an acid chloride by a known method and then mixed with a diamine compound; and a method in which a dicarboxylic acid component is reacted with an active esterifying agent in the presence of a dehydrating condensing agent to form an active ester and then mixed with a diamine compound.

[0053] Preferred examples of the dehydration condensation agent include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1'-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate.

[0054] The chlorinating agent includes thionyl chloride.

[0055] Examples of the active esterifying agent include N-hydroxysuccinimide or 1-hydroxybenzotriazole, N-hydroxy-5-norbornene-2,3-dicarboxylic acid imide, 2-hydroxyimino-2-cyanoethyl acetate, and 2-hydroxyimino-2-cyanoacetic acid amide.

[0056] The diamine compound having the organic group Y2 is preferably at least one diamine compound selected from the group consisting of aromatic diamine compounds, aromatic bisaminophenol compounds, alicyclic diamine compounds, linear aliphatic diamine compounds, and siloxane diamine compounds, and multiple compounds can be used in combination as desired.

[0057] Examples of aromatic diamine compounds include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane,

[0058] 3,3'-Diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4- Examples of the diamine compounds include 2,2-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, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, and diamine compounds in which some of the hydrogen atoms on the benzene rings of these compounds have been substituted with one or more groups selected from the group consisting of a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, and a halogen atom.

[0059] Examples of diamine compounds in which the hydrogen atoms on the benzene ring are substituted include 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'-dimethytoxy-4,4'-diaminobiphenyl, and 3,3'-dichloro-4,4'-diaminobiphenyl.

[0060] Examples of aromatic bisaminophenol compounds include 3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-dihydroxy-4,4'-diaminodiphenyl sulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis-(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(3-hydroxy-4-aminophenyl)hexafluoropropane, and bis-(3-hydroxy-4-aminophenyl)methane. 4,4'-dihydroxy-3,3'-diaminodiphenyl ether, 2,5-dihydroxy-1,4-diaminobenzene, 4,6-diaminoresorcinol, 1,1-bis(3-amino-4-hydroxyphenyl)cyclohexane, 4,4-(α-methylbenzylidene)-bis(2-aminophenol), and the like.

[0061] Examples of alicyclic diamine compounds include 1,3-diaminocyclopentane, 1,3-diaminocyclohexane, 1,3-diamino-1-methylcyclohexane, 3,5-diamino-1,1-dimethylcyclohexane, 1,5-diamino-1,3-dimethylcyclohexane, 1,3-diamino-1-methyl-4-isopropylcyclohexane, 1,2-diamino-4-methylcyclohexane, 1,4-diaminocyclohexane, 1,4-diamino-2,5-diethylcyclohexane, and 1,3-bis(aminomethyl)cyclohexyl. Examples of suitable amines include 1,4-bis(aminomethyl)cyclohexane, 2-(3-aminocyclopentyl)-2-propylamine, menthenediamine, isophoronediamine, norbornanediamine, 1-cycloheptene-3,7-diamine, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), 1,4-bis(3-aminopropyl)piperazine, and 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro-[5,5]-undecane.

[0062] Examples of the linear aliphatic diamine compound include hydrocarbon-type diamines such as 1,2-diaminoethane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane, and 1,12-diaminododecane, and alkylene oxide-type diamines such as 2-(2-aminoethoxy)ethylamine, 2,2'-(ethylenedioxy)diethylamine, and bis[2-(2-aminoethoxy)ethyl]ether.

[0063] Examples of the siloxane diamine compound include dimethyl(poly)siloxane diamine, such as PAM-E, KF-8010, and X-22-161A, manufactured by Shin-Etsu Chemical Co., Ltd.

[0064] After the amide polycondensation reaction is completed, precipitates derived from the dehydration condensation agent that have precipitated in the reaction solution are filtered off as needed. Next, a poor solvent for polyamide, such as water, aliphatic lower alcohol, or a mixture thereof, is added to the reaction solution to precipitate the polyamide. The precipitated polyamide is then purified by redissolving it in a solvent and repeating the reprecipitation procedure, followed by vacuum drying to isolate the desired polyamide. To further improve the degree of purification, the polyamide solution may be passed through a column filled with an ion exchange resin to remove ionic impurities.

[0065] The polyamide preferably has a weight-average molecular weight of 7,000 to 70,000, more preferably 10,000 to 50,000, as measured by gel permeation chromatography (GPC) in terms of polystyrene. A weight-average molecular weight of 7,000 or more in terms of polystyrene ensures the basic physical properties of the cured relief pattern. Furthermore, a weight-average molecular weight of 70,000 or less in terms of polystyrene ensures the development solubility required for forming the relief pattern.

[0066] Tetrahydrofuran or N-methyl-2-pyrrolidone is recommended as the eluent for GPC. The weight-average molecular weight can be determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended to select the standard monodisperse polystyrene from Showa Denko's organic solvent-based standard sample, STANDARD SM-105.

[0067] [(A) Polyhydroxyamide] Another example of a preferable resin (A) in the photosensitive resin composition of the present invention is a resin represented by the following general formula (5): [ka] {wherein Y3 is a tetravalent organic group having a carbon atom, preferably a tetravalent organic group having two or more carbon atoms; Y4, X3, and X4 are each independently a divalent organic group having two or more carbon atoms; n3 is an integer from 1 to 1,000; n4 is an integer from 0 to 500; n3 / (n3+n4)>0.5; and the n3 dihydroxydiamide units including X3 and Y3 and the n4 diamide units including X4 and Y4 may be arranged in any order.}

[0068] The polyoxazole precursor is a polymer having n3 dihydroxydiamide units (hereinafter sometimes simply referred to as dihydroxydiamide units) in the above general formula (5), and may also have n4 diamide units (hereinafter sometimes simply referred to as diamide units) in the above general formula (5).

[0069] The number of carbon atoms in X3 is preferably 2 or more and 40 or less in order to obtain photosensitive properties, the number of carbon atoms in X4 is preferably 2 or more and 40 or less in order to obtain photosensitive properties, the number of carbon atoms in Y3 is preferably 2 or more and 40 or less in order to obtain photosensitive properties, and the number of carbon atoms in Y4 is preferably 2 or more and 40 or less in order to obtain photosensitive properties.

[0070] The dihydroxydiamide unit can be synthesized from a diaminodihydroxy compound (preferably a bisaminophenol) having the structure Y(NH)(OH) and a dicarboxylic acid having the structure X(COOH). A typical embodiment will be described below, taking as an example a case where the diaminodihydroxy compound is a bisaminophenol. The two pairs of amino and hydroxy groups of the bisaminophenol are ortho-positioned relative to each other, and the dihydroxydiamide unit undergoes ring closure upon heating at approximately 250 to 400°C, converting to a heat-resistant polyoxazole structure. n3 in general formula (5) is 1 or greater and 1000 or less for the purpose of achieving photosensitivity. n3 is preferably in the range of 2 to 1000, more preferably 3 to 50, and most preferably 3 to 20.

[0071] The polyoxazole precursor may optionally be condensed with n4 of the above diamide units. The diamide units can be formed by synthesis from a diamine having the structure Y(NH) and a dicarboxylic acid having the structure X(COOH). In general formula (5), n is in the range of 0 to 500, and when n is 500 or less, good photosensitive properties can be obtained. n is more preferably in the range of 0 to 10. If the ratio of diamide units to dihydroxydiamide units is too high, solubility in an alkaline aqueous solution used as a developer decreases. Therefore, the value of n / (n+n) in general formula (5) is greater than 0.5, more preferably 0.7 or greater, and most preferably 0.8 or greater.

[0072] Examples of bisaminophenols as diaminodihydroxy compounds having the structure Y3(NH2)2(OH)2 include 3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis-(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoro ... Examples of the bisaminophenols include bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, and 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenols can be used alone or in combination of two or more. The Y3 group in the bisaminophenol can be represented by the following formula (37): [ka] {wherein Rs1 and Rs2 each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, or a trifluoromethyl group} is preferred in terms of photosensitive properties.

[0073] Examples of diamines having the structure Y4(NH2)2 include aromatic diamines, silicon diamines, etc. Among these, examples of aromatic diamines include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4 ,4'-Diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4-methyl-2,4-bis(4-aminophenyl)-1-pentene,

[0074] 4-methyl-2,4-bis(4-aminophenyl)-2-pentene, 1,4-bis(α,α-dimethyl-4-aminobenzyl)benzene, imino-di-p-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4-methyl-2,4-bis(4-aminophenyl)pentane, 5(or 6)-amino-1-(4-aminophenyl)-1,3,3-trimethylindane, bis(p-aminophenyl)phosphine oxide, 4,4'-diaminoazobenzene, 4,4'-diaminodiphenylurea, 4,4'-bis(4-aminophenyl)-2-pentene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]benzophenone, 4,4'-bis(4-aminophenoxy)diphenyl sulfone, 4,4'-bis[4-(α,α-dimethyl-4-aminobenzyl)phenoxy]benzophenone, 4,4'-bis[4-(α,α-dimethyl-4-aminobenzyl)phenoxy]diphenyl sulfone, 4,4'-diaminobiphenyl,

[0075] Examples of aromatic diamines include 4,4'-diaminobenzophenone, phenylindanediamine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, o-toluidine sulfone, 2,2-bis(4-aminophenoxyphenyl)propane, bis(4-aminophenoxyphenyl)sulfone, bis(4-aminophenoxyphenyl)sulfide, 1,4-(4-aminophenoxyphenyl)benzene, 1,3-(4-aminophenoxyphenyl)benzene, 9,9-bis(4-aminophenyl)fluorene, 4,4'-di-(3-aminophenoxy)diphenyl sulfone, 4,4'-diaminobenzanilide, and compounds in which the hydrogen atoms of the aromatic nuclei of these aromatic diamines are substituted with at least one group or atom selected from the group consisting of chlorine atoms, fluorine atoms, bromine atoms, methyl groups, methoxy groups, cyano groups, and phenyl groups.

[0076] Furthermore, silicon diamines can be selected as the diamines to enhance adhesion to the substrate. Examples of silicon diamines include bis(4-aminophenyl)dimethylsilane, bis(4-aminophenyl)tetramethylsiloxane, bis(4-aminophenyl)tetramethyldisiloxane, bis(γ-aminopropyl)tetramethyldisiloxane, 1,4-bis(γ-aminopropyldimethylsilyl)benzene, bis(4-aminobutyl)tetramethyldisiloxane, and bis(γ-aminopropyl)tetraphenyldisiloxane.

[0077] In addition, preferred dicarboxylic acids having the structure X3(COOH)2 or X4(COOH)2 include those in which X3 and X4 are aliphatic or aromatic groups having a linear, branched, or cyclic structure, respectively. Among these, organic groups having 2 to 40 carbon atoms and optionally containing an aromatic or aliphatic ring are preferred, and X3 and X4 are each represented by the following formula (38): [ka] {where, R 41 represents a divalent group selected from the group consisting of -CH2-, -O-, -S-, -SO2-, -CO-, -NHCO-, and -C(CF3)2-. These are preferred in terms of photosensitive properties.

[0078] The polyoxazole precursor may have its terminal groups blocked with a specific organic group. When a polyoxazole precursor blocked with a blocking group is used, the photosensitive resin composition of the present invention is expected to have good mechanical properties (especially elongation) and a good cured relief pattern after heat curing. Suitable examples of such blocking groups include those represented by the following formula (39): [ka] Examples include those represented by the following formula:

[0079] The polystyrene-equivalent weight-average molecular weight of the polyoxazole precursor, as determined by gel permeation chromatography, is preferably 3,000 to 70,000, more preferably 6,000 to 50,000. From the viewpoint of the physical properties of the cured relief pattern, this weight-average molecular weight is preferably 3,000 or more. Furthermore, from the viewpoint of resolution, it is preferably 70,000 or less. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. Furthermore, the molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended that the standard monodisperse polystyrene be selected from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko K.K.

[0080] [(A) Polyimide] Another example of a preferable (A) resin in the photosensitive resin composition of the present invention is a resin represented by the general formula (6): [ka] wherein X5 is a tetravalent to tetratetravalent organic group, Y5 is a divalent to ditetravalent organic group, R 10 and R 11 represents an organic group having at least one group selected from a phenolic hydroxyl group, a sulfonic acid group, or a thiol group, and may be the same or different; n5 is an integer of 3 to 200; and m3 and m4 are integers of 0 to 10. The polyimide has a structure represented by the following general formula (6): Here, the resin represented by the general formula (6) is particularly preferred in that it does not require chemical changes in the heat treatment process in order to exhibit sufficient film properties, and is therefore suitable for treatment at lower temperatures. X5 in the structural unit represented by the general formula (6) is preferably a tetravalent to tetratetravalent organic group having 4 to 40 carbon atoms, and more preferably an organic group having 5 to 40 carbon atoms and containing an aromatic ring or an aliphatic ring, in order to achieve both heat resistance and photosensitive properties.

[0081] The polyimide represented by the general formula (6) can be obtained by reacting a tetracarboxylic acid, the corresponding tetracarboxylic dianhydride, a tetracarboxylic diester dichloride, or the like with a diamine, the corresponding diisocyanate compound, and a trimethylsilylated diamine. Polyimides can be obtained by dehydrating and cyclizing a polyamic acid, which is one of the polyimide precursors generally obtained by reacting a tetracarboxylic dianhydride with a diamine, by heating or chemical treatment with an acid or a base.

[0082] Suitable tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, Pan dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride,

[0083] Aromatic tetracarboxylic dianhydrides such as 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, or aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride and 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, and compounds represented by the following general formula (40): [ka] {where, R 42 represents a group selected from an oxygen atom, C(CF3)2, C(CH3)2, or SO2, and R 43 and R 44 may be the same or different and represent a group selected from a hydrogen atom, a hydroxyl group, or a thiol group.

[0084] Among these, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride,

[0085] Bis(3,4-dicarboxyphenyl)ether dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, and compounds represented by the following general formula (41): [ka] {where, R 45 represents a group selected from an oxygen atom, C(CF3)2, C(CH3)2, or SO2, and R 46 and R 47 may be the same or different and represent a group selected from a hydrogen atom, a hydroxyl group, or a thiol group. Acid dianhydrides having a structure represented by the following formula are preferred. These may be used alone or in combination of two or more.

[0086] Y5 in the general formula (6) above represents a structural component of a diamine, and this diamine represents a divalent to dodecavalent organic group containing an aromatic ring or an aliphatic ring, and among these, an organic group having 5 to 40 carbon atoms is preferred.

[0087] Specific examples of diamines include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl,

[0088] 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, or compounds in which the aromatic ring of these is substituted with an alkyl group or a halogen atom, or aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and compounds represented by the following general formula (42): [ka] {where, R 48 represents a group selected from an oxygen atom, C(CF3)2, C(CH3)2, or SO2, and R 49 ~R 52 may be the same or different and represent a group selected from a hydrogen atom, a hydroxyl group, or a thiol group.

[0089] Among these, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, m-phenylenediamine, p-phenylenediamine, 1,4-bis(4-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)fluorene, and compounds represented by the following general formula (43): [ka] {where, R 53 represents a group selected from an oxygen atom, C(CF3)2, C(CH3)2, or SO2, and R 54 ~R 57 may be the same or different and represent a group selected from a hydrogen atom, a hydroxyl group, or a thiol group. Diamines having the structure represented by the following formula are preferred.

[0090] Among these, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 1,4-bis(4-aminophenoxy)benzene, and compounds represented by the following general formula (44): [ka] {where, R 58 represents a group selected from an oxygen atom, C(CF3)2, C(CH3)2, or SO2, and R 59 and R 60 may be the same or different and represent a group selected from a hydrogen atom, a hydroxyl group, or a thiol group. Particularly preferred are diamines having the structure represented by the following formula: These may be used alone or in combination of two or more.

[0091] R in general formula (6) 10 and R11 represents a phenolic hydroxyl group, a sulfonic acid group, or a thiol group. 10 and R 11 As the alkyl group, a phenolic hydroxyl group, a sulfonic acid group and / or a thiol group can be present.

[0092] R 10 and R 11 By controlling the amount of alkali-soluble groups, the dissolution rate in an alkaline aqueous solution can be changed, and by adjusting this, a photosensitive resin composition having an appropriate dissolution rate can be obtained.

[0093] Furthermore, to improve adhesion to the substrate, aliphatic groups having a siloxane structure may be copolymerized as X5 and Y5 within a range that does not reduce heat resistance.Specific examples include those obtained by copolymerizing 1 to 10 mol % of bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like as a diamine component.

[0094] The polyimide can be synthesized by, for example, reacting a tetracarboxylic dianhydride with a diamine compound (partially substituted with a monoamine end-capping agent) at low temperature, reacting a tetracarboxylic dianhydride with a diamine compound (partially substituted with an acid anhydride, a monoacid chloride compound, or a monoactive ester compound) at low temperature, obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then reacting the diamine (partially substituted with a monoamine end-capping agent) in the presence of a condensing agent, or obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then converting the remaining dicarboxylic acid into an acid chloride and reacting the diamine (partially substituted with a monoamine end-capping agent). The polyimide can then be fully imidized by a known imidization reaction method. Alternatively, the imidization reaction can be terminated midway to partially introduce an imide structure (in this case, a polyamideimide). Alternatively, the fully imidized polymer can be blended with the polyimide precursor to partially introduce an imide structure.

[0095] The polyimide preferably has an imidization rate of 15% or more relative to the total resin constituting the photosensitive resin composition. More preferably, it is 20% or more. Here, the imidization rate refers to the proportion of imidization present in the total resin constituting the photosensitive resin composition. If the imidization rate is less than 15%, the amount of shrinkage during thermal curing becomes large, making it unsuitable for producing thick films.

[0096] The imidization rate can be easily calculated by the following method. First, the infrared absorption spectrum of the polymer is measured to confirm the presence of absorption peaks (near 1780 cm-1 and 1377 cm-1) of the imide structure resulting from polyimide. Next, the polymer is heat-treated at 350°C for 1 hour, and the infrared absorption spectrum after the heat treatment is measured. The peak intensity near 1377 cm-1 is compared with the intensity before the heat treatment to calculate the imidization rate in the polymer before the heat treatment.

[0097] The molecular weight of the polyimide, as measured by gel permeation chromatography in terms of polystyrene equivalent weight average molecular weight, is preferably 3,000 to 200,000, and more preferably 5,000 to 50,000. When the weight average molecular weight is 3,000 or more, the mechanical properties are good, and when it is 50,000 or less, the dispersibility in a developer is good and the resolution performance of the relief pattern is good.

[0098] Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended that the standard monodisperse polystyrene be selected from the organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko K.K. Furthermore, in the present invention, phenolic resins can also be suitably used.

[0099] [(A) Phenolic resin] The phenolic resin in this embodiment refers to a resin having a repeating unit with a phenolic hydroxyl group. (A) The phenolic resin has the advantage that it can be cured at low temperatures (for example, 250°C or lower) because it does not undergo structural changes such as cyclization (imidization) of the polyimide precursor during thermal curing.

[0100] In this embodiment, the weight-average molecular weight of the (A) phenolic resin is preferably 700 to 100,000, more preferably 1,500 to 80,000, and even more preferably 2,000 to 50,000. From the viewpoint of the reflow treatment applicability of the cured film, the weight-average molecular weight is preferably 700 or more, while from the viewpoint of the alkali solubility of the photosensitive resin composition, it is preferably 100,000 or less. In the present disclosure, the weight average molecular weight can be measured by gel permeation chromatography (GPC) and calculated using a calibration curve prepared using standard polystyrene.

[0101] From the viewpoints of solubility in an alkaline aqueous solution, sensitivity and resolution when forming a resist pattern, and residual stress in a cured film, the (A) phenolic resin is selected from novolak, polyhydroxystyrene, and compounds represented by the following general formula (7): [ka] wherein a is an integer of 1 to 3, b is an integer of 0 to 3, 1≦(a+b)≦4, and R 12 represents a monovalent substituent selected from the group consisting of a monovalent organic group having 1 to 20 carbon atoms, a halogen atom, a nitro group, and a cyano group, and when b is 2 or 3, a plurality of R 12 may be the same or different, and X represents a divalent aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic group having 3 to 20 carbon atoms, or a group represented by the following general formula (8): [ka] (wherein p is an integer of 1 to 10), and a divalent organic group selected from the group consisting of a divalent alkylene oxide group represented by the formula: and phenolic resins modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms.

[0102] (Novolac) In this disclosure, novolac refers to any polymer obtained by condensing phenols with formaldehyde in the presence of a catalyst. Generally, novolac can be obtained by condensing 1 mole of phenols with less than 1 mole of formaldehyde. Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, catechol, resorcinol, pyrogallol, α-naphthol, and β-naphthol. Specific examples of novolac include phenol / formaldehyde condensed novolac resin, cresol / formaldehyde condensed novolac resin, and phenol-naphthol / formaldehyde condensed novolac resin.

[0103] The weight-average molecular weight of the novolak is preferably 700 to 100,000, more preferably 1,500 to 80,000, and even more preferably 2,000 to 50,000. From the viewpoint of the reflow treatment applicability of the cured film, the weight-average molecular weight is preferably 700 or more, while from the viewpoint of the alkali solubility of the photosensitive resin composition, it is preferably 100,000 or less.

[0104] (Polyhydroxystyrene) In the present disclosure, polyhydroxystyrene refers to all polymers containing hydroxystyrene as a polymer unit. A preferred example of polyhydroxystyrene is poly(paravinylphenol). Poly(paravinylphenol) refers to all polymers containing paravinylphenol as a polymer unit. Therefore, to constitute polyhydroxystyrene (e.g., poly(paravinylphenol)), polymer units other than hydroxystyrene (e.g., paravinylphenol) can be used, provided that the objectives of the present invention are not violated. In polyhydroxystyrene, the molar ratio of hydroxystyrene units based on the total molar ratio of polymer units is preferably 10 mol% to 99 mol%, more preferably 20 to 97 mol%, and even more preferably 30 to 95 mol%. A ratio of 10 mol% or more is advantageous in terms of the alkali solubility of the photosensitive resin composition, while a ratio of 99 mol% or less is advantageous in terms of the reflow applicability of a cured film obtained by curing a composition containing the copolymerization component described below. Polymer units other than hydroxystyrene (e.g., paravinylphenol) can be any polymer units copolymerizable with hydroxystyrene (e.g., paravinylphenol).Copolymerization components that provide polymerized units other than hydroxystyrene (e.g., paravinylphenol) include, but are not limited to, methyl acrylate, methyl methacrylate, hydroxyethyl acrylate, butyl methacrylate, octyl acrylate, 2-ethoxyethyl methacrylate, t-butyl acrylate, 1,5-pentanediol diacrylate, N,N-diethylaminoethyl acrylate, ethylene glycol diacrylate, 1,3-propanediol diacrylate, decamethylene glycol diacrylate, decamethylene glycol dimethacrylate, 1,4-cyclohexanediol diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripropylene glycol diacrylate, glycerol triacrylate, 2,2-di(p-hydroxyphenyl)-propane dimethacrylate, triethylene glycol diacrylate, polyoxyethyl-2-2-di(p-hydroxyphenyl)-propane dimethacrylate, triethylene glycol diacrylate, esters of acrylic acid such as ethylene glycol dimethacrylate, polyoxypropyl trimethylolpropane triacrylate, ethylene glycol dimethacrylate, butylene glycol dimethacrylate, 1,3-propanediol dimethacrylate, butylene glycol dimethacrylate, 1,3-propanediol dimethacrylate, 1,2,4-butanetriol trimethacrylate, 2,2,4-trimethyl-1,3-pentanediol dimethacrylate, pentaerythritol trimethacrylate, 1-phenylethylene-1,2-dimethacrylate, pentaerythritol tetramethacrylate, trimethylolpropane trimethacrylate, 1,5-pentanediol dimethacrylate, and 1,4-benzenediol dimethacrylate; styrene and substituted styrenes such as 2-methylstyrene and vinyltoluene; vinyl ester monomers such as vinyl acrylate and vinyl methacrylate; and o-vinylphenol, m-vinylphenol, and the like.

[0105] The novolak and polyhydroxystyrene described above may each be used alone or in combination of two or more.

[0106] The weight-average molecular weight of the polyhydroxystyrene is preferably 700 to 100,000, more preferably 1,500 to 80,000, and even more preferably 2,000 to 50,000. From the viewpoint of the reflow treatment applicability of the cured film, the weight-average molecular weight is preferably 700 or more, while from the viewpoint of the alkali solubility of the photosensitive resin composition, it is preferably 100,000 or less.

[0107] (Phenol resin represented by general formula (7)) In this embodiment, the phenolic resin (A) is a phenolic resin represented by the following general formula (7): [ka] wherein a is an integer of 1 to 3, b is an integer of 0 to 3, 1≦(a+b)≦4, and R 12 represents a monovalent substituent selected from the group consisting of a monovalent organic group having 1 to 20 carbon atoms, a halogen atom, a nitro group, and a cyano group, and when b is 2 or 3, a plurality of R 12 may be the same or different, and X represents a divalent aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic group having 3 to 20 carbon atoms, or a group represented by the following general formula (8): [ka] (wherein p is an integer of 1 to 10), and a divalent organic group selected from the group consisting of a divalent alkylene oxide group represented by the formula: {wherein p is an integer of 1 to 10), and a divalent organic group having an aromatic ring and having 6 to 12 carbon atoms. It is also preferable to include a phenolic resin having a repeating unit represented by the formula:}. Phenol resins having the above repeating units are particularly advantageous in that they can be cured at lower temperatures than, for example, conventionally used polyimide resins and polybenzoxazole resins, and can form cured films with good elongation. The above repeating units present in the phenolic resin molecule can be one type or a combination of two or more types.

[0108] In the above general formula (7), R 12 R is a monovalent substituent selected from the group consisting of a monovalent organic group having 1 to 20 carbon atoms, a halogen atom, a nitro group, and a cyano group, from the viewpoint of reactivity during synthesis of the resin of general formula (7). 12 From the viewpoint of alkali solubility, the group is selected from the group consisting of a halogen atom, a nitro group, a cyano group, an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, an aromatic group having 6 to 20 carbon atoms, and a group represented by the following general formula (45): [ka] {where, R 61 , R 62 and R 63 each independently represents a hydrogen atom, an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, an alicyclic group having 3 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms, and R 64 represents a divalent aliphatic group having 1 to 10 carbon atoms, a divalent alicyclic group having 3 to 20 carbon atoms, or a divalent aromatic group having 6 to 20 carbon atoms, which may have an unsaturated bond.

[0109] In this embodiment, in the general formula (7), a is an integer of 1 to 3, preferably 2 from the viewpoints of alkali solubility and elongation. When a is 2, the substitution positions of the hydroxyl groups may be any of the ortho, meta, and para positions. When a is 3, the substitution positions of the hydroxyl groups may be any of the 1,2,3-positions, 1,2,4-positions, and 1,3,5-positions.

[0110] In this embodiment, when a is 1 in the above general formula (7), in order to improve alkali solubility, a phenolic resin selected from novolak and polyhydroxystyrene (hereinafter also referred to as (a2) resin) can be further mixed with a phenolic resin having a repeating unit represented by general formula (7) (hereinafter also referred to as (a1) resin).

[0111] The mixing ratio of the (a1) resin to the (a2) resin is preferably in the range of (a1) / (a2)=10 / 90 to 90 / 10 by mass. From the viewpoints of solubility in an alkaline aqueous solution and elongation of the cured film, this mixing ratio is preferably (a1) / (a2)=10 / 90 to 90 / 10, more preferably (a1) / (a2)=20 / 80 to 80 / 20, and even more preferably (a1) / (a2)=30 / 70 to 70 / 30.

[0112] As the novolac and polyhydroxystyrene as the resin (a2), the same resins as those listed in the above (novolac) and (polyhydroxystyrene) sections can be used.

[0113] In this embodiment, in the general formula (7), b is an integer of 0 to 3, but from the viewpoint of alkali solubility and elongation, it is preferably 0 or 1. When b is 2 or 3, a plurality of R 12 may be the same or different from each other.

[0114] Furthermore, in this embodiment, in the general formula (7), a and b satisfy the relationship 1≦(a+b)≦4.

[0115] In this embodiment, in the above general formula (7), X is a divalent organic group selected from the group consisting of a divalent aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic group having 3 to 20 carbon atoms, an alkylene oxide group represented by the above general formula (8), and a divalent organic group having an aromatic ring having 6 to 12 carbon atoms, from the viewpoint of the shape of the cured relief pattern and the elongation of the cured film. Among these divalent organic groups, X is preferably a divalent organic group represented by the following general formula (9): [ka] {where, R 13 , R 14 , R 15 and R 16 are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a monovalent aliphatic group having 1 to 10 carbon atoms in which some or all of the hydrogen atoms have been substituted with fluorine atoms, and n6 is an integer of 0 to 4. When n6 is an integer of 1 to 4, R 17 is a halogen atom, a hydroxyl group, or a monovalent organic group having 1 to 12 carbon atoms, and at least one R 17 is a hydroxyl group, and when n6 is an integer of 2 to 4, multiple R 17 may be the same or different from each other.} and a divalent group represented by the following general formula (10): [ka] {where, R 18 , R 19 , R 20 and R 21 each independently represents a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a monovalent aliphatic group having 1 to 10 carbon atoms in which some or all of the hydrogen atoms have been substituted with fluorine atoms; W represents a single bond, an aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, an alicyclic group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, or a group represented by the following general formula (8): [ka] (wherein p is an integer of 1 to 10), and a divalent alkylene oxide group represented by the following formula (11): [ka] The divalent organic group X having an aromatic ring with 6 to 12 carbon atoms preferably has a carbon number of 8 to 75, more preferably 8 to 40. The structure of the divalent organic group X having an aromatic ring with 6 to 12 carbon atoms is generally such that, in the general formula (7), an OH group and an optional R 12 This is different from the structure in which the group is bonded to an aromatic ring.

[0116] Furthermore, from the viewpoint of achieving good pattern formability of the resin composition and good elongation of the cured film after curing, the divalent organic group represented by the above general formula (10) may be a divalent organic group represented by the following formula (12): [ka] and more preferably a divalent organic group represented by the following formula (13): [ka] It is particularly preferable that the divalent organic group is represented by the following formula:

[0117] In the structure represented by general formula (7), X is particularly preferably a structure represented by formula (12) or (13), and the proportion of the moiety represented by the structure represented by formula (12) or (13) in X is preferably 20% by mass or more, more preferably 30% by mass or more, from the viewpoint of elongation. From the viewpoint of alkali solubility of the composition, this proportion is preferably 80% by mass or less, more preferably 70% by mass or less.

[0118] Furthermore, among the phenolic resins having a structure represented by the above general formula (7), a structure having both a structure represented by the following general formula (14) and a structure represented by the following general formula (15) in the same resin skeleton is particularly preferred from the viewpoints of the alkali solubility of the composition and the elongation of the cured film. [ka] {where, R 21 is a monovalent group having 1 to 10 carbon atoms selected from the group consisting of hydrocarbon groups and alkoxy groups, n7 is 2 or 3, n8 is an integer of 0 to 2, m5 is an integer of 1 to 500, and 2≦(n7+n8)≦4. When n8 is 2, a plurality of R 21 may be the same or different from each other. [ka] {where, R 22 and R 23 are each independently a monovalent group having 1 to 10 carbon atoms selected from the group consisting of hydrocarbon groups and alkoxy groups, n9 is an integer of 1 to 3, and n 10 is an integer between 0 and 2, and n 11 is an integer between 0 and 3, m6 is an integer between 1 and 500, and 2≦(n9+n 10 )≦4, and n 10 If is 2, multiple R 22 may be the same or different, and n 11 If is 2 or 3, multiple R 23 may be the same or different from each other.

[0119] m5 in the general formula (14) and m6 in the general formula (15) represent the total number of repeating units in the main chain of the phenolic resin. That is, in the (A) phenolic resin, for example, the repeating units in parentheses in the structure represented by the general formula (14) and the repeating units in parentheses in the structure represented by the general formula (15) can be arranged randomly, in blocks, or a combination thereof. m5 and m6 are each independently an integer of 1 to 500, with the lower limit being preferably 2, more preferably 3, and the upper limit being preferably 450, more preferably 400, and even more preferably 350. m5 and m6 are each independently preferably 2 or greater from the viewpoint of toughness of the cured film, and preferably 450 or less from the viewpoint of solubility in an alkaline aqueous solution. The sum of m5 and m6 is preferably 2 or greater, more preferably 4 or greater, and even more preferably 6 or greater from the viewpoint of toughness of the cured film, and is preferably 200 or less, more preferably 175 or less, and even more preferably 150 or less from the viewpoint of solubility in an alkaline aqueous solution.

[0120] In (A) phenolic resins having both the structure represented by general formula (14) and the structure represented by general formula (15) in the same resin skeleton, the higher the molar ratio of the structure represented by general formula (14), the better the film properties after curing and the more excellent the heat resistance. On the other hand, the higher the molar ratio of the structure represented by general formula (15), the better the alkali solubility and the more excellent the pattern shape after curing. Therefore, the ratio m5 / m6 of the structure represented by general formula (14) to the structure represented by general formula (15) is preferably 20 / 80 or more, more preferably 40 / 60 or more, and particularly preferably 50 / 50 or more, from the viewpoint of the film properties after curing. From the viewpoint of alkali solubility and the shape of the cured relief pattern, it is preferably 90 / 10 or less, more preferably 80 / 20 or less, and even more preferably 70 / 30 or less.

[0121] Phenolic resins having a repeating unit represented by general formula (7) typically contain a phenolic compound and a copolymerization component (specifically, one or more compounds selected from the group consisting of compounds having an aldehyde group (including compounds that decompose to produce an aldehyde compound, such as trioxane), compounds having a ketone group, compounds having two methylol groups in the molecule, compounds having two alkoxymethyl groups in the molecule, and compounds having two haloalkyl groups in the molecule), and more typically can be synthesized by polymerizing a monomer component comprising these. For example, a phenolic resin (A) can be obtained by polymerizing a copolymerization component such as an aldehyde compound, a ketone compound, a methylol compound, an alkoxymethyl compound, a diene compound, or a haloalkyl compound with phenol and / or a phenol derivative (hereinafter collectively referred to as a "phenolic compound") as shown below. In this case, in the general formula (7), the OH group and any R 12 The portion represented by the structure in which a group is bonded to an aromatic ring is derived from the phenol compound, and the portion represented by X is derived from the copolymerization component. From the viewpoints of reaction control and the stability of the obtained (A) phenolic resin and photosensitive resin composition, the molar ratio of the phenol compound to the copolymerization component (phenol compound):(copolymerization component) is preferably 5:1 to 1.01:1, and more preferably 2.5:1 to 1.1:1.

[0122] The weight-average molecular weight of the phenolic resin having a repeating unit represented by general formula (7) is preferably 700 to 100,000, more preferably 1,500 to 80,000, and even more preferably 2,000 to 50,000. From the viewpoint of the reflow treatment applicability of the cured film, the weight-average molecular weight is preferably 700 or more, while from the viewpoint of the alkali solubility of the photosensitive resin composition, it is preferably 100,000 or less.

[0123] Examples of phenolic compounds that can be used to obtain a phenolic resin having a repeating unit represented by general formula (7) include cresol, ethylphenol, propylphenol, butylphenol, amylphenol, cyclohexylphenol, hydroxybiphenyl, benzylphenol, nitrobenzylphenol, cyanobenzylphenol, adamantanephenol, nitrophenol, fluorophenol, chlorophenol, bromophenol, trifluoromethylphenol, N-(hydroxyphenyl)-5-norbornene-2,3-dicarboximide, N-(hydroxyphenyl)-5-methyl-5-norbornene-2,3-dicarboximide, trifluoromethylphenol, hydroxybenzoic acid, methyl hydroxybenzoate, ethyl hydroxybenzoate, benzyl hydroxybenzoate, hydroxybenzamide, hydroxybenzaldehyde, hydroxyacetophenone, hydroxybenzophenone, hydroxybenzonitrile, resorcinol, xylenol, catechol, methyl catechol, ethyl catechol, hexyl benzoate, methyl hydroxy ... Benzylcatechol, nitrobenzylcatechol, methylresorcinol, ethylresorcinol, hexylresorcinol, benzylresorcinol, nitrobenzylresorcinol, hydroquinone, caffeic acid, dihydroxybenzoic acid, methyl dihydroxybenzoate, ethyl dihydroxybenzoate, butyl dihydroxybenzoate, propyl dihydroxybenzoate, benzyl dihydroxybenzoate, dihydroxybenzamide, dihydroxybenzaldehyde, dihydroxyacetophenone, dihydroxybenzyl N-benzophenone, dihydroxybenzonitrile, N-(dihydroxyphenyl)-5-norbornene-2,3-dicarboximide, N-(dihydroxyphenyl)-5-methyl-5-norbornene-2,3-dicarboximide, nitrocatechol, fluorocatechol, chlorocatechol, bromocatechol, trifluoromethylcatechol, nitroresorcinol, fluororesorcinol, chlororesorcinol, bromoresorcinol, trifluoromethylresorcinol, pyrogallol, phloroglucinol, 1,2,Examples of the trihydroxybenzoic acid include 4-trihydroxybenzene, trihydroxybenzoic acid, methyl trihydroxybenzoate, ethyl trihydroxybenzoate, butyl trihydroxybenzoate, propyl trihydroxybenzoate, benzyl trihydroxybenzoate, trihydroxybenzamide, trihydroxybenzaldehyde, trihydroxyacetophenone, trihydroxybenzophenone, and trihydroxybenzonitrile.

[0124] Examples of the aldehyde compounds include acetaldehyde, propionaldehyde, pivalaldehyde, butyraldehyde, pentanal, hexanal, trioxane, glyoxal, cyclohexylaldehyde, diphenylacetaldehyde, ethylbutyraldehyde, benzaldehyde, glyoxylic acid, 5-norbornene-2-carboxaldehyde, malondialdehyde, succindialdehyde, glutaraldehyde, salicylaldehyde, naphthaldehyde, and terephthalaldehyde.

[0125] Examples of the ketone compound include acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, dicyclohexyl ketone, dibenzyl ketone, cyclopentanone, cyclohexanone, bicyclohexanone, cyclohexanedione, 3-butyn-2-one, 2-norbornanone, adamantanone, and 2,2-bis(4-oxocyclohexyl)propane.

[0126] Examples of the methylol compound include 2,6-bis(hydroxymethyl)-p-cresol, 2,6-bis(hydroxymethyl)-4-ethylphenol, 2,6-bis(hydroxymethyl)-4-propylphenol, 2,6-bis(hydroxymethyl)-4-n-butylphenol, 2,6-bis(hydroxymethyl)-4-t-butylphenol, 2,6-bis(hydroxymethyl)-4-methoxyphenol, 2,6-bis(hydroxymethyl)-4-ethoxyphenol, 2,6-bis(hydroxymethyl)-4-methyl ... 2,6-bis(hydroxymethyl)-4-propoxyphenol, 2,6-bis(hydroxymethyl)-4-n-butoxyphenol, 2,6-bis(hydroxymethyl)-4-t-butoxyphenol, 1,3-bis(hydroxymethyl)urea, ribitol, arabitol, allitol, 2,2-bis(hydroxymethyl)butyric acid, 2-benzyloxy-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, monoacetin, 2-methyl-2-nitro-1,3- Propanediol, 5-norbornene-2,2-dimethanol, 5-norbornene-2,3-dimethanol, pentaerythritol, 2-phenyl-1,3-propanediol, trimethylolethane, trimethylolpropane, 3,6-bis(hydroxymethyl)durene, 2-nitro-p-xylylene glycol, 1,10-dihydroxydecane, 1,12-dihydroxydodecane, 1,4-bis(hydroxymethyl)cyclohexane, 1,4-bis(hydroxymethyl)cyclohexene, 1,6-bis( (hydroxymethyl)adamantane, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 2,6-bis(hydroxymethyl)-1,4-dimethoxybenzene, 2,3-bis(hydroxymethyl)naphthalene, 2,6-bis(hydroxymethyl)naphthalene, 1,8-bis(hydroxymethyl)anthracene, 2,2'-bis(hydroxymethyl)diphenyl ether, 4,4'-bis(hydroxymethyl)diphenyl ether, 4,4'-bis(hydroxymethyl)diphenyl thioether, 4,Examples of the alkyl acrylate include 4'-bis(hydroxymethyl)benzophenone, 4'-hydroxymethylphenyl 4-hydroxymethylbenzoate, 4'-hydroxymethylanilide 4-hydroxymethylbenzoate, 4,4'-bis(hydroxymethyl)phenylurea, 4,4'-bis(hydroxymethyl)phenylurethane, 1,8-bis(hydroxymethyl)anthracene, 4,4'-bis(hydroxymethyl)biphenyl, 2,2'-dimethyl-4,4'-bis(hydroxymethyl)biphenyl, 2,2-bis(4-hydroxymethylphenyl)propane, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and tetrapropylene glycol.

[0127] Examples of the alkoxymethyl compound include 2,6-bis(methoxymethyl)-p-cresol, 2,6-bis(methoxymethyl)-4-ethylphenol, 2,6-bis(methoxymethyl)-4-propylphenol, 2,6-bis(methoxymethyl)-4-n-butylphenol, 2,6-bis(methoxymethyl)-4-t-butylphenol, 2,6-bis(methoxymethyl)-4-methoxyphenol, 2,6-bis(methoxymethyl)-4-ethoxyphenol, 2,6-bis(methoxymethyl)-4-methyl ... bis(methoxymethyl)-4-propoxyphenol, 2,6-bis(methoxymethyl)-4-n-butoxyphenol, 2,6-bis(methoxymethyl)-4-t-butoxyphenol, 1,3-bis(methoxymethyl)urea, 2,2-bis(methoxymethyl)butyric acid, 2,2-bis(methoxymethyl)-5-norbornene, 2,3-bis(methoxymethyl)-5-norbornene, 1,4-bis(methoxymethyl)cyclohexane, 1,4-bis(methoxymethyl)cyclohexene, 1,6- Bis(methoxymethyl)adamantane, 1,4-bis(methoxymethyl)benzene, 1,3-bis(methoxymethyl)benzene, 2,6-bis(methoxymethyl)-1,4-dimethoxybenzene, 2,3-bis(methoxymethyl)naphthalene, 2,6-bis(methoxymethyl)naphthalene, 1,8-bis(methoxymethyl)anthracene, 2,2'-bis(methoxymethyl)diphenyl ether, 4,4'-bis(methoxymethyl)diphenyl ether, 4,4'-bis(methoxymethyl) Diphenyl thioether, 4,4'-bis(methoxymethyl)benzophenone, 4'-methoxymethylphenyl 4-methoxymethylbenzoate, 4'-methoxymethylanilide 4-methoxymethylbenzoate, 4,4'-bis(methoxymethyl)phenylurea, 4,4'-bis(methoxymethyl)phenylurethane, 1,8-bis(methoxymethyl)anthracene, 4,4'-bis(methoxymethyl)biphenyl, 2,2'-dimethyl-4,4'-bis(methoxymethyl)biphenyl, 2,Examples of the dimethyl ether include 2-bis(4-methoxymethylphenyl)propane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, and tetrapropylene glycol dimethyl ether.

[0128] Examples of the diene compound include butadiene, pentadiene, hexadiene, heptadiene, octadiene, 3-methyl-1,3-butadiene, 1,3-butanediol dimethacrylate, 2,4-hexadiene-1-ol, methylcyclohexadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene, dicyclopentadiene, 1-hydroxydicyclopentadiene, 1-methylcyclopentadiene, methyldicyclopentadiene, diallyl ether, diallyl sulfide, diallyl adipate, 2,5-norbornadiene, tetrahydroindene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, triallyl cyanurate, diallyl isocyanurate, triallyl isocyanurate, and diallylpropyl isocyanurate.

[0129] Examples of the haloalkyl compound include xylene dichloride, bischloromethyldimethoxybenzene, bischloromethyldurene, bischloromethylbiphenyl, bischloromethyl-biphenylcarboxylic acid, bischloromethyl-biphenyldicarboxylic acid, bischloromethyl-methylbiphenyl, bischloromethyl-dimethylbiphenyl, bischloromethylanthracene, ethylene glycol bis(chloroethyl)ether, diethylene glycol bis(chloroethyl)ether, triethylene glycol bis(chloroethyl)ether, and tetraethylene glycol bis(chloroethyl)ether.

[0130] The phenolic resin (A) can be obtained by condensing the phenolic compound with the copolymerization component through dehydration, dehydrohalogenation, or dealcoholization, or by polymerizing the phenolic compound while cleaving the unsaturated bond. A catalyst may be used during polymerization. Examples of acidic catalysts include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, methanesulfonic acid, p-toluenesulfonic acid, dimethyl sulfate, diethyl sulfate, acetic acid, oxalic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid, zinc acetate, boron trifluoride, boron trifluoride-phenol complex, and boron trifluoride-ether complex. On the other hand, examples of alkaline catalysts include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, triethylamine, pyridine, 4-N,N-dimethylaminopyridine, piperidine, piperazine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene, ammonia, and hexamethylenetetramine.

[0131] The amount of catalyst used to obtain a phenolic resin having a repeating structure represented by general formula (7) is preferably in the range of 0.01 mol % to 100 mol % relative to the total number of moles of copolymerization components (i.e., components other than phenolic compounds), preferably the total number of moles of aldehyde compounds, ketone compounds, methylol compounds, alkoxymethyl compounds, diene compounds, and haloalkyl compounds (100 mol %).

[0132] In the synthesis reaction of (A) phenolic resin, the reaction temperature is usually preferably 40°C to 250°C, more preferably 100°C to 200°C, and the reaction time is preferably about 1 hour to 10 hours. If necessary, a solvent that can sufficiently dissolve the resin can be used.

[0133] The phenolic resin having the repeating unit represented by general formula (7) may be obtained by further polymerizing a phenolic compound that is not a raw material for the structure of general formula (7) as long as the effect of the present invention is not impaired. The range that does not impair the effect of the present invention is, for example, 30% or less of the total number of moles of the phenolic compounds that are raw materials for the (A) phenolic resin.

[0134] (Phenol resin modified with a compound having an unsaturated hydrocarbon group with 4 to 100 carbon atoms) The phenolic resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms is a condensation polymerization product of a reaction product (hereinafter also referred to as an "unsaturated hydrocarbon group-modified phenol derivative") between phenol or a derivative thereof and a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms (hereinafter sometimes simply referred to as an "unsaturated hydrocarbon group-containing compound") and an aldehyde, or a reaction product between a phenolic resin and an unsaturated hydrocarbon group-containing compound.

[0135] The phenol derivatives that can be used are the same as those mentioned above as raw materials for the phenol resin having a repeating unit represented by general formula (7).

[0136] The unsaturated hydrocarbon group of the unsaturated hydrocarbon group-containing compound preferably contains two or more unsaturated groups from the viewpoints of residual stress in the cured film and applicability to reflow treatment. Furthermore, from the viewpoints of compatibility when formed into a resin composition and residual stress in the cured film, the unsaturated hydrocarbon group preferably has 4 to 100 carbon atoms, more preferably 8 to 80 carbon atoms, and even more preferably 10 to 60 carbon atoms.

[0137] Examples of unsaturated hydrocarbon group-containing compounds include unsaturated hydrocarbons having 4 to 100 carbon atoms, polybutadiene having a carboxyl group, epoxidized polybutadiene, linoleyl alcohol, oleyl alcohol, unsaturated fatty acids, and unsaturated fatty acid esters. Suitable unsaturated fatty acids include crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, erucic acid, nervonic acid, linoleic acid, α-linolenic acid, eleostearic acid, stearidonic acid, arachidonic acid, eicosapentaenoic acid, sardine acid, and docosahexaenoic acid. Among these, vegetable oils, which are unsaturated fatty acid esters, are particularly preferred from the viewpoint of the elongation and flexibility of the cured film.

[0138] Vegetable oils typically contain esters of glycerin and unsaturated fatty acids and are non-drying oils with an iodine value of 100 or less, semi-drying oils with an iodine value of more than 100 but less than 130, or drying oils with an iodine value of 130 or more. Examples of non-drying oils include olive oil, morning glory seed oil, cashew seed oil, camellia oil, castor oil, and peanut oil. Examples of semi-drying oils include corn oil, cottonseed oil, and sesame oil. Examples of drying oils include tung oil, linseed oil, soybean oil, walnut oil, safflower oil, sunflower oil, perilla oil, and mustard oil. Processed vegetable oils obtained by processing these vegetable oils may also be used.

[0139] Among the above vegetable oils, it is preferable to use non-drying oils from the viewpoint of preventing gelation due to excessive reaction in the reaction between phenol or its derivatives or phenolic resins and vegetable oils, and improving yield. On the other hand, it is preferable to use drying oils from the viewpoint of improving the adhesion, mechanical properties, and thermal shock resistance of the resist pattern. Among drying oils, tung oil, linseed oil, soybean oil, walnut oil, and safflower oil are preferred, and tung oil and linseed oil are more preferred, as they can more effectively and reliably exhibit the effects of the present invention. These vegetable oils can be used alone or in combination of two or more.

[0140] The reaction between phenol or a derivative thereof and an unsaturated hydrocarbon group-containing compound is preferably carried out at 50 to 130°C. From the viewpoint of reducing the residual stress of the cured film, the reaction ratio between phenol or a derivative thereof and an unsaturated hydrocarbon group-containing compound is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass, of the unsaturated hydrocarbon group-containing compound per 100 parts by mass of phenol or a derivative thereof. If the amount of the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease, while if it exceeds 100 parts by mass, the heat resistance of the cured film tends to decrease. In the above reaction, a catalyst such as p-toluenesulfonic acid or trifluoromethanesulfonic acid may be used as needed.

[0141] The unsaturated hydrocarbon group-modified phenol derivative produced by the above reaction is polycondensed with an aldehyde to produce a phenolic resin modified with an unsaturated hydrocarbon group-containing compound. The aldehyde may be selected from the group consisting of formaldehyde, acetaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde, hydroxyphenylacetaldehyde, methoxyphenylacetaldehyde, crotonaldehyde, chloroacetaldehyde, chlorophenylacetaldehyde, acetone, glyceraldehyde, glyoxylic acid, methyl glyoxylate, phenyl glyoxylate, hydroxyphenyl glyoxylate, formylacetic acid, methyl formylacetate, 2-formylpropionic acid, methyl 2-formylpropionate, pyruvic acid, leplicic acid, 4-acetylbutyric acid, acetonedicarboxylic acid, and 3,3'-4,4'-benzophenonetetracarboxylic acid. Furthermore, precursors of formaldehyde such as paraformaldehyde, trioxane, etc. may also be used. These aldehydes may be used alone or in combination of two or more.

[0142] The reaction between the aldehydes and the unsaturated hydrocarbon group-modified phenol derivative is a polycondensation reaction, and conventionally known synthesis conditions for phenolic resins can be used. The reaction is preferably carried out in the presence of a catalyst such as an acid or a base, and from the viewpoint of the degree of polymerization (molecular weight) of the resin, it is more preferable to use an acid catalyst. Examples of acid catalysts include hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, and oxalic acid. These acid catalysts can be used alone or in combination of two or more.

[0143] The reaction is preferably carried out at a temperature of 100 to 120°C. The reaction time varies depending on the type and amount of catalyst used, but is usually 1 to 50 hours. After the reaction is completed, the reaction product is dehydrated under reduced pressure at a temperature of 200°C or less to obtain a phenolic resin modified with an unsaturated hydrocarbon group-containing compound. A solvent such as toluene, xylene, or methanol can be used for the reaction.

[0144] The phenolic resin modified with an unsaturated hydrocarbon group-containing compound can also be obtained by polycondensing the above-mentioned unsaturated hydrocarbon group-modified phenol derivative with an aldehyde together with a compound other than phenol, such as m-xylene. In this case, the molar ratio of the compound other than phenol to the compound obtained by reacting the phenol derivative with the unsaturated hydrocarbon group-containing compound is preferably less than 0.5.

[0145] A phenolic resin modified with an unsaturated hydrocarbon group-containing compound can also be obtained by reacting a phenolic resin with an unsaturated hydrocarbon group-containing compound. The phenolic resin used in this case is a polycondensation product of a phenolic compound (i.e., phenol and / or a phenol derivative) and an aldehyde. In this case, the phenolic derivative and the aldehyde can be the same as those described above, and the phenolic resin can be synthesized under the conventionally known conditions as described above.

[0146] Specific examples of phenolic resins obtained from phenolic compounds and aldehydes, which are suitable for use in forming the phenolic resin modified with the unsaturated hydrocarbon group-containing compound, include phenol / formaldehyde novolac resin, cresol / formaldehyde novolac resin, xylylenol / formaldehyde novolac resin, resorcinol / formaldehyde novolac resin, and phenol-naphthol / formaldehyde novolac resin.

[0147] The unsaturated hydrocarbon group-containing compound to be reacted with the phenol resin may be the same as the unsaturated hydrocarbon group-containing compound described above in relation to the production of the unsaturated hydrocarbon group-modified phenol derivative to be reacted with an aldehyde.

[0148] The reaction between the phenolic resin and the unsaturated hydrocarbon group-containing compound is preferably carried out at 50 to 130°C. Furthermore, from the viewpoint of improving the flexibility of the cured film (resist pattern), the reaction ratio between the phenolic resin and the unsaturated hydrocarbon group-containing compound is preferably 1 to 100 parts by mass of the unsaturated hydrocarbon group-containing compound per 100 parts by mass of the phenolic resin, more preferably 2 to 70 parts by mass, and even more preferably 5 to 50 parts by mass. If the amount of the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease. If the amount of the unsaturated hydrocarbon group-containing compound exceeds 100 parts by mass, the possibility of gelation during the reaction tends to increase, and the heat resistance of the cured film tends to decrease. When the phenolic resin and the unsaturated hydrocarbon group-containing compound are reacted, a catalyst such as p-toluenesulfonic acid or trifluoromethanesulfonic acid may be used as needed. As will be described in detail later, solvents such as toluene, xylene, methanol, and tetrahydrofuran can be used for the reaction.

[0149] A phenolic resin can also be used that has been acid-modified by further reacting a polybasic acid anhydride with the phenolic hydroxyl groups remaining in the phenolic resin modified with the unsaturated hydrocarbon group-containing compound produced by the above method. Acid modification with a polybasic acid anhydride introduces carboxyl groups, further improving the solubility in an alkaline aqueous solution (used as a developer).

[0150] The polybasic acid anhydride is not particularly limited as long as it has an acid anhydride group formed by dehydration condensation of the carboxy groups of a polybasic acid having a plurality of carboxy groups. Examples of the polybasic acid anhydride include dibasic acid anhydrides such as phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride, and trimellitic anhydride, and aromatic tetrabasic acid dianhydrides such as biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenylethertetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic anhydride, and benzophenonetetracarboxylic dianhydride. These may be used alone or in combination of two or more. Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride, and more preferably one or more selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride, and hexahydrophthalic anhydride. In this case, there is an advantage that a resist pattern with a better shape can be formed.

[0151] The reaction between the phenolic hydroxyl group and the polybasic acid anhydride can be carried out at 50 to 130° C. In this reaction, 0.10 to 0.80 mol of the polybasic acid anhydride is preferably reacted with 1 mol of the phenolic hydroxyl group, more preferably 0.15 to 0.60 mol, and even more preferably 0.20 to 0.40 mol. If the amount of the polybasic acid anhydride is less than 0.10 mol, developability tends to decrease, while if it exceeds 0.80 mol, the alkali resistance of the unexposed area tends to decrease.

[0152] In order to speed up the reaction, the reaction may contain a catalyst as needed. Examples of the catalyst include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, and phosphorus compounds such as triphenylphosphine.

[0153] The acid value of the phenolic resin further modified with a polybasic acid anhydride is preferably 30 to 200 mgKOH / g, more preferably 40 to 170 mgKOH / g, and even more preferably 50 to 150 mgKOH / g. If the acid value is less than 30 mgKOH / g, alkaline development tends to take a longer time than when the acid value is in the above range, and if it exceeds 200 mgKOH / g, the developer resistance of the unexposed area tends to decrease compared to when the acid value is in the above range.

[0154] The molecular weight of the phenolic resin modified with an unsaturated hydrocarbon group-containing compound is preferably a weight average molecular weight of 1,000 to 100,000, more preferably 2,000 to 100,000, taking into consideration the solubility in an alkaline aqueous solution and the balance between photosensitive characteristics and physical properties of the cured film.

[0155] The (A) phenolic resin of this embodiment is also preferably a mixture of at least one phenolic resin selected from the group consisting of phenolic resins having a repeating unit represented by general formula (7) above and phenolic resins modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms (hereinafter also referred to as (a3) resin) and a phenolic resin selected from novolak and polyhydroxystyrene (hereinafter also referred to as (a4) resin). The mixing ratio of the (a3) resin to the (a4) resin is, by mass, (a3) / (a4) = 5 / 95 to 95 / 5. From the viewpoints of solubility in alkaline aqueous solutions, sensitivity and resolution during resist pattern formation, residual stress in the cured film, and reflow treatment applicability, this mixing ratio is preferably (a3) / (a4) = 5 / 95 to 95 / 5, more preferably (a3) / (a4) = 10 / 90 to 90 / 10, and even more preferably (a3) / (a4) = 15 / 85 to 85 / 15. As the novolac and polyhydroxystyrene as the (a4) resin, the same resins as those listed in the above (novolac) and (polyhydroxystyrene) sections can be used.

[0156] (B) Cyclic compounds containing carbonyl groups The (B) compound is at least one compound selected from the group consisting of cyclic compounds having two or more carbonyl groups, the carbonyl groups being directly bonded to the cyclic structure, and in the case of a monocyclic compound, at least one-third of the atoms forming the cyclic structure are nitrogen atoms, and in the case of a fused ring compound, at least one-third of the atoms forming the cyclic structure having the carbonyl group are nitrogen atoms. When classified based on the ring structure, at least one compound selected from the group consisting of 5-membered ring compounds, 6-membered ring compounds, fused ring compounds of two 5-membered rings, fused ring compounds of two 5-membered rings, and fused ring compounds of two 6-membered rings is preferred from the viewpoint of migration resistance. By having two or more carbonyl groups, the area of voids on the copper surface can be reduced. Furthermore, from the viewpoints of developability, sensitivity, in-plane uniformity after curing, elongation after reflow, etc., it is preferable to have two or more carbonyl groups. When there are two or more carbonyl groups, the area of voids on the copper surface is significantly reduced compared to when there is one carbonyl group. Furthermore, when there is one carbonyl group, two or more carbonyl groups are preferable from the viewpoints of developability, sensitivity, in-plane uniformity after curing, elongation after reflow, etc.

[0157] Specific examples of (B) compounds include 5-membered ring compounds such as hydantoin, allantoin, and parabanic acid; 6-membered ring compounds such as barbituric acid, 1,3-dimethylbarbituric acid, 1,3-dicyclohexylbarbituric acid, uramil, alloxan, cyanuric acid, and tris(2-hydroxyethyl) isocyanurate; 5-membered ring and 5-membered ring condensed ring compounds such as glycoluril; and 6-membered ring and 5-membered ring condensed ring compounds such as cyclohexyl benzoate. Examples of fused ring compounds include xanthine, 1-methylxanthine, 3-methylxanthine, 8-bromo-3-methylxanthine, theobromine, theophylline, 7-(2-chloroethyl)theophylline, caffeine, uric acid, and 8-azaxanthine, and examples of fused ring compounds of two 6-membered rings include lumazine, 7,8-dimethylalloxazine, and 1,4-dihydro-6-methylquinoxaline-2,3-dione, as well as mixtures thereof. Among these, fused ring compounds are preferred.

[0158] Furthermore, the compound (B) is represented by the following general formula (60): [ka] {In the formula, Rs3, Rs4, and Rs5 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an amino group which may be substituted with an aromatic group, an alkoxy group or hydroxyalkyl group having 1 to 6 carbon atoms, or an alkyl group or aromatic group having 1 to 10 carbon atoms.} A compound represented by the following general formula (61): [ka] {In the formula, Rs6, Rs7, and Rs8 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an amino group which may be substituted with an aromatic group, an alkoxy group or hydroxyalkyl group having 1 to 6 carbon atoms, or an alkyl group or aromatic group having 1 to 10 carbon atoms.} A compound represented by the following general formula (62): [ka] {In the formula, Rs9, Rs10, Rs11, and Rs12 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an amino group which may be substituted with an aromatic group, an alkoxy group or hydroxyalkyl group having 1 to 6 carbon atoms, or an alkyl group or aromatic group having 1 to 10 carbon atoms.} A compound represented by the following general formula (63): [ka] {where, R 21 , R 22 , R 23 and R 24 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an amino group which may be substituted with an aromatic group, an alkoxy group or hydroxyalkyl group having 1 to 6 carbon atoms, or an alkyl group or aromatic group having 1 to 10 carbon atoms.} From the viewpoint of migration resistance, it is preferable that the compound be at least one compound selected from the group consisting of compounds represented by the following formula:

[0159] Specific examples of the compounds represented by the general formulas (70) to (73) include xanthine, 1-methylxanthine, 3-methylxanthine, theobromine, theophylline, caffeine, uric acid, 8-azaxanthine, lumazine, and derivatives thereof.

[0160] The amount of the (B) compound is 0.01 to 10 parts by mass, preferably 0.05 to 2 parts by mass, per 100 parts by mass of the (A) resin. From the viewpoint of migration resistance, it is desirable that the amount be 0.01 part by mass or more, and from the viewpoint of solubility, it is desirable that the amount be less than 10 parts by mass. It is believed that these (B) components, with their carbonyl groups and nitrogen atoms contained in the ring structure, coordinate with copper, changing the surface state of the copper and suppressing copper migration during high-temperature storage tests. In particular, in the case of fused rings, the concerted action of multiple carbonyl groups and nitrogen atoms is thought to enhance migration resistance.

[0161] (C) Photosensitizer The photosensitizer (C) used in the present invention will be explained below. The photosensitizer (C) varies depending on whether the photosensitive resin composition of the present invention is a negative type that mainly uses, for example, a polyimide precursor and / or a polyamide as the resin (A), or a positive type that mainly uses, for example, at least one of a polyoxazole precursor, a soluble polyimide, and a phenolic resin as the resin (A).

[0162] The amount of the (C) photosensitizer in the photosensitive resin composition is 1 to 50 parts by mass relative to 100 parts by mass of the (A) resin. The amount is 1 part by mass or more from the viewpoint of photosensitivity or patterning ability, and 50 parts by mass or less from the viewpoint of curability of the photosensitive resin composition or the physical properties of the cured photosensitive resin layer.

[0163] [(C) Negative-type photosensitizer: photopolymerization initiator and / or photoacid generator] First, the case where a negative tone is desired will be described. In this case, a photopolymerization initiator and / or a photoacid generator is used as the (C) photosensitizer, and the photopolymerization initiator is preferably a photoradical polymerization initiator, and examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone and other benzophenone derivatives, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone and other acetophenone derivatives, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone and other thioxanthone derivatives, benzil, benzil dimethyl ketal, benzyl-β-methoxyethyl acetal and other benzyl derivatives,

[0164] Benzoin, benzoin derivatives such as benzoin methyl ether, 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2- Preferred examples of the photopolymerization initiator include, but are not limited to, oximes such as (o-ethoxycarbonyl)oxime and 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime, N-arylglycines such as N-phenylglycine, peroxides such as benzoyl perchloride, aromatic biimidazoles, titanocenes, and photoacid generators such as α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide. Among the above photopolymerization initiators, oximes are more preferred, particularly in terms of photosensitivity.

[0165] When a photoacid generator is used as the (C) photosensitizer in a negative-tone photosensitive resin composition, it exhibits acidity upon exposure to actinic rays such as ultraviolet light, and by this action, it crosslinks the crosslinking agent (described below) with the resin (A) or polymerizes crosslinking agents themselves. Examples of such photoacid generators include diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonates, nitrobenzyl esters, oximesulfonates, aromatic N-oxyimidosulfonates, aromatic sulfamides, haloalkyl-containing hydrocarbon compounds, haloalkyl-containing heterocyclic compounds, and naphthoquinone diazide-4-sulfonates. Two or more of these compounds can be used in combination, or in combination with other sensitizers, as needed. Among the above photoacid generators, aromatic oximesulfonates and aromatic N-oxyimidosulfonates are more preferred, particularly in terms of photosensitivity.

[0166] The amount of these photosensitizers to be blended is 1 to 50 parts by mass per 100 parts by mass of the (A) resin, and from the viewpoint of photosensitivity, it is preferably 2 to 15 parts by mass. Blending 1 part by mass or more of the (C) photosensitizer per 100 parts by mass of the (A) resin provides excellent photosensitivity, while blending 50 parts by mass or less provides excellent thick-film curing properties.

[0167] Furthermore, as mentioned above, when the (A) resin represented by general formula (1) is an ionic bond type, a (meth)acrylic compound having an amino group is used to provide a photopolymerizable group to the side chain of the (A) resin via an ionic bond. In this case, the (meth)acrylic compound having an amino group is used as the (C) photosensitizer, and as mentioned above, for example, dialkylaminoalkyl acrylates or methacrylates such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, diethylaminopropyl methacrylate, dimethylaminobutyl acrylate, dimethylaminobutyl methacrylate, diethylaminobutyl acrylate, and diethylaminobutyl methacrylate are preferred. Among them, from the viewpoint of photosensitivity, dialkylaminoalkyl acrylates or methacrylates in which the alkyl group on the amino group has 1 to 10 carbon atoms and the alkyl chain has 1 to 10 carbon atoms are preferred.

[0168] The blending amount of these (meth)acrylic compounds having an amino group is 1 to 20 parts by mass per 100 parts by mass of the (A) resin, and from the viewpoint of photosensitivity characteristics, it is preferably 2 to 15 parts by mass. Blending 1 part by mass or more of the (meth)acrylic compound having an amino group as the (C) photosensitizer per 100 parts by mass of the (A) resin provides excellent photosensitivity, and blending 20 parts by mass or less provides excellent thick-film curing properties.

[0169] Next, a case where a positive tone is desired will be described. In this case, a photoacid generator is used as the (C) photosensitizer. Specifically, a diazoquinone compound, an onium salt, a halogen-containing compound, etc. can be used. From the viewpoints of solvent solubility and storage stability, a compound having a diazoquinone structure is preferred.

[0170] [(C) Positive-type photosensitizer: Compound having a quinone diazide group] Examples of compounds having a (C) quinone diazide group (hereinafter also referred to as "(C) quinone diazide compound") include compounds having a 1,2-benzoquinone diazide structure and compounds having a 1,2-naphthoquinone diazide structure, which are known substances from U.S. Pat. Nos. 2,772,972, 2,797,213, and 3,669,658. The (C) quinone diazide compound is preferably at least one compound selected from the group consisting of 1,2-naphthoquinone diazide-4-sulfonic acid esters of polyhydroxy compounds having a specific structure described in detail below and 1,2-naphthoquinone diazide-5-sulfonic acid esters of the polyhydroxy compounds (hereinafter also referred to as "NQD compound").

[0171] The NQD compound can be obtained by converting a naphthoquinone diazide sulfonic acid compound into a sulfonyl chloride with chlorosulfonic acid or thionyl chloride, and then condensing the resulting naphthoquinone diazide sulfonyl chloride with a polyhydroxy compound, according to a conventional method. For example, the polyhydroxy compound can be esterified by reacting a predetermined amount of 1,2-naphthoquinone diazide-5-sulfonyl chloride or 1,2-naphthoquinone diazide-4-sulfonyl chloride with a solvent such as dioxane, acetone, or tetrahydrofuran in the presence of a basic catalyst such as triethylamine, and then washing the resulting product with water and drying it.

[0172] In this embodiment, from the viewpoint of sensitivity and resolution when forming a resist pattern, it is preferable that the (C) compound having a quinonediazide group is a 1,2-naphthoquinonediazide-4-sulfonic acid ester and / or a 1,2-naphthoquinonediazide-5-sulfonic acid ester of a hydroxy compound represented by the following general formulas (70) to (74). The general formula (70) is [ka] {where, X 11 and X 12 each independently represents a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms (preferably 1 to 30 carbon atoms), and X 13 and X 14 each independently represents a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms (preferably 1 to 30 carbon atoms), r1, r2, r3, and r4 each independently represents an integer of 0 to 5, at least one of r3 and r4 is an integer of 1 to 5, (r1+r3)≦5, and (r2+r4)≦5. The general formula (71) is [ka] In the formula, Z represents a tetravalent organic group having 1 to 20 carbon atoms, and X 15 , X 16 , X 17 and X 18 each independently represent a monovalent organic group having 1 to 30 carbon atoms, r6 is an integer of 0 or 1, r5, r7, r8, and r9 are each independently an integer of 0 to 3, r10, r11, r12, and r13 are each independently an integer of 0 to 2, and r10, r11, r12, and r13 are not all 0. And the general formula (72) is [ka] In the formula, r14 represents an integer of 1 to 5, r15 represents an integer of 3 to 8, (r14 × r15) Ls each independently represent a monovalent organic group having 1 to 20 carbon atoms, and (r15) Ts 1and (r15) T 2 each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. And the general formula (73) is [ka] wherein A represents a divalent organic group containing an aliphatic tertiary or quaternary carbon, and M represents a divalent organic group, preferably represented by the following chemical formula: [ka] represents a divalent group selected from the three groups represented by the following formula: Furthermore, the general formula (74) is [ka] wherein r17, r18, r19, and r20 each independently represent an integer of 0 to 2, and at least one of r17, r18, r19, and r20 is 1 or 2; 20 ~X 29 each independently represents a monovalent group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group, and an acyl group, and Y 10 , Y 11 and Y 12 each independently represents a divalent group selected from the group consisting of a single bond, -O-, -S-, -SO-, -SO2-, -CO-, -CO2-, cyclopentylidene, cyclohexylidene, phenylene, and a divalent organic group having 1 to 20 carbon atoms.

[0173] In a further embodiment, in the above general formula (74), Y 10 ~Y 12 are each independently represented by the following general formula: [ka] [ka] [ka] {where, X 30 and X 31 each independently represents at least one monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, and a substituted aryl group; X 32 , X 33 , X 34 and X 35 each independently represents a hydrogen atom or an alkyl group; r21 is an integer of 1 to 5; and X 36 , X 37 , X 38 and X 39 each independently represents a hydrogen atom or an alkyl group. It is preferable that the divalent organic group is selected from the three divalent organic groups represented by the following formula:

[0174] Examples of the compound represented by the above general formula (70) include hydroxy compounds represented by the following formulae (75) to (79). Here, the general formula (75) is [ka] wherein each r16 is independently an integer of 0 to 2, and X 40 each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms; X 40 If there are multiple Xs, 40 may be the same or different from each other, and X 40 is represented by the following general formula:

[0175] [ka] (wherein r18 is an integer of 0 to 2, and X 41 represents a monovalent organic group selected from the group consisting of a hydrogen atom, an alkyl group, and a cycloalkyl group, and when r18 is 2, two X 41 may be the same or different from each other.) It is preferable that the alkyl group is a monovalent organic group represented by the following formula: The general formula (76) is

[0176] [ka] {where, X 42 represents a monovalent organic group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a cycloalkyl group having 1 to 20 carbon atoms. Moreover, the general formula (77) is

[0177] [ka] wherein each r19 is independently an integer of 0 to 2, and X 43 are each independently a hydrogen atom or a group represented by the following general formula:

[0178] [ka] (wherein r20 is an integer of 0 to 2, and X 45 is selected from the group consisting of a hydrogen atom, an alkyl group, and a cycloalkyl group, and when r20 is 2, two X 45 may be the same or different from each other.) and X represents a monovalent organic group represented by the formula: 44 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 1 to 20 carbon atoms.}, and formulas (78) and (79) have the following structures.

[0179] [ka]

[0180] [ka]

[0181] As the compound represented by the general formula (70) above, hydroxy compounds represented by the following formulas (80) to (82) are preferred because they have high sensitivity when converted into NQDs and low precipitation tendency in the photosensitive resin composition.

[0182] The structures of formulas (80) to (82) are as follows: [ka]

[0183] [ka]

[0184] [ka]

[0185] The compound represented by the general formula (76) includes the compound represented by the following formula (83): [ka] The hydroxy compound represented by the formula (I) is preferred because it has high sensitivity when converted into an NQD product and is less prone to precipitation in a photosensitive resin composition.

[0186] As the compound represented by the general formula (77) above, hydroxy compounds represented by the following formulas (84) to (86) are preferred because they have high sensitivity when converted into NQDs and low precipitation tendency in the photosensitive resin composition. The structures of formulas (84) to (86) are as follows: [ka] [ka] [ka]

[0187] In the above general formula (71), Z is not particularly limited as long as it is a tetravalent organic group having 1 to 20 carbon atoms. From the viewpoint of sensitivity, however, Z is preferably a tetravalent organic group having the following formula: [ka] It is preferable that the aryl group is a tetravalent group having a structure represented by the following formula:

[0188] Among the compounds represented by the general formula (71) above, the hydroxy compounds represented by the following formulae (87) to (90) are preferred because they have high sensitivity when converted into NQDs and low precipitation tendency in the photosensitive resin composition. The structures of formulas (87) to (90) are as follows: [ka] [ka] [ka] [ka]

[0189] The compound represented by the general formula (72) above includes compounds represented by the following formula (91): [ka] {wherein each r40 is independently an integer of 0 to 9.} is preferred because it has high sensitivity when converted into an NQD product and low precipitation tendency in a photosensitive resin composition.

[0190] As the compound represented by the above general formula (73), hydroxy compounds represented by the following formulas (92) and (93) are preferred because they have high sensitivity when converted into NQDs and low precipitation tendency in a photosensitive resin composition. The structures of formulas (92) and (93) are as follows: [ka] [ka]

[0191] Specific examples of the compound represented by the general formula (74) include compounds represented by the following formula (94): [ka] NQD products of polyhydroxy compounds represented by the following formula are preferred because they have high sensitivity and low precipitation in photosensitive resin compositions.

[0192] (C) When the compound having a quinone diazide group has a 1,2-naphthoquinone diazide sulfonyl group, this group may be either a 1,2-naphthoquinone diazide-5-sulfonyl group or a 1,2-naphthoquinone diazide-4-sulfonyl group. The 1,2-naphthoquinone diazide-4-sulfonyl group can absorb light in the i-line region of a mercury lamp and is therefore suitable for exposure to i-line. On the other hand, the 1,2-naphthoquinone diazide-5-sulfonyl group can absorb light even in the g-line region of a mercury lamp and is therefore suitable for exposure to g-line.

[0193] In this embodiment, it is preferable to select one or both of a 1,2-naphthoquinone diazide-4-sulfonic acid ester compound and a 1,2-naphthoquinone diazide-5-sulfonic acid ester compound depending on the wavelength of the exposure light. Also, a 1,2-naphthoquinone diazide sulfonic acid ester compound having both a 1,2-naphthoquinone diazide-4-sulfonyl group and a 1,2-naphthoquinone diazide-5-sulfonyl group in the same molecule can be used, or a mixture of a 1,2-naphthoquinone diazide-4-sulfonic acid ester compound and a 1,2-naphthoquinone diazide-5-sulfonic acid ester compound can be used.

[0194] In the compound (C) having a quinone diazide group, the average esterification rate of the naphthoquinone diazide sulfonyl ester of the hydroxy compound is preferably 10% to 100%, more preferably 20% to 100%, from the viewpoint of development contrast.

[0195] Examples of NQD compounds that are preferable in terms of cured film properties such as sensitivity and elongation include those represented by the following general formulae: [ka] wherein Q is a hydrogen atom or a group represented by the following formulae: [ka] However, all Qs cannot be hydrogen atoms at the same time.

[0196] In this case, a naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule can be used as the NQD compound, or a mixture of a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound can be used.

[0197] Among the naphthoquinone diazide sulfonate ester groups described in paragraph

[0196] above, those having the following general formula (95): [ka] Particularly preferred are those represented by the following formula:

[0198] The onium salts include iodonium salts, sulfonium salts, phosphinium salts, phosphonium salts, ammonium salts, and diazonium salts, and are preferably onium salts selected from the group consisting of diaryliodonium salts, triarylsulfonium salts, and trialkylsulfonium salts.

[0199] Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds, and trichloromethyltriazine is preferred.

[0200] The amount of the photoacid generator blended is 1 to 50 parts by mass, and preferably 5 to 30 parts by mass, per 100 parts by mass of the (A) resin. When the amount of the photoacid generator blended as the (C) photosensitizer is 1 part by mass or more, the patterning properties of the photosensitive resin composition are good, and when it is 50 parts by mass or less, the tensile elongation of the film after curing of the photosensitive resin composition is good and there is little development residue (scum) in the exposed area.

[0201] The above NQD compounds may be used alone or in combination of two or more.

[0202] In this embodiment, the amount of the compound having a quinone diazide group (C) in the photosensitive resin composition is 0.1 to 70 parts by mass, preferably 1 to 40 parts by mass, more preferably 3 to 30 parts by mass, and even more preferably 5 to 30 parts by mass, relative to 100 parts by mass of the resin (A). If the amount is 0.1 part by mass or more, good sensitivity can be obtained, while if it is 70 parts by mass or less, the mechanical properties of the cured film can be good.

[0203] The photosensitive resin composition of the present invention may further contain components other than the above components (A) to (C), the preferred components of which vary depending on whether the (A) resin is a negative-type resin using, for example, a polyimide precursor and a polyamide, or a positive-type resin using, for example, a polyoxazole precursor and a soluble polyimide.

[0204] The above-described polyimide precursor resin composition and polyamide resin composition, which are negative-type resin compositions in this embodiment, and the polyoxazole resin composition, soluble polyimide resin composition, and phenolic resin composition, which are positive-type photosensitive resin compositions, can contain a solvent for dissolving these resins.

[0205] Examples of the solvent include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and alcohols, such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, and γ-butyronitrile. Lactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene, etc. Among these, from the viewpoints of resin solubility, resin composition stability, and substrate adhesion, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenyl glycol, and tetrahydrofurfuryl alcohol are preferred.

[0206] Among these solvents, those which completely dissolve the produced polymer are particularly preferred, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, and gamma-butyrolactone.

[0207] Examples of solvents that are more suitable for the phenolic resin include bis(2-methoxyethyl) ether, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, toluene, xylene, γ-butyrolactone, and N-methyl-2-pyrrolidone.

[0208] In the photosensitive resin composition of the present invention, the amount of the solvent used is preferably 100 to 1000 parts by mass, more preferably 120 to 700 parts by mass, and even more preferably 125 to 500 parts by mass, relative to 100 parts by mass of the resin (A).

[0209] The photosensitive resin composition of the present invention may further contain components other than the above components (A) to (C). For example, when the photosensitive resin composition of the present invention is used to form a cured film on a substrate made of copper or a copper alloy, an azole compound and a nitrogen-containing heterocyclic compound such as a purine derivative can be optionally blended in order to suppress discoloration on the copper.

[0210] Examples of azole compounds include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, and triazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, and the like.

[0211] Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or in combination of two or more.

[0212] Specific examples of purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-aminoadenine, 9-methyladenine, 2-hydroxy ... 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, 8-aminoadenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine, and derivatives thereof.

[0213] When the photosensitive resin composition of the present invention contains the above-mentioned azole compound or purine derivative, the blending amount is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) resin, and more preferably 0.5 to 5 parts by mass from the viewpoint of photosensitivity characteristics. When the blending amount of the azole compound relative to 100 parts by mass of the (A) resin is 0.1 part by mass or more, discoloration of the copper or copper alloy surface is suppressed when the photosensitive resin composition of the present invention is formed on copper or a copper alloy, while when the blending amount is 20 parts by mass or less, excellent photosensitivity is achieved.

[0214] In addition, a hindered phenol compound can be optionally blended to suppress discoloration on the copper surface. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), triethylene glycol bis(methyl methyl ester), and 2,5-di-t-butyl-hydroxyquinone. [3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol),

[0215] Pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5 -tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione,

[0216] 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione,

[0217] Examples of the hydroxybenzoates include, but are not limited to, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione. Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione is particularly preferred.

[0218] The amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) resin, and from the viewpoint of photosensitivity, more preferably 0.5 to 10 parts by mass. When the amount of the hindered phenol compound relative to 100 parts by mass of the (A) resin is 0.1 part by mass or more, for example, when the photosensitive resin composition of the present invention is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented, while when the amount is 20 parts by mass or less, excellent photosensitivity is achieved.

[0219] The photosensitive resin composition of the present invention may contain a crosslinking agent. The crosslinking agent may be capable of crosslinking the (A) resin or of forming a crosslinked network by itself when a relief pattern formed using the photosensitive resin composition of the present invention is heat-cured. The crosslinking agent can further enhance the heat resistance and chemical resistance of a cured film formed from the photosensitive resin composition.

[0220] Examples of crosslinking agents include compounds containing a methylol group and / or an alkoxymethyl group, such as Cymel (registered trademark) 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, and 1174; UFR65 and 300; Mycoat 102 and 105 (all manufactured by Mitsui Cytec Co., Ltd.), and Nikalac (registered trademark) MX-270 and -280. , -290; Nikalak MS-11; Nikalak MW-30, -100, -300, -390, -750 (manufactured by Sanwa Chemical Co., Ltd.), DML-OCHP, DML-MBPC, DML-BPC, DML-PEP, DML-34X, DML-PSBP, DML-PTBP, DML-PCHP, DML-POP, DML-PFP, DML-MBOC, BisCMP-F, DML-BisOC-Z, DML-BisOCHP-Z, D Examples of suitable methyl methyl benzoates include ML-BisOC-P, DMOM-PTBT, TMOM-BP, TMOM-BPA, and TML-BPAF-MF (all manufactured by Honshu Chemical Industry Co., Ltd.), benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, and dimethylbis(methoxymethyl)biphenyl.

[0221] In addition, oxirane compounds such as phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol epoxy resins, trisphenol epoxy resins, tetraphenol epoxy resins, phenol-xylylene epoxy resins, naphthol-xylylene epoxy resins, phenol-naphthol epoxy resins, phenol-dicyclopentadiene epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, diethylene glycol diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, 1,1,2,2-tetra(p-hydroxyphenyl)ethane tetraglycidyl ether, glycerol triglycidyl ether, ortho-secondary butylphenyl glycidyl ether, 1,6-bis(2,3-Epoxypropoxy)naphthalene, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, YDB-340, YDB-412, YDF-2001, YDF-2004 (all trade names, manufactured by Nippon Steel Chemical Co., Ltd.), NC-3000-H, EPPN-501H, EOCN-1020, NC-7000L, EPPN-201L, XD-1000, EOCN-4600 (all trade names, manufactured by Nippon Kayaku Co., Ltd.), Epicoat (registered trademark) 1001, Epicoat 1007, Epicoat 1009, Epicoat 5050, Epicoat 5051, Epicoat 1031S , Epicoat 180S65, Epicoat 157H70, YX-315-75 (all trade names, manufactured by Japan Epoxy Resins Co., Ltd.), EHPE3150, Plaxel G402, PUE101, PUE105 (all trade names, manufactured by Daicel Chemical Industries, Ltd.), Epiclon (registered trademark) 830, 850, 1050, N-680, N-690, N-695, N-770, HP-7200, HP-820, EXA-4850-1000 (all trade names, manufactured by DIC Corporation), Denacol (registered trademark) EX-201, EX-251, EX-203 , EX-313, EX-314, EX-321, EX-411, EX-511, EX-512, EX-612, EX-614, EX-614B, EX-711, EX-731, EX-810, EX-911, EM-150 (all trade names, manufactured by Nagase ChemteX Corporation), Epolite (registered trademark) 70P, Epolite 100MF (all trade names, manufactured by Kyoeisha Chemical Co., Ltd.), etc.

[0222] Further examples include isocyanate group-containing compounds such as 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, 1,3-phenylenebismethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, Takenate (registered trademark) 500, 600, Cosmonate (registered trademark) NBDI, and ND (all trade names, manufactured by Mitsui Chemicals, Inc.), and Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, and E402-B80T (all trade names, manufactured by Asahi Kasei Chemicals Corporation).

[0223] In addition, bismaleimide compounds such as 4,4'-diphenylmethane bismaleimide, phenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenyl Examples of the crosslinking agent include bis(4-maleimidophenoxy)phenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, BMI-1000, BMI-1100, BMI-2000, BMI-2300, BMI-3000, BMI-4000, BMI-5100, BMI-7000, BMI-TMH, BMI-6000, and BMI-8000 (all trade names, manufactured by Daiwa Chemical Industry Co., Ltd.), but are not limited to these, as long as they are thermally crosslinkable compounds as described above.

[0224] When a crosslinking agent is used, the amount to be added is preferably 0.5 to 20 parts by mass, more preferably 2 to 10 parts by mass, relative to 100 parts by mass of the (A) resin. When the amount is 0.5 part by mass or more, good heat resistance and chemical resistance are exhibited, while when the amount is 20 parts by mass or less, excellent storage stability is achieved.

[0225] The photosensitive resin composition of the present invention may contain an organotitanium compound. By containing an organotitanium compound, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at a low temperature of about 250°C. In particular, by containing both (B) a cyclic compound having a carbonyl group and an organotitanium compound in the photosensitive resin composition, the cured resin layer has the effect of having excellent substrate adhesion and chemical resistance.

[0226] Usable organotitanium compounds include those in which an organic chemical is bonded to a titanium atom via a covalent or ionic bond.

[0227] Specific examples of the organotitanium compound are shown below in I) to VII): I) Titanium chelate compounds: Among these, titanium chelates having two or more alkoxy groups are more preferred because they provide a negative photosensitive resin composition with good storage stability and a good pattern. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), etc.

[0228] II) Tetraalkoxytitanium compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], etc.

[0229] III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.

[0230] IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.

[0231] V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.

[0232] VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate.

[0233] VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate.

[0234] Among these, it is preferable that the organic titanium compound is at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of exhibiting better chemical resistance. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium is preferred.

[0235] When an organotitanium compound is added, the amount added is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the (A) resin. When the amount added is 0.05 part by mass or more, good heat resistance and chemical resistance are exhibited, while when it is 10 parts by mass or less, excellent storage stability is achieved.

[0236] Furthermore, an adhesion promoter can be optionally blended to improve the adhesion between the film formed using the photosensitive resin composition of the present invention and the substrate. Examples of the adhesion promoter include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propyl)propanol, and the like. silane coupling agents such as benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and 3-(trialkoxysilyl)propyl succinic anhydride; and aluminum-based adhesion promoters such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0237] Among these adhesion aids, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength. When the photosensitive resin composition contains an adhesion aid, the amount of the adhesion aid blended is preferably in the range of 0.5 to 25 parts by mass per 100 parts by mass of the (A) resin.

[0238] Examples of silane coupling agents include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM803, manufactured by Chisso Corporation: trade name Sila-Ace S810), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Corporation: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS1375, manufactured by Azmax Corporation: trade name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Corporation: trade name SIM6473.5C), and mercaptomethylmethyldimethoxysilane (manufactured by Azmax Corporation: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethyltrimethoxysilane triethylethoxydimethoxysilane, 2-mercaptoethyltrippropoxysilane, 2-mercaptoethyltrippropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltrippropoxysilane, N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name) LS3610, manufactured by Azmax Corporation: trade name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Corporation: trade name SIU9058.0), N-(3-diethoxymethoxysilylpropyl)urea, N-(3-ethoxydimethoxysilylpropyl)urea, N-(3-tripropoxysilylpropyl)urea, N-(3-diethoxypropoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-dimethoxypropoxysilylpropyl)urea,N-(3-methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea, N-(3-ethoxydimethoxysilylethyl)urea, N-(3-trippropoxysilylethyl)urea, N-(3-trippropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-trippropoxysilylbutyl)urea, 3-(m-aminophenoxy)propyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0598.0), SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.1), aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.2), 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax Corporation: trade name SIT8396.0), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylmethylethyl)pyridine, (3-triethoxysilylpropyl)-t-butylcarbamate, (3-glycidoxypropyl)triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, tetrakis(methoxyethoxysilane), tetra tetrakis(methoxy-n-propoxysilane), tetrakis(ethoxyethoxysilane), tetrakis(methoxyethoxyethoxysilane), bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane, bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane, bis(triethoxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide, bis[3-(triethoxysilyl)propyl]tetrasulfide,Di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane, bis(pentadionate)titanium-O,O'-bis(oxyethyl)-aminopropyltriethoxysilane, phenyl silanetriol, methylphenyl silanediol, ethylphenyl silanediol, n-propylphenyl silanediol, isopropylphenyl silanediol, n-butyldiphenyl silanediol, isobutylphenyl silanediol, tert-butylphenyl silanediol, diphenyl silanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol , isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol, and the like, but are not limited to these. These may be used alone or in combination.

[0239] Among the above-mentioned silane coupling agents, from the viewpoint of storage stability, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and silane coupling agents represented by the following structures are preferred. [ka]

[0240] When a silane coupling agent is used, the amount to be added is preferably 0.01 to 20 parts by mass per 100 parts by mass of the (A) resin.

[0241] The photosensitive resin composition of the present invention may further contain components other than those described above, the preferred components of which vary depending on whether the (A) resin is a negative-type resin using, for example, a polyimide precursor and a polyamide, or a positive-type resin using, for example, a polyoxazole precursor, a soluble polyimide, a phenolic resin, or the like.

[0242] In the case of a negative type resin (A) using a polyimide precursor or polyamide, a sensitizer can be optionally blended to improve photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylaminocinnamylidene indole. Non, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetone methyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, and the like. These may be used alone or in combination of, for example, 2 to 5 types.

[0243] When the photosensitive resin composition contains a sensitizer for improving photosensitivity, the amount of the sensitizer added is preferably 0.1 to 25 parts by mass per 100 parts by mass of the (A) resin.

[0244] In order to improve the resolution of the relief pattern, a monomer having a photopolymerizable unsaturated bond can be optionally blended. Such a monomer is preferably a (meth)acrylic compound that undergoes a radical polymerization reaction in the presence of a photopolymerization initiator, and includes, but is not limited to, mono- or diacrylates and methacrylates of ethylene glycol or polyethylene glycol, such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, mono- or diacrylates and methacrylates of propylene glycol or polypropylene glycol, mono-, di- or triacrylates and methacrylates of glycerol, cyclohexane diacrylate and dimethacrylate, diacrylate and dimethacrylate of 1,4-butanediol, 1,6-hexane Examples of such compounds include diacrylates and dimethacrylates of diols, diacrylates and dimethacrylates of neopentyl glycol, mono- or diacrylates and methacrylates of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and derivatives thereof, methacrylamide and derivatives thereof, trimethylolpropane triacrylate and methacrylate, di- or triacrylates and methacrylates of glycerol, di-, tri-, or tetraacrylates and methacrylates of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds.

[0245] When the photosensitive resin composition contains the above-mentioned monomer having a photopolymerizable unsaturated bond for improving the resolution of the relief pattern, the blending amount of the monomer having a photopolymerizable unsaturated bond is preferably 1 to 50 parts by mass per 100 parts by mass of the (A) resin.

[0246] In the case of a negative-tone photosensitive resin composition using a polyimide precursor or the like as the (A) resin, a thermal polymerization inhibitor can be optionally blended to improve the viscosity and photosensitivity stability of the photosensitive resin composition, particularly during storage in a solvent-containing solution. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

[0247] The amount of the thermal polymerization inhibitor to be added to the photosensitive resin composition is preferably in the range of 0.005 to 12 parts by mass per 100 parts by mass of the (A) resin.

[0248] On the other hand, in the photosensitive resin composition of the present invention, when a polyoxazole precursor or the like is used as the (A) resin, additives conventionally used in photosensitive resin compositions, such as dyes, surfactants, thermal acid generators, dissolution promoters, and adhesion aids for improving adhesion to substrates, can be added as needed.

[0249] <Dyes, surfactants, adhesive aids> More specifically, examples of the additives include dyes such as methyl violet, crystal violet, and malachite green. Examples of surfactants include nonionic surfactants such as polyglycols (e.g., polypropylene glycol or polyoxyethylene lauryl ether) or their derivatives, fluorine-containing surfactants such as Fluorad (trade name, manufactured by Sumitomo 3M Co., Ltd.), Megafac (trade name, manufactured by Dainippon Ink and Chemicals, Inc.), and Lumiflon (trade name, manufactured by Asahi Glass Co., Ltd.), and organic siloxane surfactants such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso Corporation), and Granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). Examples of adhesive aids include alkylimidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy silane, epoxy polymer, and various silane coupling agents.

[0250] The blending amount of the dye and surfactant is preferably 0.1 to 30 parts by mass per 100 parts by mass of the (A) resin.

[0251] Furthermore, from the viewpoint of achieving good thermal and mechanical properties of the cured product even when the curing temperature is lowered, a thermal acid generator can be optionally blended. The addition of a thermal acid generator is preferred from the viewpoint of providing a cured product with good thermal and mechanical properties even when the curing temperature is lowered.

[0252] Examples of the thermal acid generator include salts formed from a strong acid and a base, such as onium salts, which have the function of generating an acid by heat, and imidosulfonates.

[0253] Examples of onium salts include aryl diazonium salts, diaryliodonium salts such as diphenyliodonium salts; di(alkylaryl)iodonium salts such as di(t-butylphenyl)iodonium salts; trialkylsulfonium salts such as trimethylsulfonium salts; dialkylmonoarylsulfonium salts such as dimethylphenylsulfonium salts; diarylmonoalkyliodonium salts such as diphenylmethylsulfonium salts; and triarylsulfonium salts.

[0254] Among these, di(t-butylphenyl)iodonium salt of paratoluenesulfonic acid, di(t-butylphenyl)iodonium salt of trifluoromethanesulfonic acid, trimethylsulfonium salt of trifluoromethanesulfonic acid, dimethylphenylsulfonium salt of trifluoromethanesulfonic acid, diphenylmethylsulfonium salt of trifluoromethanesulfonic acid, di(t-butylphenyl)iodonium salt of nonafluorobutanesulfonic acid, diphenyliodonium salt of camphorsulfonic acid, diphenyliodonium salt of ethanesulfonic acid, dimethylphenylsulfonium salt of benzenesulfonic acid, diphenylmethylsulfonium salt of toluenesulfonic acid, and the like are preferred.

[0255] Furthermore, as the salt formed from a strong acid and a base, in addition to the onium salts described above, salts formed from the following strong acids and bases, for example, pyridinium salts, can also be used. Examples of strong acids include arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, perfluoroalkylsulfonic acids such as camphorsulfonic acid, trifluoromethanesulfonic acid and nonafluorobutanesulfonic acid, and alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid and butanesulfonic acid. Examples of bases include alkylpyridines such as pyridine and 2,4,6-trimethylpyridine, N-alkylpyridines such as 2-chloro-N-methylpyridine, and halogenated N-alkylpyridines.

[0256] As the imidosulfonate, for example, naphthoyl imidosulfonate, phthalimidosulfonate, etc. can be used, but there is no limitation as long as it is a compound that generates an acid when heated.

[0257] When a thermal acid generator is used, the amount added is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 1 to 5 parts by mass, per 100 parts by mass of the (A) resin.

[0258] In the case of a positive-type photosensitive resin composition, a dissolution promoter can be used to facilitate the removal of unnecessary resin after exposure. For example, a compound having a hydroxyl group or a carboxyl group is preferred. Examples of compounds having a hydroxyl group include the ballast agent used in the naphthoquinone diazide compound described above, as well as paracumylphenol, bisphenols, resorcinols, linear phenolic compounds such as MtrisPC and MtetraPC, non-linear phenolic compounds such as TrisP-HAP, TrisP-PHBA, and TrisP-PA (all manufactured by Honshu Chemical Industry Co., Ltd.), 2- to 5-phenol-substituted diphenylmethane, 1- to 5-phenol-substituted 3,3-diphenylpropane, Examples of the compound include a compound obtained by reacting 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane with 5-norbornene-2,3-dicarboxylic anhydride in a molar ratio of 1:2, a compound obtained by reacting bis-(3-amino-4-hydroxyphenyl)sulfone with 1,2-cyclohexyldicarboxylic anhydride in a molar ratio of 1:2, N-hydroxysuccinimide, N-hydroxyphthalimide, and N-hydroxy-5-norbornene-2,3-dicarboxylic imide. Examples of compounds having a carboxyl group include 3-phenyllactic acid, 4-hydroxyphenyllactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid, 2-methoxy-2-(1-naphthyl)propionic acid, mandelic acid, atrolactic acid, α-methoxyphenylacetic acid, O-acetylmandelic acid, and itaconic acid.

[0259] When a dissolution accelerator is used, the amount to be added is preferably 0.1 to 30 parts by mass per 100 parts by mass of the (A) resin.

[0260] (Mode B) In another aspect of this embodiment, a sulfur-containing compound (B) can be used in place of the cyclic compound (B) having a carbonyl group. More specifically, (A) 100 parts by mass of at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, novolak, polyhydroxystyrene, and phenolic resin, (B) a sulfur-containing compound in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the (A) resin; and (C) 1 to 50 parts by mass of a photosensitizer based on 100 parts by mass of the (A) resin, A photosensitive resin composition comprising:

[0261] In this embodiment, the (A) resin is preferably at least one selected from the group consisting of a polyimide precursor containing the general formula (1), a polyamide containing the general formula (4), a polyoxazole precursor containing the general formula (5), a polyimide containing the general formula (6), and a novolak, a polyhydroxystyrene, and a phenolic resin containing the general formula (7).

[0262] It is also preferred that the photosensitive resin composition contains a phenolic resin having a repeating unit represented by the general formula (7), and that X in the general formula (7) is a divalent organic group selected from the group consisting of the divalent group represented by the general formula (9) and the divalent group represented by the general formula (10).

[0263] By incorporating a sulfur-containing compound into the photosensitive resin composition, it is possible to obtain a photosensitive resin composition that gives a cured film in which the generation of voids at the interface in contact with the Cu layer is suppressed after a high-temperature storage test.

[0264] (B) The sulfur-containing compound is an organic compound containing sulfur, preferably sulfur and nitrogen, and the sulfur is preferably contained as one atom forming a ring structure or as a thiocarbonyl group.

[0265] (B) Examples of compounds that can be used as sulfur-containing compounds include compounds containing sulfur as one atom forming a five-membered ring structure, such as thiazole, 2-aminothiazole, 2-(4-thiazolyl)benzimidazole, 1,3,4-thiadiazole, 2-amino-1,3,4-thiadiazole, 5-amino-1,2,3-thiadiazole, 2,4-thiazolidinedione, benzothiazole, and 2-aminobenzothiazole; compounds containing sulfur as one atom forming a six-membered ring structure, such as thiazole, 2-aminothiazole, 2-(4-thiazolyl)benzimidazole, 1,3,4-thiadiazole, 2-amino-1,3,4-thiadiazole, 5-amino-1,2,3-thiadiazole, 2,4-thiazolidinedione, benzothiazole, and 2-aminobenzothiazole; Examples of compounds containing sulfur as one of the atoms include phenothiazine and N-methylphenothiazine, and examples of compounds containing sulfur as a thiocarbonyl group include rhodanine, N-allylrhodanine, diethylthiourea, dibutylthiourea, dicyclohexylthiourea, diphenylthiourea, 2-thiouracil, 4-thiouracil, 2,4-dithiopyrimidine, 2-thioxanthone, 2-mercapto-4(3H)-quinazolinone, etc. Among these, compounds containing a thiourea structure are preferably used.

[0266] The amount of the sulfur-containing compound (B) is 0.01 to 10 parts by mass, preferably 0.05 to 2 parts by mass, per 100 parts by mass of the resin (A). From the viewpoint of migration resistance, it is desirable that the amount be 0.01 part by mass or more, and from the viewpoint of solubility, it is desirable that the amount be less than 10 parts by mass. Sulfur-containing compounds, especially thiourea, can coordinate with copper via sulfur atoms, thereby changing the state of the copper surface and suppressing copper migration during high-temperature storage tests.

[0267] (Aspect C) In another aspect of this embodiment, in place of the aforementioned (B) cyclic compound having a carbonyl group, (B) at least one compound selected from the following general formulas (B-1), (B-2), and (B-3) can be used. More specifically, (A) 100 parts by mass of at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, novolak, polyhydroxystyrene, and phenolic resin, (B) The following general formula (B-1): [ka] {where, R q1 is represented by an organic group having 1 to 10 carbon atoms and formed from carbon atoms, hydrogen atoms, nitrogen atoms, and oxygen atoms. The following general formula (B-2): [ka] {where, R q2 , R q3 are each an organic group selected from a hydroxyl group, an alkyl group or an alkoxy group having 1 to 10 carbon atoms, and 11 is an integer selected from 1 to 10.}, and The following general formula (B-3): [ka] {where, R q4 , R q5 are an organic group selected from a hydroxyl group, an alkyl group or an alkoxy group having 1 to 10 carbon atoms, and X S is a divalent hydrocarbon group having 1 to 10 carbon atoms, and mm and nn are each an integer selected from 1 to 10.} in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the (A) resin; and (C) 1 to 50 parts by mass of a photosensitizer based on 100 parts by mass of the (A) resin, A photosensitive resin composition comprising:

[0268] In this embodiment, the (A) resin is preferably at least one selected from the group consisting of a polyimide precursor containing the general formula (1), a polyamide containing the general formula (4), a polyoxazole precursor containing the general formula (5), a polyimide containing the general formula (6), and a novolak, a polyhydroxystyrene, and a phenolic resin containing the general formula (7).

[0269] It is also preferred that the photosensitive resin composition contains a phenolic resin having a repeating unit represented by the general formula (7), and that X in the general formula (7) is a divalent organic group selected from the group consisting of the divalent group represented by the general formula (9) and the divalent group represented by the general formula (10).

[0270] (B) The compounds represented by general formulas (B-1), (B-2), and (B-3), preferably (B-1), can change the surface state of copper by interacting with the copper surface through nitrogen atoms or oxygen atoms, thereby suppressing copper migration during high-temperature storage tests.

[0271] Specific examples of (B-1) include organic compounds formed from carbon atoms, hydrogen atoms, nitrogen atoms, and oxygen atoms having a ureido group, such as methylurea, ethylurea, butylurea, phenylurea, hydroxyethylurea, hydantoic acid, allantoin, citrulline, and mixtures thereof.

[0272] (B-2) is a polycondensate of ethylene glycol or a terminally etherified product thereof, and examples thereof include diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, triethylene glycol, triethylene glycol monoethyl ether, triethylene glycol diethyl ether, tetraethylene glycol, tetraethylene glycol dimethyl ether, and mixtures thereof.

[0273] Furthermore, (B-3) is an alkoxypolyethylene oxide ester or alkoxyethyl ester of a dicarboxylic acid, such as bis(2-methoxyethyl) adipate, bis(2-butoxyethyl) adipate, bis(2-ethoxyethyl) sebacate, etc., and mixtures thereof.

[0274] Among these (B) at least one compound selected from general formulas (B-1), (B-2) and (B-3), the compound represented by general formula (B-1) can be preferably used.

[0275] The amount of (B) at least one compound selected from general formulas (B-1), (B-2), and (B-3) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 2 parts by mass, based on 100 parts by mass of (A) resin. From the viewpoint of migration resistance, it is desirable that the amount be 0.01 part by mass or more, and from the viewpoint of solubility, it is desirable that the amount be 10 parts by mass or less.

[0276] (Aspect D) In another aspect of this embodiment, instead of the aforementioned (B) cyclic compound having a carbonyl group, (B) aromatic amine compound can be used, which is at least one selected from the group consisting of aniline derivatives represented by the following general formula (I), triazole derivatives represented by the following general formula (II), and triazole derivatives represented by the following general formula (III). More specifically, (A) 100 parts by mass of at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, and polybenzoxazole; (B) An aromatic amine compound represented by the following general formula (I): [ka] {Ra1 to Ra5 may be the same or different and are each a hydrogen atom, a hydroxyl group, or a saturated hydrocarbon group, unsaturated hydrocarbon group, aromatic group, or amide group having an integer of 1 to 15 carbon atoms; and Ra6 to Ra7 may be the same or different and are each a hydrogen atom, or a saturated hydrocarbon group, unsaturated hydrocarbon group, or aromatic group having an integer of 1 to 5 carbon atoms.} or an aniline derivative represented by the following general formula (II): [ka] {Ra8 to Ra10 may be the same or different and each represent a hydrogen atom, a hydroxyl group, or a saturated hydrocarbon group, unsaturated hydrocarbon group, aromatic group, or amide group having an integer of 1 to 15 carbon atoms.} or a triazole derivative represented by the following general formula (III): [ka] {R11 to R13 may be the same or different and each represent a hydrogen atom, a hydroxyl group, or a saturated hydrocarbon group, unsaturated hydrocarbon group, aromatic group, or amide group having an integer of 1 to 15 carbon atoms.} and 0.01 to 15 parts by mass based on 100 parts by mass of the (A) resin, (C) 1 to 50 parts by mass of a photosensitizer based on 100 parts by mass of the (A) resin, A photosensitive resin composition comprising:

[0277] In this embodiment, the (A) resin is preferably at least one selected from the group consisting of a polyimide precursor containing the general formula (1), a polyamide containing the general formula (4), a polyoxazole precursor containing the general formula (5), and a polyimide containing the general formula (6).

[0278] In the embodiment using (B) an aromatic amine compound, the photosensitive resin may be polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, or polybenzoxazole. Among these, polyamic acid, polyamic acid ester, polyamic acid salt, polyamide, polyhydroxyamide, or polyimide resin is preferably used because the resin after heat treatment has excellent heat resistance and mechanical properties, and polyimide precursor or polyimide resin is most preferably used.

[0279] (B) By using an aromatic amine compound, it is possible to suppress the generation of voids at the interface between the rewired Cu layer and the resin layer after a high-temperature storage test. The reason for this is unclear, but it is thought that the lone electron pair of the aromatic amine compound coordinates with the Cu element on the surface of the Cu layer, blocking the active Cu reaction sites, thereby suppressing the generation of voids.

[0280] (B) The aromatic amine compound is represented by the following general formula (I): [ka] {Ra1 to Ra5 may be the same or different and are a hydrogen atom, a hydroxyl group, or a saturated hydrocarbon group, unsaturated hydrocarbon group, aromatic group, or amide group having a carbon number of 1 or more and an integer of 15 or less, and Ra6 to Ra7 may be the same or different and are a hydrogen atom, or a saturated hydrocarbon group, unsaturated hydrocarbon group, or aromatic group having a carbon number of 1 or more and an integer of 5 or less.} is preferably used.

[0281] Among the aniline derivatives represented by general formula (I), examples of compounds that are preferably used include N-phenylbenzylamine, salicylanilide, naphthol AS, 2-acetamidofluorene, oxanilide, N-allylaniline, N-methylaniline, N-ethylaniline, indoline, Nn-butylaniline, 2-anilinoethanol, 4-methoxyacetanilide, acetoacetanilide, 1,2,3,4-tetrahydroquinoline, tert-butylphenylcarbamate, tert-butyl(3-hydroxyphenyl)carbamate, oxanilide, and N,N'-diphenylethane-1,2-diamine. Among these, N-phenylbenzylamine ((B)-1), N,N'-diphenylethane-1,2-diamine ((B)-2), tert-butylphenylcarbamate ((B)-3), and tert-butyl(3-hydroxyphenyl)carbamate ((B)-4) are particularly preferably used.

[0282] [ka] [ka] [ka] [ka]

[0283] (B) The triazole derivative is represented by the following general formula (II): [ka] {Ra8 to Ra10 may be the same or different and each represent a hydrogen atom, a hydroxyl group, or a saturated hydrocarbon group, unsaturated hydrocarbon group, aromatic group, or amide group having an integer of 1 to 15 carbon atoms.} or a triazole derivative represented by the following general formula (III): [ka] {Ra11 to Ra13 may be the same or different and each represent a hydrogen atom, a hydroxyl group, or a saturated hydrocarbon group, unsaturated hydrocarbon group, aromatic group, or amide group having an integer of 1 to 15 carbon atoms.} A triazole derivative represented by the following formula is preferably used.

[0284] Specific examples of the triazole derivative represented by the general formula (II) that are preferably used include benzotriazole, 1-hydroxybenzotriazole, 1-aminobenzotriazole, 5-methyl-1H-benzotriazole, 1H-1,2,3-triazole, 2-hydroxy-N-(1H-1,2,4-triazol-3-yl)benzamide (ADEKA CORPORATION, ADK STAB CDA-1), 2-(2H-benzo[d][1,2,3]triazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol (ADEKA CORPORATION, ADK STAB LA-29), 2-(2'-hydroxy-3',5'-di-tert-aminophenyl)benzotriazole, and 2-(2'-hydroxy-5'-methylphenyl)benzotriazole. Among these, 2-hydroxy-N-(1H-1,2,4-triazol-3-yl)benzamide ((B)-5) and 2-(2H-benzo[d][1,2,3]triazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol ((B)-6) are particularly preferably used.

[0285] [ka] [ka]

[0286] Specific examples of the triazole derivative represented by the general formula (III) include (4-((1H-1,2,4-triazol-1-ylmethyl)phenyl)methanol, tricyclazole, 1,2,4-1H-triazole, triapentenol, bitertanol, 4-(1H-1,2,4-triazol-1-yl)benzaldehyde, 4-(1H-1,2,4-triazol-1-yl)benzoic acid, 3-(1H-1,2,4-triazol-1-ylmethyl)benzoic acid, 4-[(1H-1,2,4

[0033] Among these, (4-((1H-1,2,4-triazol-1-ylmethyl)phenyl)methanol, 3-(1H-1,2,4-triazol-1-yl)benzaldehyde, 3-(1H-1,2,4-triazol-1-ylmethyl)benzaldehyde, 3-(1H-1,2,4-triazol-1-yl)benzoic acid, and 2-(1H-1,2,4-triazol-1-yl)aniline are preferably used. Among these, (4-((1H-1,2,4-triazol-1-ylmethyl)phenyl)methanol ((B)-7) is particularly preferably used.

[0287] [ka]

[0288] In the aromatic amine compound (B), it is preferable that either the amine atom constituting the aniline derivative or the triazole derivative is a secondary amine in view of its ability to coordinate to Cu element.

[0289] The content of the aromatic amine compound (B) is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 1 to 8 parts by mass, relative to 100 parts by mass of the resin (A). A content higher than this range is not preferred because storage stability decreases, while a content lower than this range is likely to cause voids to form between the copper surface.

[0290] <Method for producing cured relief pattern and semiconductor device> The present invention also provides a method for producing a cured relief pattern, comprising the steps of: (1) forming a resin layer on a substrate by applying the above-described photosensitive resin composition of the present invention onto the substrate; (2) exposing the resin layer to light; (3) developing the exposed resin layer to form a relief pattern; and (4) heat-treating the relief pattern to form a cured relief pattern. Typical aspects of each step are described below.

[0291] (1) A step of forming a resin layer on a substrate by applying a photosensitive resin composition onto the substrate. In this step, the photosensitive resin composition of the present invention is applied to a substrate, and then dried as necessary to form a resin layer. As the application method, a method conventionally used for applying a photosensitive resin composition, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., or spray application using a spray coater, can be used.

[0292] If necessary, the coating film made of the photosensitive resin composition can be dried. Drying methods include air drying, heat drying using an oven or a hot plate, vacuum drying, etc. Specifically, when air drying or heat drying is performed, drying can be carried out under conditions of 20°C to 140°C for 1 minute to 1 hour. As described above, a resin layer can be formed on a substrate.

[0293] (2) A step of exposing the resin layer to light In this step, the resin layer formed above is exposed to an ultraviolet light source or the like using an exposure device such as a contact aligner, mirror projection, or stepper, either directly or through a photomask or reticle having a pattern.

[0294] Thereafter, post-exposure baking (PEB) and / or pre-development baking may be performed at any temperature and time combination as necessary for the purpose of improving photosensitivity, etc. The baking conditions preferably range from 40 to 120°C for a temperature of 10 to 240 seconds, but are not limited to these ranges as long as they do not impair the properties of the photosensitive resin composition of the present invention.

[0295] (3) A step of developing the exposed resin layer to form a relief pattern. In this step, the exposed or unexposed portion of the photosensitive resin layer after exposure is developed and removed. When a negative-type photosensitive resin composition is used (for example, when a polyimide precursor or polyamide is used as the (A) resin), the unexposed portion is developed and removed. When a positive-type photosensitive resin composition is used (for example, when a polyoxazole precursor or a soluble polyimide is used as the (A) resin), the exposed portion is developed and removed. As the development method, any method can be selected from conventionally known photoresist development methods, such as the rotary spray method, the paddle method, and the immersion method accompanied by ultrasonic treatment. Furthermore, after development, post-development baking may be performed at any combination of temperature and time, as necessary, for the purpose of adjusting the shape of the relief pattern, etc.

[0296] The developer used for development is preferably a good solvent for the photosensitive resin composition, or a combination of the good solvent and a poor solvent. For example, in the case of a photosensitive resin composition that is insoluble in an alkaline aqueous solution, good solvents such as N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone are preferred, while poor solvents such as toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water are preferred. When a good solvent and a poor solvent are used in combination, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the photosensitive resin composition. Furthermore, two or more types of each solvent, for example, several types, can also be used in combination.

[0297] On the other hand, in the case of a photosensitive resin composition that is soluble in an alkaline aqueous solution, the developer used for development dissolves and removes the alkaline aqueous solution-soluble polymer, and is typically an alkaline aqueous solution containing an alkaline compound dissolved therein. The alkaline compound dissolved in the developer may be either an inorganic alkaline compound or an organic alkaline compound.

[0298] Examples of the inorganic alkali compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, and ammonia.

[0299] Examples of the organic alkali compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, ethanolamine, and triethanolamine.

[0300] Furthermore, if necessary, the alkaline aqueous solution may contain an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, propanol, or ethylene glycol, a surfactant, a storage stabilizer, or a resin dissolution inhibitor. A relief pattern can be formed in this manner.

[0301] (4) A step of forming a hardened relief pattern by heat treating the relief pattern. In this step, the relief pattern obtained by the development is heated to convert it into a hardened relief pattern. Various methods can be selected for heat curing, such as using a hot plate, an oven, or a temperature-programmable heating oven. Heating can be performed, for example, at 180°C to 400°C for 30 minutes to 5 hours. The atmospheric gas used for heat curing may be air, or an inert gas such as nitrogen or argon.

[0302] <Semiconductor device> The present invention also provides a semiconductor device including a cured relief pattern obtained by the above-described method for producing a cured relief pattern of the present invention. The present invention also provides a semiconductor device including a substrate that is a semiconductor element and a cured relief pattern of resin formed on the substrate by the above-described method for producing a cured relief pattern. The present invention is also applicable to a method for producing a semiconductor device that uses a semiconductor element as the substrate and includes the above-described method for producing a cured relief pattern as part of its process. The semiconductor device of the present invention can be produced by forming the cured relief pattern formed by the above-described method for producing a cured relief pattern as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure, and combining the method with a known method for producing a semiconductor device.

[0303] The photosensitive resin composition of the present invention is useful not only for application to the semiconductor devices described above, but also for applications such as interlayer insulation in multilayer circuits, cover coatings for flexible copper-clad boards, solder resist films, and liquid crystal alignment films. Furthermore, although the above description has been divided into modes A to D, combinations of the modes are also included in the present invention. [Example]

[0304] The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. In the examples, comparative examples, and production examples, the physical properties of the photosensitive resin compositions were measured and evaluated according to the following methods.

[0305] (1) Weight average molecular weight The weight-average molecular weight (Mw) of each resin was measured by gel permeation chromatography (standard polystyrene equivalent). The column used was a "Shodex 805M / 806M series" column manufactured by Showa Denko K.K. The standard monodisperse polystyrene was "Shodex STANDARD SM-105" manufactured by Showa Denko K.K. The developing solvent was N-methyl-2-pyrrolidone, and the detector was "Shodex RI-930" manufactured by Showa Denko K.K.

[0306] (2) Creation of hardened relief patterns on Cu A 6-inch silicon wafer (Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputtered with a 200 nm thick Ti layer and a 400 nm thick Cu layer, in that order, using a sputtering device (L-440S-FHL model, Canon Anelva Corporation). Subsequently, a photosensitive resin composition prepared by the method described below was spin-coated onto the wafer using a coater developer (D-Spin60A model, SOKUDO Co., Ltd.), and dried to form a coating film 6 to 10 μm thick. A test patterned mask was used to apply a parallel beam of 300 mJ / cm2 to this coating film using a parallel beam mask aligner (PLA-501FA model, Canon Inc.). 2 The coating was then spray-developed using a coater developer (D-Spin 60A, manufactured by SOKUDO Co., Ltd.) with cyclopentanone as the developer for negative-tone films and 2.38% TMAH as the developer for positive-tone films, and rinsed with propylene glycol methyl ether acetate for negative-tone films and pure water for positive-tone films to obtain a relief pattern on Cu.

[0307] The wafer with the relief pattern formed on Cu was heat-treated in a temperature-programmable curing furnace (VF-2000 model, manufactured by Koyo Lindberg) in a nitrogen atmosphere at the temperature specified in each example for 2 hours to obtain a cured relief pattern made of resin approximately 6 to 7 μm thick on Cu.

[0308] (3) High temperature storage test and subsequent evaluation of hardened relief patterns on Cu The wafer with the cured relief pattern formed on Cu was heated in air at 150°C for 168 hours using a temperature-programmable curing furnace (VF-2000, manufactured by Koyo Lindberg). Subsequently, the resin layer on Cu was entirely removed by plasma etching using a plasma surface treatment device (EXAM, manufactured by Shinko Seiki Co., Ltd.). The plasma etching conditions were as follows: Output: 133W Gas type and flow rate: O2: 40 ml / min + CF4: 1 ml / min Gas pressure: 50Pa Mode: Hard Mode Etching time: 1800 seconds

[0309] The Cu surface from which the resin layer had been completely removed was observed using a FE-SEM (S-4800 model, manufactured by Hitachi High-Technologies Corporation), and the area ratio of voids on the surface of the Cu layer was calculated using image analysis software (Azo-kun, manufactured by Asahi Kasei Corporation).

[0310] (4) Evaluation of varnish storage stability The photosensitive resin compositions obtained in the examples and comparative examples were left to stand in an atmosphere of 23°C and 50% RH for 3 weeks, and the change in viscosity was observed.

[0311] The viscosity was measured at 23°C using a TV-25 viscometer (manufactured by Toki Sangyo Co., Ltd.). ◯: The viscosity change rate (described below) of the composition after standing is within 10%. ×: The rate of change in viscosity of the composition after standing is more than 10%. Viscosity change rate (%) = {(initial viscosity) - (absolute value of viscosity after standing)} x 100 / (initial viscosity)

[0312] Example A <Production Example A1> ((A) Synthesis of Polymer A as Polyimide Precursor) 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 L separable flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added, and the mixture was stirred at room temperature. 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature and left to stand for 16 hours.

[0313] Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by the addition of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 350 ml of γ-butyrolactone over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour, followed by the addition of 400 ml of γ-butyrolactone. The precipitate that formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0314] The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered off and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 28 L of water to precipitate the polymer. The resulting precipitate was filtered off and then vacuum dried to obtain a powdered polymer (Polymer A). The molecular weight of Polymer A was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight average molecular weight (Mw) was found to be 20,000.

[0315] The weight average molecular weight of the resin obtained in each production example was measured using gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight was calculated in terms of standard polystyrene. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Column: Shodex KD-806M, two in series Mobile phase: 0.1mol / l LiBr / NMP Flow rate: 1ml / min.

[0316] <Production Example A2> ((A) Synthesis of Polymer B as Polyimide Precursor) Except for using 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example A1, a reaction was carried out in the same manner as in the above Production Example A1 to obtain Polymer B. The molecular weight of Polymer B was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 22,000.

[0317] <Production Example A3> ((A) Synthesis of Polymer C as Polyimide Precursor) Except for using 147.8 g of 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl (TFMB) instead of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in Production Example A1, the reaction was carried out in the same manner as in the above Production Example A1 to obtain Polymer C. The molecular weight of Polymer C was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 21,000.

[0318] <Production Example A4> ((A) Synthesis of Polymer D as Polyamide) (Synthesis of phthalic acid compound-capped AIPA-MO) A 5-liter separable flask was charged with 543.5 g of 5-aminoisophthalic acid (hereafter abbreviated as AIPA) and 1,700 g of N-methyl-2-pyrrolidone, which were then mixed and stirred and heated to 50°C in a water bath. 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate diluted with 500 g of γ-butyrolactone was added dropwise to the flask using a dropping funnel, and the mixture was stirred at 50°C for approximately 2 hours.

[0319] After confirming the completion of the reaction (disappearance of 5-aminoisophthalic acid) by low-molecular-weight gel permeation chromatography (hereafter referred to as low-molecular-weight GPC), the reaction solution was poured into 15 L of ion-exchanged water, stirred, and allowed to stand. After waiting for the reaction product to crystallize and precipitate, it was filtered, washed appropriately with water, and then vacuum-dried at 40°C for 48 hours to obtain AIPA-MO, in which the amino group of 5-aminoisophthalic acid and the isocyanate group of 2-methacryloyloxyethyl isocyanate had reacted. The low-molecular-weight GPC purity of the resulting AIPA-MO was approximately 100%.

[0320] (Synthesis of Polymer D) A 2-liter separable flask was charged with 100.89 g (0.3 mol) of the resulting AIPA-MO, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL, mixed, and cooled to 5°C in an ice bath. A solution of 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) dissolved in 125 g of GBL was added dropwise over approximately 20 minutes under ice cooling. Subsequently, a solution of 103.16 g (0.28 mol) of 4,4'-bis(4-aminophenoxy)biphenyl (hereinafter referred to as BAPB) dissolved in 168 g of NMP was added dropwise over approximately 20 minutes. The mixture was stirred for 3 hours while maintaining the temperature below 5°C in an ice bath, and then the ice bath was removed and the mixture was stirred for 5 hours at room temperature. The precipitate that formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0321] A mixture of 840 g of water and 560 g of isopropanol was added dropwise to the resulting reaction solution, and the precipitated polymer was separated and redissolved in 650 g of NMP. The resulting crude polymer solution was added dropwise to 5 L of water to precipitate the polymer. The resulting precipitate was filtered and then vacuum dried to obtain a powdered polymer (Polymer E). The molecular weight of Polymer D was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight average molecular weight (Mw) was 34,700.

[0322] <Production Example A5> ((A) Synthesis of Polymer E as Polyoxazole Precursor) In a 3 L separable flask, 183.1 g of 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, 640.9 g of N,N-dimethylacetamide (DMAc), and 63.3 g of pyridine were mixed and stirred at room temperature (25°C) to form a homogeneous solution. A solution of 118.0 g of 4,4'-diphenyl ether dicarbonyl chloride in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise from a dropping funnel. The separable flask was cooled in a water bath at 15-20°C. The addition took 40 minutes, and the reaction temperature reached a maximum of 30°C.

[0323] Three hours after the completion of the dropwise addition, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic anhydride was added to the reaction mixture and stirred at room temperature for 15 hours. 99% of the total amine end groups on the polymer chain were capped with carboxycyclohexylamide groups. The conversion rate was easily calculated by monitoring the remaining amount of 1,2-cyclohexyldicarboxylic anhydride by high-performance liquid chromatography (HPLC). The reaction mixture was then added dropwise to 2 L of water with high-speed stirring to precipitate a polymer. The polymer was then recovered, washed appropriately with water, dehydrated, and vacuum dried to obtain a crude polybenzoxazole precursor with a weight-average molecular weight of 9,000 (polystyrene equivalent) as measured by gel permeation chromatography (GPC).

[0324] The crude polybenzoxazole precursor obtained above was redissolved in γ-butyrolactone (GBL), and then treated with a cation exchange resin and an anion exchange resin. The resulting solution was poured into ion-exchanged water, and the precipitated polymer was filtered off, washed with water, and vacuum dried to obtain a purified polybenzoxazole precursor (polymer E).

[0325] <Production Example A6> ((A) Synthesis of Polymer F as Polyimide) A separable four-neck glass flask equipped with a Teflon (registered trademark) anchor stirrer and a condenser with a Dean-Stark trap was attached. The flask was immersed in a silicone oil bath and stirred while nitrogen gas was passed through.

[0326] 72.28 g (280 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane (Clariant Japan) (hereinafter referred to as BAP), 70.29 g (266 mmol) of 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride (Tokyo Chemical Industry Co., Ltd.) (hereinafter referred to as MCTC), 254.6 g of γ-butyrolactone, and 60 g of toluene were added and stirred at 100 rpm at room temperature for 4 hours. Then, 4.6 g (28 mmol) of 5-norbornene-2,3-dicarboxylic anhydride (Tokyo Chemical Industry Co., Ltd.) was added and heated and stirred at 100 rpm for 8 hours while passing nitrogen gas through a silicon bath at 50°C. The silicon bath was then heated to 180°C and heated and stirred at 100 rpm for 2 hours. Toluene and water were removed during the reaction. After the imidization reaction was completed, the temperature was returned to room temperature.

[0327] The reaction solution was then added dropwise to 3 L of water under high speed stirring to disperse and precipitate the polymer, which was then recovered, washed appropriately with water, dehydrated, and then vacuum dried to obtain a crude polyimide (Polymer F) having a weight-average molecular weight of 23,000 (polystyrene equivalent) as measured by gel permeation chromatography (GPC).

[0328] <Production Example A7> ((A) Synthesis of Polymer G as Phenolic Resin) In a 0.5-liter separable flask equipped with a Dean-Stark apparatus, 128.3 g (0.76 mol) of methyl 3,5-dihydroxybenzoate, 121.2 g (0.5 mol) of 4,4'-bis(methoxymethyl)biphenyl (hereinafter also referred to as "BMMB"), 3.9 g (0.025 mol) of diethyl sulfate, and 140 g of diethylene glycol dimethyl ether were mixed and stirred at 70°C to dissolve the solids.

[0329] The mixed solution was heated to 140°C in an oil bath, and the generation of methanol from the reaction solution was confirmed. The reaction solution was stirred at 140°C for 2 hours.

[0330] The reaction vessel was then cooled in the air, and 100 g of tetrahydrofuran was added and stirred. The diluted reaction solution was added dropwise to 4 L of water with high-speed stirring to disperse and precipitate the resin. This resin was recovered, washed appropriately with water, dehydrated, and then vacuum dried to obtain a copolymer (Polymer G) consisting of methyl 3,5-dihydroxybenzoate / BMMB in 70% yield. The weight-average molecular weight of this polymer G, calculated using standard polystyrene standards as GPC, was 21,000.

[0331] <Production Example A8> ((A) Synthesis of Polymer H as Phenolic Resin) A 1.0 L separable flask equipped with a Dean-Stark apparatus was purged with nitrogen, and then 81.3 g (0.738 mol) of resorcinol, 84.8 g (0.35 mol) of BMMB, 3.81 g (0.02 mol) of p-toluenesulfonic acid, and 116 g of propylene glycol monomethyl ether (hereinafter also referred to as PGME) were mixed and stirred in the separable flask at 50°C to dissolve the solid matter.

[0332] The mixed solution was heated to 120°C in an oil bath, and the generation of methanol from the reaction solution was confirmed. The reaction solution was stirred at 120°C for 3 hours.

[0333] Next, 24.9 g (0.150 mol) of 2,6-bis(hydroxymethyl)-p-cresol and 249 g of PGME were mixed and stirred in a separate container, and the resulting solution was uniformly dissolved. The solution was added dropwise to the separable flask over 1 hour using a dropping funnel, and then stirred for an additional 2 hours after the dropwise addition.

[0334] After the reaction was completed, the same treatment as in Production Example A7 was carried out to obtain a copolymer consisting of resorcinol / BMMB / 2,6-bis(hydroxymethyl)-p-cresol (Polymer H) in a yield of 77%. The weight-average molecular weight of this Polymer H, calculated as standard polystyrene by the GPC method, was 9,900.

[0335] Example A1 Negative-tone photosensitive resin compositions were prepared using polymers A and B by the following method, and the resulting photosensitive resin compositions were evaluated. 50 g of polyimide precursors, polymers A and B (corresponding to (A) resin), were dissolved in a mixed solvent consisting of 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of ethyl lactate, along with 0.2 g of xanthine (corresponding to (B) cyclic compound having a carbonyl group), 4 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (referred to as "PDO" in Table 1) (corresponding to (C) photosensitizer), 8 g of tetraethylene glycol dimethacrylate, and 1.5 g of N-[3-(triethoxysilyl)propyl]phthalamic acid. The viscosity of the resulting solution was adjusted to approximately 35 poise by adding a small amount of the mixed solvent, yielding a negative-tone photosensitive resin composition. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.2%. Example A2 A negative photosensitive resin composition solution was prepared in the same manner as in Example A1, except that the amount of xanthine added as component (B) was changed to 0.05 g. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 6.4%. Example A3 A negative photosensitive resin composition solution was prepared in the same manner as in Example A1 above, except that the amount of xanthine added as component (B) was changed to 5 g. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 4.9%. Example A4 A negative photosensitive resin composition solution was prepared in the same manner as in Example A1, except that 8-azaxanthine was used as component (B) instead of xanthine. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.1%. Example A5 A negative photosensitive resin composition solution was prepared in the same manner as in Example A1, except that uric acid was used instead of xanthine as component (B). This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.4%. Example A6 A negative photosensitive resin composition solution was prepared in the same manner as in Example A1, except that lumazine was used as component (B) instead of xanthine. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.5%. Example A7 A negative photosensitive resin composition solution was prepared in the same manner as in Example A1, except that barbituric acid was used as component (B) instead of xanthine. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 7.3%. Example A8 A negative photosensitive resin composition solution was prepared in the same manner as in Example A1 above, and this composition was cured at 350°C using the method described above to create a cured relief pattern on the Cu layer. After a high-temperature storage test was performed, the area ratio of voids on the surface of the Cu layer was evaluated, and the result was 4.5%. Example A9 A negative photosensitive resin composition solution was prepared in the same manner as in Example A1, except that in Example A1, 50 g of polymer A and 50 g of polymer B were changed to 100 g of polymer A as the (A) resin, and 4 g of PDO was changed to 2.5 g of 1,2-octanedione, 1-{4-(phenylthio)-, 2-(O-benzoyloxime)} (Irgacure OXE01 (trade name, manufactured by BASF)) as the (C) component. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.1%. Example A10 A negative photosensitive resin composition solution was prepared in the same manner as in Example A1 above, except that in Example A1, 50 g of Polymer A and 50 g of Polymer B were replaced with 100 g of Polymer A as the (A) resin, 4 g of PDO was replaced with 2.5 g of 1,2-octanedione, 1-{4-(phenylthio)-, 2-(O-benzoyloxime)} (Irgacure OXE01 (BASF, trade name)) as the (C) component, and further the solvent was changed to 85 g of γ-butyrolactone and 15 g of dimethyl sulfoxide. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.2%. <Example A11> A negative photosensitive resin composition solution was prepared in the same manner as in Example A1, except that 50 g of polymer A and 50 g of polymer B were replaced with 100 g of polymer C as the resin (A). This composition was cured at 350°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 4.9%. Example A12 A negative photosensitive resin composition solution was prepared in the same manner as in Example A1, except that 50 g of polymer A and 50 g of polymer B were replaced with 100 g of polymer D as the resin (A). This composition was cured at 250°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.0%. Example A13 A positive photosensitive resin composition was prepared using polymer E by the following method, and the prepared photosensitive resin composition was evaluated. 100 g of polymer E (corresponding to resin (A)), which is a polyoxazole precursor, was added to a compound represented by the following formula (96): [ka] 20 g of a photosensitive diazoquinone compound (C1) (manufactured by Toyo Gosei Co., Ltd., corresponding to (C) photosensitizer) in which 77% of the phenolic hydroxyl groups have been converted to naphthoquinone diazide-4-sulfonic acid ester, represented by the formula (1), 0.2 g of xanthine (corresponding to (B) cyclic compound having a carbonyl group), and 6 g of 3-t-butoxycarbonylaminopropyltriethoxysilane were dissolved in 100 g of γ-butyrolactone (as a solvent). The viscosity of the resulting solution was adjusted to approximately 20 poise by further adding a small amount of γ-butyrolactone, yielding a positive photosensitive resin composition. This composition was cured at 350°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.5%. Example A14 A positive photosensitive resin composition solution was prepared in the same manner as in Example A13, except that 100 g of Polymer E was changed to 100 g of Polymer F as the resin (A). This composition was cured at 250°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.7%. Example A15 A positive photosensitive resin composition solution was prepared in the same manner as in Example A13, except that 100 g of Polymer G was used instead of 100 g of Polymer E as the resin (A). This composition was cured at 220°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.3%. Example A16 A positive photosensitive resin composition solution was prepared in the same manner as in Example A13, except that 100 g of Polymer E was changed to 100 g of Polymer H as the resin (A). This composition was cured at 220°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.2%. <Comparative Example A1> A negative photosensitive resin composition was prepared in the same manner as in Example A1, except that 0.2 g of benzotriazole was added instead of 0.2 g of xanthine in the composition of Example A1, and the composition was evaluated in the same manner as in Example A1. The evaluation result was 15.2% because the composition did not contain the compound (B) of the present invention. <Comparative example A2> A negative photosensitive resin composition was prepared in the same manner as in Example A1, except that xanthine was not added to the composition of Example A1, and the composition was evaluated in the same manner as in Example A1. The evaluation result was 14.3% because the composition did not contain the compound (B) of the present invention. <Comparative example A3> A negative photosensitive resin composition was prepared in the same manner as in Example A10, except that xanthine was not added to the composition of Example A10, and the composition was evaluated in the same manner as in Example A10. The evaluation result was 15.7% because the compound (B) of the present invention was not contained. <Comparative example A4> A negative photosensitive resin composition was prepared in the same manner as in Example A11, except that xanthine was not added to the composition of Example A11, and the composition was evaluated in the same manner as in Example A11. The evaluation result was 14.9% because the composition did not contain the compound (B) of the present invention. The results of Examples A1 to A16 and Comparative Examples A1 to A4 are summarized in Table 1.

[0336] Example B <Production Example B1> ((A) Synthesis of Polymer A as Polyimide Precursor) 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 L separable flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added, and the mixture was stirred at room temperature. 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature and left to stand for 16 hours.

[0337] Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by the addition of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 350 ml of γ-butyrolactone over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour, followed by the addition of 400 ml of γ-butyrolactone. The precipitate that formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0338] The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered off and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 28 L of water to precipitate the polymer. The resulting precipitate was filtered off and then vacuum dried to obtain a powdered polymer (Polymer A). The molecular weight of Polymer A was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight average molecular weight (Mw) was found to be 20,000.

[0339] The weight average molecular weight of the resin obtained in each Production Example B was measured using gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight was calculated in terms of standard polystyrene. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Column: Shodex KD-806M, two in series Mobile phase: 0.1mol / l LiBr / NMP Flow rate: 1ml / min.

[0340] <Production Example B2> ((A) Synthesis of Polymer B as Polyimide Precursor) A reaction was carried out in the same manner as in the above-described Production Example B1, except that 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example B1, to obtain Polymer B. The molecular weight of Polymer B was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 22,000.

[0341] <Production Example B3> ((A) Synthesis of Polymer C as Polyimide Precursor) Except for using 147.8 g of 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl (TFMB) instead of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in Production Example B1, a reaction was carried out in the same manner as in the above Production Example B1 to obtain Polymer C. The molecular weight of Polymer C was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 21,000.

[0342] <Production Example B4> ((A) Synthesis of Polymer D as Polyamide) (Synthesis of phthalic acid compound-capped AIPA-MO) A 5-liter separable flask was charged with 543.5 g of 5-aminoisophthalic acid (hereafter abbreviated as AIPA) and 1,700 g of N-methyl-2-pyrrolidone, which were then mixed and stirred and heated to 50°C in a water bath. 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate diluted with 500 g of γ-butyrolactone was added dropwise to the flask using a dropping funnel, and the mixture was stirred at 50°C for approximately 2 hours.

[0343] After confirming the completion of the reaction (disappearance of 5-aminoisophthalic acid) by low-molecular-weight gel permeation chromatography (hereafter referred to as low-molecular-weight GPC), the reaction solution was poured into 15 L of ion-exchanged water, stirred, and allowed to stand. After waiting for the reaction product to crystallize and precipitate, it was filtered, washed appropriately with water, and then vacuum-dried at 40°C for 48 hours to obtain AIPA-MO, in which the amino group of 5-aminoisophthalic acid and the isocyanate group of 2-methacryloyloxyethyl isocyanate had reacted. The low-molecular-weight GPC purity of the resulting AIPA-MO was approximately 100%.

[0344] (Synthesis of Polymer D) A 2-liter separable flask was charged with 100.89 g (0.3 mol) of the resulting AIPA-MO, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL, mixed, and cooled to 5°C in an ice bath. A solution of 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) dissolved in 125 g of GBL was added dropwise over approximately 20 minutes under ice cooling. Subsequently, a solution of 103.16 g (0.28 mol) of 4,4'-bis(4-aminophenoxy)biphenyl (hereinafter referred to as BAPB) dissolved in 168 g of NMP was added dropwise over approximately 20 minutes. The mixture was stirred for 3 hours while maintaining the temperature below 5°C in an ice bath, and then the ice bath was removed and the mixture was stirred for 5 hours at room temperature. The precipitate that formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0345] A mixture of 840 g of water and 560 g of isopropanol was added dropwise to the resulting reaction solution, and the precipitated polymer was separated and redissolved in 650 g of NMP. The resulting crude polymer solution was added dropwise to 5 L of water to precipitate the polymer. The resulting precipitate was filtered and then vacuum dried to obtain a powdered polymer (Polymer E). The molecular weight of Polymer D was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight average molecular weight (Mw) was 34,700.

[0346] <Production Example B5> ((A) Synthesis of Polymer E as Polyoxazole Precursor) In a 3 L separable flask, 183.1 g of 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, 640.9 g of N,N-dimethylacetamide (DMAc), and 63.3 g of pyridine were mixed and stirred at room temperature (25°C) to form a homogeneous solution. A solution of 118.0 g of 4,4'-diphenyl ether dicarbonyl chloride in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise from a dropping funnel. The separable flask was cooled in a water bath at 15-20°C. The addition took 40 minutes, and the reaction temperature reached a maximum of 30°C.

[0347] Three hours after the completion of the dropwise addition, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic anhydride was added to the reaction mixture and stirred at room temperature for 15 hours. 99% of the total amine end groups on the polymer chain were capped with carboxycyclohexylamide groups. The conversion rate was easily calculated by monitoring the remaining amount of 1,2-cyclohexyldicarboxylic anhydride by high-performance liquid chromatography (HPLC). The reaction mixture was then added dropwise to 2 L of water with high-speed stirring to precipitate a polymer. The polymer was then recovered, washed appropriately with water, dehydrated, and vacuum dried to obtain a crude polybenzoxazole precursor with a weight-average molecular weight of 9,000 (polystyrene equivalent) as measured by gel permeation chromatography (GPC).

[0348] The crude polybenzoxazole precursor obtained above was redissolved in γ-butyrolactone (GBL), and then treated with a cation exchange resin and an anion exchange resin. The resulting solution was poured into ion-exchanged water, and the precipitated polymer was filtered off, washed with water, and vacuum dried to obtain a purified polybenzoxazole precursor (polymer E).

[0349] <Production Example B6> ((A) Synthesis of Polymer F as Polyimide) A separable four-neck glass flask equipped with a Teflon (registered trademark) anchor stirrer and a condenser with a Dean-Stark trap was attached. The flask was immersed in a silicone oil bath and stirred while nitrogen gas was passed through.

[0350] 72.28 g (280 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane (Clariant Japan) (hereinafter referred to as BAP), 70.29 g (266 mmol) of 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride (Tokyo Chemical Industry Co., Ltd.) (hereinafter referred to as MCTC), 254.6 g of γ-butyrolactone, and 60 g of toluene were added and stirred at 100 rpm at room temperature for 4 hours. Then, 4.6 g (28 mmol) of 5-norbornene-2,3-dicarboxylic anhydride (Tokyo Chemical Industry Co., Ltd.) was added and heated and stirred at 100 rpm for 8 hours while passing nitrogen gas through a silicon bath at 50°C. The silicon bath was then heated to 180°C and heated and stirred at 100 rpm for 2 hours. Toluene and water were removed during the reaction. After the imidization reaction was completed, the temperature was returned to room temperature.

[0351] The reaction solution was then added dropwise to 3 L of water under high speed stirring to disperse and precipitate the polymer, which was then recovered, washed appropriately with water, dehydrated, and then vacuum dried to obtain a crude polyimide (Polymer F) having a weight-average molecular weight of 23,000 (polystyrene equivalent) as measured by gel permeation chromatography (GPC).

[0352] <Production Example B7> ((A) Synthesis of Polymer G as Phenolic Resin) In a 0.5-liter separable flask equipped with a Dean-Stark apparatus, 128.3 g (0.76 mol) of methyl 3,5-dihydroxybenzoate, 121.2 g (0.5 mol) of 4,4'-bis(methoxymethyl)biphenyl (hereinafter also referred to as "BMMB"), 3.9 g (0.025 mol) of diethyl sulfate, and 140 g of diethylene glycol dimethyl ether were mixed and stirred at 70°C to dissolve the solids.

[0353] The mixed solution was heated to 140°C in an oil bath, and the generation of methanol from the reaction solution was confirmed. The reaction solution was stirred at 140°C for 2 hours.

[0354] The reaction vessel was then cooled in the air, and 100 g of tetrahydrofuran was added and stirred. The diluted reaction solution was added dropwise to 4 L of water with high-speed stirring to disperse and precipitate the resin. This resin was recovered, washed appropriately with water, dehydrated, and then vacuum dried to obtain a copolymer (Polymer G) consisting of methyl 3,5-dihydroxybenzoate / BMMB in 70% yield. The weight-average molecular weight of this polymer G, calculated using standard polystyrene standards as GPC, was 21,000.

[0355] <Production Example B8> ((A) Synthesis of Polymer H as Phenolic Resin) A 1.0 L separable flask equipped with a Dean-Stark apparatus was purged with nitrogen, and then 81.3 g (0.738 mol) of resorcinol, 84.8 g (0.35 mol) of BMMB, 3.81 g (0.02 mol) of p-toluenesulfonic acid, and 116 g of propylene glycol monomethyl ether (hereinafter also referred to as PGME) were mixed and stirred in the separable flask at 50°C to dissolve the solid matter.

[0356] The mixed solution was heated to 120°C in an oil bath, and the generation of methanol from the reaction solution was confirmed. The reaction solution was stirred at 120°C for 3 hours.

[0357] Next, 24.9 g (0.150 mol) of 2,6-bis(hydroxymethyl)-p-cresol and 249 g of PGME were mixed and stirred in a separate container, and the resulting solution was uniformly dissolved. The solution was added dropwise to the separable flask over 1 hour using a dropping funnel, and then stirred for an additional 2 hours after the dropwise addition.

[0358] After the reaction was completed, the same treatment as in Production Example B7 was carried out to obtain a copolymer consisting of resorcinol / BMMB / 2,6-bis(hydroxymethyl)-p-cresol (Polymer H) in a yield of 77%. The weight-average molecular weight of this Polymer H, calculated as standard polystyrene by the GPC method, was 9,900.

[0359] Example B1 Negative-tone photosensitive resin compositions were prepared using polymers A and B by the following method, and the resulting photosensitive resin compositions were evaluated. 50 g of polyimide precursors, polymers A and B (corresponding to (A) resin), were dissolved in a mixed solvent consisting of 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of ethyl lactate, along with 0.5 g of dicyclohexylthiourea (corresponding to (B) sulfur-containing compound), 4 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (referred to as "PDO" in Table 2) (corresponding to (C) photosensitizer), 8 g of tetraethylene glycol dimethacrylate, and 1.5 g of N-[3-(triethoxysilyl)propyl]phthalamic acid. The viscosity of the resulting solution was adjusted to approximately 35 poise by adding a small amount of the mixed solvent, yielding a negative-tone photosensitive resin composition. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.5%. Example B2 A negative photosensitive resin composition solution was prepared in the same manner as in Example B1 above, except that the amount of dicyclohexylthiourea added as component (B) was changed to 0.1 g. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 6.9%. Example B3 A negative photosensitive resin composition solution was prepared in the same manner as in Example B1 above, except that the amount of dicyclohexylthiourea added as component (B) was changed to 4 g. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 4.8%. Example B4 A negative photosensitive resin composition solution was prepared in the same manner as in Example B1, except that benzothiazole was used as the component (B) instead of dicyclohexylthiourea. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 7.3%. Example B5 A negative photosensitive resin composition solution was prepared in the same manner as in Example B1 above, except that rhodanine was used as the component (B) instead of dicyclohexylthiourea. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 7.2%. Example B6 A negative photosensitive resin composition solution was prepared in the same manner as in Example B1 above, except that 2-thioxanthone was used as the component (B) instead of dicyclohexylthiourea. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 7.3%. Example B7 A negative photosensitive resin composition solution was prepared in the same manner as in Example B1 above, and this composition was cured at 350°C by the method described above to create a cured relief pattern on the Cu layer. After a high-temperature storage test was performed, the area ratio of voids on the surface of the Cu layer was evaluated, and the result was 4.9%. <Example B8> A negative photosensitive resin composition solution was prepared in the same manner as in Example B1, except that in Example B1, 50 g of Polymer A and 50 g of Polymer B were changed to 100 g of Polymer A as the (A) resin, and 4 g of PDO was changed to 2.5 g of 1,2-octanedione, 1-{4-(phenylthio)-, 2-(O-benzoyloxime)} (Irgacure OXE01 (BASF, trade name)) as the (C) component. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.7%. <Example B9> A negative photosensitive resin composition solution was prepared in the same manner as in Example B1 above, except that in Example B1, 50 g of Polymer A and 50 g of Polymer B were replaced with 100 g of Polymer A as the (A) resin, 4 g of PDO was replaced with 2.5 g of 1,2-octanedione, 1-{4-(phenylthio)-, 2-(O-benzoyloxime)} (Irgacure OXE01 (BASF, trade name)) as the (C) component, and the solvent was changed to 85 g of γ-butyrolactone and 15 g of dimethyl sulfoxide. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.6%. <Example B10> A negative photosensitive resin composition solution was prepared in the same manner as in Example B1, except that 50 g of polymer A and 50 g of polymer B were replaced with 100 g of polymer C as the resin (A). This composition was cured at 350°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 4.9%. <Example B11> A negative photosensitive resin composition solution was prepared in the same manner as in Example B1, except that 50 g of polymer A and 50 g of polymer B in Example B1 were changed to 100 g of polymer D as the resin (A). This composition was cured at 250°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.3%. <Example B12> A positive photosensitive resin composition was prepared using polymer E by the following method, and the prepared photosensitive resin composition was evaluated. 100 g of polymer E (corresponding to resin (A)), which is a polyoxazole precursor, was added to a compound represented by the following formula (96): [ka] 15 g of a photosensitive diazoquinone compound (C1) (manufactured by Toyo Gosei Co., Ltd., corresponding to (C) photosensitizer) in which 77% of the phenolic hydroxyl groups have been converted to naphthoquinone diazide-4-sulfonic acid ester, represented by the formula (1), 0.5 g of dicyclohexylthiourea (corresponding to (B) sulfur-containing compound), and 6 g of 3-t-butoxycarbonylaminopropyltriethoxysilane were dissolved in 100 g of γ-butyrolactone (as a solvent). The viscosity of the resulting solution was adjusted to approximately 20 poise by further adding a small amount of γ-butyrolactone, yielding a positive-type photosensitive resin composition. This composition was cured at 350°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.4%. <Example B13> A positive photosensitive resin composition solution was prepared in the same manner as in Example B12, except that 100 g of Polymer E was changed to 100 g of Polymer F as the resin (A). This composition was cured at 250°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.5%. <Example B14> A positive photosensitive resin composition solution was prepared in the same manner as in Example B12, except that 100 g of Polymer G was used instead of 100 g of Polymer E as the resin (A). This composition was cured at 220°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.7%. <Example B15> A positive photosensitive resin composition solution was prepared in the same manner as in Example B12, except that 100 g of Polymer E was changed to 100 g of Polymer H as the resin (A). This composition was cured at 220°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.6%. <Comparative Example B1> A negative photosensitive resin composition was prepared in the same manner as in Example B1, except that dicyclohexylthiourea was not added to the composition of Example B1, and the composition was evaluated in the same manner as in Example B1. The evaluation result was 14.3% because the composition did not contain the compound (B) of the present invention. <Comparative example B2> A negative photosensitive resin composition was prepared in the same manner as in Example B11, except that dicyclohexylthiourea was not added to the composition of Example B11, and the composition was evaluated in the same manner as in Example B11. The evaluation result was 15.5% because the composition did not contain the compound (B) of the present invention. <Comparative Example B3> A positive photosensitive resin composition was prepared in the same manner as in Example B12, except that dicyclohexylthiourea was not added to the composition of Example B12, and the composition was evaluated in the same manner as in Example B12. The evaluation result was 14.6% because the composition did not contain the compound (B) of the present invention. The results of Examples B1 to B15 and Comparative Examples B1 to B3 are summarized in Table 2.

[0360] Example C <Production Example C1> ((A) Synthesis of Polymer A as Polyimide Precursor) 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 L separable flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added, and the mixture was stirred at room temperature. 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature and left to stand for 16 hours.

[0361] Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by the addition of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 350 ml of γ-butyrolactone over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour, followed by the addition of 400 ml of γ-butyrolactone. The precipitate that formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0362] The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered off and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 28 L of water to precipitate the polymer. The resulting precipitate was filtered off and then vacuum dried to obtain a powdered polymer (Polymer A). The molecular weight of Polymer A was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight average molecular weight (Mw) was found to be 20,000.

[0363] The weight average molecular weight of the resin obtained in each Production Example C was measured by gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight was calculated in terms of standard polystyrene. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Column: Shodex KD-806M, two in series Mobile phase: 0.1mol / l LiBr / NMP Flow rate: 1ml / min.

[0364] <Production Example C2> ((A) Synthesis of Polymer B as Polyimide Precursor) Except for using 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example C1, a reaction was carried out in the same manner as in the above Production Example C1 to obtain Polymer B. The molecular weight of Polymer B was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 22,000.

[0365] <Production Example C3> ((A) Synthesis of Polymer C as Polyimide Precursor) Except for using 147.8 g of 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl (TFMB) instead of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in Production Example C1, the reaction was carried out in the same manner as in the above Production Example C1 to obtain Polymer C. The molecular weight of Polymer C was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 21,000.

[0366] <Production Example C4> ((A) Synthesis of Polymer D as Polyamide) (Synthesis of phthalic acid compound-capped AIPA-MO) A 5-liter separable flask was charged with 543.5 g of 5-aminoisophthalic acid (hereafter abbreviated as AIPA) and 1,700 g of N-methyl-2-pyrrolidone, which were then mixed and stirred and heated to 50°C in a water bath. 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate diluted with 500 g of γ-butyrolactone was added dropwise to the flask using a dropping funnel, and the mixture was stirred at 50°C for approximately 2 hours.

[0367] After confirming the completion of the reaction (disappearance of 5-aminoisophthalic acid) by low-molecular-weight gel permeation chromatography (hereafter referred to as low-molecular-weight GPC), the reaction solution was poured into 15 L of ion-exchanged water, stirred, and allowed to stand. After waiting for the reaction product to crystallize and precipitate, it was filtered, washed appropriately with water, and then vacuum-dried at 40°C for 48 hours to obtain AIPA-MO, in which the amino group of 5-aminoisophthalic acid and the isocyanate group of 2-methacryloyloxyethyl isocyanate had reacted. The low-molecular-weight GPC purity of the resulting AIPA-MO was approximately 100%.

[0368] (Synthesis of Polymer D) A 2-liter separable flask was charged with 100.89 g (0.3 mol) of the resulting AIPA-MO, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL, mixed, and cooled to 5°C in an ice bath. A solution of 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) dissolved in 125 g of GBL was added dropwise over approximately 20 minutes under ice cooling. Subsequently, a solution of 103.16 g (0.28 mol) of 4,4'-bis(4-aminophenoxy)biphenyl (hereinafter referred to as BAPB) dissolved in 168 g of NMP was added dropwise over approximately 20 minutes. The mixture was stirred for 3 hours while maintaining the temperature below 5°C in an ice bath, and then the ice bath was removed and the mixture was stirred for 5 hours at room temperature. The precipitate that formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0369] A mixture of 840 g of water and 560 g of isopropanol was added dropwise to the resulting reaction solution, and the precipitated polymer was separated and redissolved in 650 g of NMP. The resulting crude polymer solution was added dropwise to 5 L of water to precipitate the polymer. The resulting precipitate was filtered and then vacuum dried to obtain a powdered polymer (Polymer E). The molecular weight of Polymer D was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight average molecular weight (Mw) was 34,700.

[0370] <Production Example C5> ((A) Synthesis of Polymer E as Polyoxazole Precursor) In a 3 L separable flask, 183.1 g of 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, 640.9 g of N,N-dimethylacetamide (DMAc), and 63.3 g of pyridine were mixed and stirred at room temperature (25°C) to form a homogeneous solution. A solution of 118.0 g of 4,4'-diphenyl ether dicarbonyl chloride in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise from a dropping funnel. The separable flask was cooled in a water bath at 15-20°C. The addition took 40 minutes, and the reaction temperature reached a maximum of 30°C.

[0371] Three hours after the completion of the dropwise addition, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic anhydride was added to the reaction mixture and stirred at room temperature for 15 hours. 99% of the total amine end groups on the polymer chain were capped with carboxycyclohexylamide groups. The conversion rate was easily calculated by monitoring the remaining amount of 1,2-cyclohexyldicarboxylic anhydride by high-performance liquid chromatography (HPLC). The reaction mixture was then added dropwise to 2 L of water with high-speed stirring to precipitate a polymer. The polymer was then recovered, washed appropriately with water, dehydrated, and vacuum dried to obtain a crude polybenzoxazole precursor with a weight-average molecular weight of 9,000 (polystyrene equivalent) as measured by gel permeation chromatography (GPC).

[0372] The crude polybenzoxazole precursor obtained above was redissolved in γ-butyrolactone (GBL), and then treated with a cation exchange resin and an anion exchange resin. The resulting solution was poured into ion-exchanged water, and the precipitated polymer was filtered off, washed with water, and vacuum dried to obtain a purified polybenzoxazole precursor (polymer E).

[0373] <Production Example C6> ((A) Synthesis of Polymer F as Polyimide) A separable four-neck glass flask equipped with a Teflon (registered trademark) anchor stirrer and a condenser with a Dean-Stark trap was attached. The flask was immersed in a silicone oil bath and stirred while nitrogen gas was passed through.

[0374] 72.28 g (280 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane (Clariant Japan) (hereinafter referred to as BAP), 70.29 g (266 mmol) of 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride (Tokyo Chemical Industry Co., Ltd.) (hereinafter referred to as MCTC), 254.6 g of γ-butyrolactone, and 60 g of toluene were added and stirred at 100 rpm at room temperature for 4 hours. Then, 4.6 g (28 mmol) of 5-norbornene-2,3-dicarboxylic anhydride (Tokyo Chemical Industry Co., Ltd.) was added and heated and stirred at 100 rpm for 8 hours while passing nitrogen gas through a silicon bath at 50°C. The silicon bath was then heated to 180°C and heated and stirred at 100 rpm for 2 hours. Toluene and water were removed during the reaction. After the imidization reaction was completed, the temperature was returned to room temperature.

[0375] The reaction solution was then added dropwise to 3 L of water under high speed stirring to disperse and precipitate the polymer, which was then recovered, washed appropriately with water, dehydrated, and then vacuum dried to obtain a crude polyimide (Polymer F) having a weight-average molecular weight of 23,000 (polystyrene equivalent) as measured by gel permeation chromatography (GPC).

[0376] <Production Example C7> ((A) Synthesis of Polymer G as Phenolic Resin) In a 0.5-liter separable flask equipped with a Dean-Stark apparatus, 128.3 g (0.76 mol) of methyl 3,5-dihydroxybenzoate, 121.2 g (0.5 mol) of 4,4'-bis(methoxymethyl)biphenyl (hereinafter also referred to as "BMMB"), 3.9 g (0.025 mol) of diethyl sulfate, and 140 g of diethylene glycol dimethyl ether were mixed and stirred at 70°C to dissolve the solids.

[0377] The mixed solution was heated to 140°C in an oil bath, and the generation of methanol from the reaction solution was confirmed. The reaction solution was stirred at 140°C for 2 hours.

[0378] The reaction vessel was then cooled in the air, and 100 g of tetrahydrofuran was added and stirred. The diluted reaction solution was added dropwise to 4 L of water with high-speed stirring to disperse and precipitate the resin. This resin was recovered, washed appropriately with water, dehydrated, and then vacuum dried to obtain a copolymer (Polymer G) consisting of methyl 3,5-dihydroxybenzoate / BMMB in 70% yield. The weight-average molecular weight of this polymer G, calculated using standard polystyrene standards as GPC, was 21,000.

[0379] <Production Example C8> ((A) Synthesis of Polymer H as Phenolic Resin) A 1.0 L separable flask equipped with a Dean-Stark apparatus was purged with nitrogen, and then 81.3 g (0.738 mol) of resorcinol, 84.8 g (0.35 mol) of BMMB, 3.81 g (0.02 mol) of p-toluenesulfonic acid, and 116 g of propylene glycol monomethyl ether (hereinafter also referred to as PGME) were mixed and stirred in the separable flask at 50°C to dissolve the solid matter.

[0380] The mixed solution was heated to 120°C in an oil bath, and the generation of methanol from the reaction solution was confirmed. The reaction solution was stirred at 120°C for 3 hours.

[0381] Next, 24.9 g (0.150 mol) of 2,6-bis(hydroxymethyl)-p-cresol and 249 g of PGME were mixed and stirred in a separate container, and the resulting solution was uniformly dissolved. The solution was added dropwise to the separable flask over 1 hour using a dropping funnel, and then stirred for an additional 2 hours after the dropwise addition.

[0382] After the reaction was completed, the same treatment as in Production Example C7 was carried out to obtain a copolymer consisting of resorcinol / BMMB / 2,6-bis(hydroxymethyl)-p-cresol (Polymer H) in a yield of 77%. The weight-average molecular weight of this Polymer H, calculated as standard polystyrene by the GPC method, was 9,900.

[0383] Example C1 Negative-tone photosensitive resin compositions were prepared using polymers A and B by the following method, and the resulting photosensitive resin compositions were evaluated. 50 g of polyimide precursors, polymers A and B (corresponding to (A) resin), were dissolved in a mixed solvent consisting of 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of ethyl lactate, along with 1 g of butylurea (corresponding to (B-1) compound), 4 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (referred to as "PDO" in Table 3) (corresponding to (C) photosensitizer), 8 g of tetraethylene glycol dimethacrylate, and 1.5 g of N-[3-(triethoxysilyl)propyl]phthalamic acid. The viscosity of the resulting solution was adjusted to approximately 35 poise by adding a small amount of the mixed solvent, yielding a negative-tone photosensitive resin composition. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.5%. Example C2 A negative photosensitive resin composition solution was prepared in the same manner as in Example C1 above, except that the amount of butylurea added as component (B) was changed to 0.1 g. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 6.8%. Example C3 A negative photosensitive resin composition solution was prepared in the same manner as in Example C1 above, except that the amount of butylurea added as component (B) was changed to 5 g. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 4.8%. Example C4 A negative photosensitive resin composition solution was prepared in the same manner as in Example C1, except that tetraethylene glycol (corresponding to the compound (B-2)) was used as the component (B) instead of butylurea in Example C1. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 6.2%. Example C5 A negative photosensitive resin composition solution was prepared in the same manner as in Example C1, except that bis(2-methoxyethyl) adipate (corresponding to compound (B-3)) was used as the component (B) instead of butylurea in Example C1. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 6.3%. Example C6 A negative photosensitive resin composition solution was prepared in the same manner as in Example C1 above, and this composition was cured at 350°C using the method described above to create a cured relief pattern on the Cu layer. After a high-temperature storage test was performed, the area ratio of voids on the surface of the Cu layer was evaluated, and the result was 4.7%. Example C7 A negative photosensitive resin composition solution was prepared in the same manner as in Example C1, except that in Example C1, 50 g of polymer A and 50 g of polymer B were changed to 100 g of polymer A as the (A) resin, and 4 g of PDO was changed to 2.5 g of 1,2-octanedione, 1-{4-(phenylthio)-, 2-(O-benzoyloxime)} (Irgacure OXE01 (BASF, trade name)) as the (C) component. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.4%. Example C8 A negative photosensitive resin composition solution was prepared in the same manner as in Example C1 above, except that in Example C1, 50 g of Polymer A and 50 g of Polymer B were replaced with 100 g of Polymer A as the (A) resin, 4 g of PDO was replaced with 2.5 g of 1,2-octanedione, 1-{4-(phenylthio)-, 2-(O-benzoyloxime)} (Irgacure OXE01 (BASF, trade name)) as the (C) component, and further the solvent was changed to 85 g of γ-butyrolactone and 15 g of dimethyl sulfoxide. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.5%. Example C9 A negative photosensitive resin composition solution was prepared in the same manner as in Example C1, except that 50 g of polymer A and 50 g of polymer B in Example C1 were changed to 100 g of polymer C as the resin (A). This composition was cured at 350°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 4.7%. Example C10 A negative photosensitive resin composition solution was prepared in the same manner as in Example C1, except that 50 g of polymer A and 50 g of polymer B in Example C1 were changed to 100 g of polymer D as the resin (A). This composition was cured at 250°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.8%. Example C11 A positive photosensitive resin composition was prepared using polymer E by the following method, and the prepared photosensitive resin composition was evaluated. 100 g of polymer E (corresponding to resin (A)), which is a polyoxazole precursor, was added to a compound represented by the following formula (96): [ka] 15 g of a photosensitive diazoquinone compound (C1) (manufactured by Toyo Gosei Co., Ltd., corresponding to (C) photosensitizer) in which 77% of the phenolic hydroxyl groups have been converted to naphthoquinone diazide-4-sulfonic acid ester, represented by the formula (C1), 1 g of butyl urea (corresponding to (B-1) compound), and 6 g of 3-t-butoxycarbonylaminopropyltriethoxysilane were dissolved in 100 g of γ-butyrolactone (as a solvent). The viscosity of the resulting solution was adjusted to approximately 20 poise by further adding a small amount of γ-butyrolactone, yielding a positive-type photosensitive resin composition. This composition was cured at 350°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.6%. Example C12 A positive photosensitive resin composition solution was prepared in the same manner as in Example C11, except that 100 g of Polymer E was changed to 100 g of Polymer F as the resin (A). This composition was cured at 250°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.9%. Example C13 A positive photosensitive resin composition solution was prepared in the same manner as in Example C11, except that 100 g of Polymer G was used instead of 100 g of Polymer E as the (A) resin in Example C11. This composition was cured at 220°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.5%. Example C14 A positive photosensitive resin composition solution was prepared in the same manner as in Example C13, except that in Example C11, 100 g of polymer E was changed to 100 g of polymer H as the resin (A). This composition was cured at 220°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in a result of 5.4%. <Comparative Example C1> A negative photosensitive resin composition was prepared in the same manner as in Example C1, except that butylurea was not added to the composition of Example C1, and the composition was evaluated in the same manner as in Example C1. The evaluation result was 14.3% because the compound (B) of the present invention was not contained. <Comparative Example C2> A positive photosensitive resin composition was prepared in the same manner as in Example C12, except that butylurea was not added to the composition of Example C12, and the composition was evaluated in the same manner as in Example C12. The evaluation result was 15.5% because the compound (B) of the present invention was not contained. <Comparative Example C3> A positive photosensitive resin composition was prepared in the same manner as in Example C13, except that butylurea was not added to the composition of Example C13, and the composition was evaluated in the same manner as in Example C11. The evaluation result was 15.7% because the compound (B) of the present invention was not contained.

[0384] Example D <Production Example D1> (Synthesis of Polymer (A)-1 as Polyimide Precursor (A)) 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 L separable flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added, and the mixture was stirred at room temperature. 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature and left to stand for 16 hours.

[0385] Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by the addition of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 350 ml of γ-butyrolactone over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour, followed by the addition of 400 ml of γ-butyrolactone. The precipitate that formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0386] The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered off and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 28 L of water to precipitate the polymer, and the resulting precipitate was filtered off and then vacuum dried to obtain a powdered polymer (polymer (A)-1). The molecular weight of polymer (A)-1 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 20,000.

[0387] The weight average molecular weight of the resin obtained in each Production Example D was measured by gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight was calculated in terms of standard polystyrene. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Column: Shodex KD-806M, two in series Mobile phase: 0.1mol / l LiBr / NMP Flow rate: 1ml / min.

[0388] <Production Example D2> (Synthesis of Polymer (A)-2 as Polyimide Precursor (A)) Polymer (A)-2 was obtained by carrying out a reaction in the same manner as in Production Example D1, except that 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example D1. The molecular weight of Polymer (A)-2 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 22,000.

[0389] <Production Example D3> (Synthesis of Polymer (A)-3 as Polyimide Precursor (A)) Polymer (A)-3 was obtained by carrying out a reaction in the same manner as in Production Example D1, except that 147.8 g of 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl (TFMB) was used instead of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) in Production Example D1. The molecular weight of Polymer (A)-3 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 21,000.

[0390] <Production Example D4> (Synthesis of Polymer (A)-4 as Polyamide (A)) (Synthesis of phthalic acid compound-capped AIPA-MO) A 5-liter separable flask was charged with 543.5 g of 5-aminoisophthalic acid (hereafter abbreviated as AIPA) and 1,700 g of N-methyl-2-pyrrolidone, which were then mixed and stirred and heated to 50°C in a water bath. 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate diluted with 500 g of γ-butyrolactone was added dropwise to the flask using a dropping funnel, and the mixture was stirred at 50°C for approximately 2 hours.

[0391] After confirming the completion of the reaction (disappearance of 5-aminoisophthalic acid) by low-molecular-weight gel permeation chromatography (hereafter referred to as low-molecular-weight GPC), the reaction solution was poured into 15 L of ion-exchanged water, stirred, and allowed to stand. After waiting for the reaction product to crystallize and precipitate, it was filtered, washed appropriately with water, and then vacuum-dried at 40°C for 48 hours to obtain AIPA-MO, in which the amino group of 5-aminoisophthalic acid and the isocyanate group of 2-methacryloyloxyethyl isocyanate had reacted. The low-molecular-weight GPC purity of the resulting AIPA-MO was approximately 100%.

[0392] (Synthesis of Polymer (A)-4) A 2-liter separable flask was charged with 100.89 g (0.3 mol) of the resulting AIPA-MO, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL, mixed, and cooled to 5°C in an ice bath. A solution of 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) dissolved in 125 g of GBL was added dropwise over approximately 20 minutes under ice cooling. Subsequently, a solution of 103.16 g (0.28 mol) of 4,4'-bis(4-aminophenoxy)biphenyl (hereinafter referred to as BAPB) dissolved in 168 g of NMP was added dropwise over approximately 20 minutes. The mixture was stirred for 3 hours while maintaining the temperature below 5°C in an ice bath, and then the ice bath was removed and the mixture was stirred for 5 hours at room temperature. The precipitate that formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0393] A mixture of 840 g of water and 560 g of isopropanol was added dropwise to the resulting reaction solution, and the precipitated polymer was separated and redissolved in 650 g of NMP. The resulting crude polymer solution was added dropwise to 5 L of water to precipitate the polymer. The resulting precipitate was filtered and then vacuum dried to obtain a powdered polymer (Polymer (A)-4). The molecular weight of Polymer (A)-4 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 34,700.

[0394] <Production Example D5> (Synthesis of Polymer (A)-5 as Polyoxazole Precursor (A)) In a 3 L separable flask, 183.1 g of 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, 640.9 g of N,N-dimethylacetamide (DMAc), and 63.3 g of pyridine were mixed and stirred at room temperature (25°C) to form a homogeneous solution. A solution of 118.0 g of 4,4'-diphenyl ether dicarbonyl chloride in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise from a dropping funnel. The separable flask was cooled in a water bath at 15-20°C. The addition took 40 minutes, and the reaction temperature reached a maximum of 30°C.

[0395] Three hours after the completion of the dropwise addition, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic anhydride was added to the reaction mixture and stirred at room temperature for 15 hours. 99% of the total amine end groups on the polymer chain were capped with carboxycyclohexylamide groups. The conversion rate was easily calculated by monitoring the remaining amount of 1,2-cyclohexyldicarboxylic anhydride by high-performance liquid chromatography (HPLC). The reaction mixture was then added dropwise to 2 L of water with high-speed stirring to precipitate a polymer. The polymer was then recovered, washed appropriately with water, dehydrated, and vacuum dried to obtain a crude polybenzoxazole precursor with a weight-average molecular weight of 9,000 (polystyrene equivalent) as measured by gel permeation chromatography (GPC).

[0396] The crude polybenzoxazole precursor obtained above was redissolved in γ-butyrolactone (GBL), and then treated with a cation exchange resin and an anion exchange resin. The resulting solution was poured into ion-exchanged water, and the precipitated polymer was filtered, washed with water, and vacuum dried to obtain a purified polybenzoxazole precursor (polymer (A)-5).

[0397] <Production Example D6> (Synthesis of Polymer (A)-6 as Polyimide (A)) A separable four-neck glass flask equipped with a Teflon (registered trademark) anchor stirrer and a condenser with a Dean-Stark trap was attached. The flask was immersed in a silicone oil bath and stirred while nitrogen gas was passed through.

[0398] 72.28 g (280 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane (Clariant Japan) (hereinafter referred to as BAP), 70.29 g (266 mmol) of 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride (Tokyo Chemical Industry Co., Ltd.) (hereinafter referred to as MCTC), 254.6 g of γ-butyrolactone, and 60 g of toluene were added and stirred at 100 rpm at room temperature for 4 hours. Then, 4.6 g (28 mmol) of 5-norbornene-2,3-dicarboxylic anhydride (Tokyo Chemical Industry Co., Ltd.) was added and heated and stirred at 100 rpm for 8 hours while passing nitrogen gas through a silicon bath at 50°C. The silicon bath was then heated to 180°C and heated and stirred at 100 rpm for 2 hours. Toluene and water were removed during the reaction. After the imidization reaction was completed, the temperature was returned to room temperature.

[0399] The reaction solution was then added dropwise to 3 L of water under high-speed stirring to disperse and precipitate the polymer, which was then recovered, washed appropriately with water, dehydrated, and then vacuum dried to obtain a crude polyimide (polymer (A)-6) having a weight-average molecular weight of 23,000 (polystyrene equivalent) as measured by gel permeation chromatography (GPC).

[0400] Example D1 Negative-tone photosensitive resin compositions were prepared using polymers (A)-1 and (A)-2 by the following method, and the photosensitive resin compositions were evaluated. 50 g of the polyimide precursor polymers (A)-1 and (A)-2 (corresponding to (A) resin) were dissolved in a mixed solvent consisting of 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of ethyl lactate, along with 3 g of N-phenylbenzylamine (manufactured by Tokyo Chemical Industry Co., Ltd., corresponding to (B)-1), 4 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (referred to as "PDO" in Table 4) (corresponding to (C) photosensitizer), 8 g of tetraethylene glycol dimethacrylate, and 1.5 g of N-[3-(triethoxysilyl)propyl]phthalamic acid. The viscosity of the resulting solution was adjusted to about 35 poise by further adding a small amount of the mixed solvent, to obtain a negative photosensitive resin composition. This composition was cured at 230°C using the method described above to create a cured relief pattern on the Cu layer, and after a high-temperature storage test, the void area ratio on the surface of the Cu layer was evaluated and found to be 4.5%. Furthermore, the viscosity change rate of the resulting varnish after a storage stability test was within 10%. Example D2 A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 above, except that the component (B) in Example D1 was changed to N,N'-diphenylethane-1,2-diamine (manufactured by Tokyo Chemical Industry Co., Ltd.). This composition was cured at 230°C using the method described above to create a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated and found to be 4.2%. Furthermore, the viscosity change rate of the resulting varnish after a storage stability test was within 10%. Example D3 A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 above, except that the component (B) in Example D1 was changed to tert-butylphenyl carbamate (manufactured by Tokyo Chemical Industry Co., Ltd.). This composition was cured at 230°C using the method described above to create a cured relief pattern on the Cu layer, and after a high-temperature storage test, the void area ratio on the surface of the Cu layer was evaluated and found to be 5.1%. Furthermore, the viscosity change rate of the resulting varnish after a storage stability test was within 10%. Example D4 A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 above, except that the component (B) in Example D1 was changed to tert-butyl(3-hydroxyphenyl)carbamate (manufactured by Tokyo Chemical Industry Co., Ltd.). This composition was cured at 230°C using the method described above to create a cured relief pattern on the Cu layer, and after a high-temperature storage test, the void area ratio on the surface of the Cu layer was evaluated and found to be 5.8%. Furthermore, the viscosity change rate of the resulting varnish after a storage stability test was within 10%. Example D5 A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 above, except that in Example D1, component (B) was changed to 2-hydroxy-N-(1H-1,2,4-triazol-3-yl)benzamide (ADEKA CORPORATION, Adeka STAB CDA-1). This composition was cured at 230°C using the method described above to create a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated and found to be 4.8%. Furthermore, the viscosity change rate of the resulting varnish after a storage stability test was within 10%. Example D6 A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 above, except that in Example D1, component (B) was changed to 2-(2H-benzo[d][1,2,3]triazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol (ADEKA CORPORATION, ADK STAB LA-29). This composition was cured at 230°C using the method described above to create a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated and found to be 4.2%. Furthermore, the viscosity change rate of the resulting varnish after a storage stability test was within 10%. Example D7 A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 above, except that in Example D1, component (B) was changed to (4-((1H-1,2,4-triazol-1-yl)methyl)phenyl)methanol (manufactured by Tokyo Chemical Industry Co., Ltd.). This composition was cured at 230°C using the method described above to create a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated and found to be 6.1%. Furthermore, the viscosity change rate of the resulting varnish after a storage stability test was within 10%. <Example D8> A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 above, except that the amount of component (B)-1 added was changed to 1 g. This composition was cured at 230°C using the method described above to create a cured relief pattern on the Cu layer, and after a high-temperature storage test, the void area ratio on the surface of the Cu layer was evaluated and found to be 8.5%. Furthermore, the viscosity change rate of the resulting varnish after a storage stability test was within 10%. Example D9 A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 above, except that the amount of component (B)-1 added was changed to 6 g. This composition was cured at 230°C using the method described above to create a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated and found to be 4.9%. Furthermore, the viscosity change rate of the resulting varnish after a storage stability test was within 10%. <Example D10> A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 above, except that the amount of component (B)-1 added was changed to 10 g. This composition was cured at 230°C using the method described above to create a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated and found to be 5.0%. Furthermore, the viscosity change rate of the resulting varnish after a storage stability test was within 10%. <Example D11> A negative photosensitive resin composition solution was prepared in the same manner as in Example D1, except that the curing temperature was changed from 230°C to 350°C. A cured relief pattern was created on a Cu layer using this composition, and after a high-temperature storage test, the void area ratio on the surface of the Cu layer was evaluated and found to be 6.1%. Furthermore, the viscosity change rate of the resulting varnish after a storage stability test was within 10%. <Example D12> A negative photosensitive resin composition solution was prepared in the same manner as in Example D1, except that in Example D1, 50 g of polymer (A)-1 and 50 g of polymer (A)-2 were used as the (A) resin, but 100 g of polymer (A)-1 was used, and 2.5 g of 1,2-octanedione, 1-{4-(phenylthio)-, 2-(O-benzoyloxime)} (Irgacure OXE01 (BASF, trade name)) was used as the (C) component instead of PDO. A cured relief pattern was created on a Cu layer using this composition, and after a high-temperature storage test, the void area ratio on the surface of the Cu layer was evaluated and found to be 5.8%. Furthermore, the viscosity change rate of the resulting varnish after a storage stability test was within 10%. <Example D13> A negative photosensitive resin composition solution was prepared in the same manner as in Example D12, except that the solvent in Example D12 was changed to 85 g of γ-butyrolactone and 15 g of dimethyl sulfoxide. A cured relief pattern was created on a Cu layer using this composition, and after a high-temperature storage test, the void area ratio on the surface of the Cu layer was evaluated and found to be 5.4%. Furthermore, the viscosity change rate of the resulting varnish after a storage stability test was within 10%. <Example D14> A negative photosensitive resin composition solution was prepared in the same manner as in Example D1, except that in Example D1, 50 g of polymer (A)-1 and 50 g of polymer (A)-2 were replaced with 100 g of polymer (A)-3 as the (A) resin, and the curing temperature was changed from 230°C to 350°C. A cured relief pattern was created on a Cu layer using this composition, and after a high-temperature storage test, the void area ratio on the surface of the Cu layer was evaluated and found to be 7.2%. Furthermore, the viscosity change rate of the resulting varnish after a storage stability test was within 10%. <Example D15> A negative photosensitive resin composition solution was prepared in the same manner as in Example D1, except that in Example D1, 50 g of polymer (A)-1 and 50 g of polymer (A)-2 were replaced with 100 g of polymer (A)-4 as the (A) resin. A cured relief pattern was created on a Cu layer using this composition, and after a high-temperature storage test, the void area ratio on the surface of the Cu layer was evaluated and found to be 4.9%. Furthermore, the viscosity change rate of the resulting varnish after a storage stability test was within 10%. <Example D16> A positive photosensitive resin composition was prepared using polymer (A)-5 by the following method, and the prepared photosensitive resin composition was evaluated. 100 g of polymer (A)-5, which is a polyoxazole precursor, was added to the following compound represented by the formula (96): [ka] 15 g of a photosensitive diazoquinone compound (C1) (manufactured by Toyo Gosei Co., Ltd., corresponding to component (C)) in which 77% of the phenolic hydroxyl groups have been converted to naphthoquinone diazide-4-sulfonic acid ester, represented by the formula: was dissolved in 100 g of γ-butyrolactone (as a solvent). The viscosity of the resulting solution was adjusted to about 20 poise by further adding a small amount of γ-butyrolactone, to obtain a positive photosensitive resin composition. This composition was cured at 350°C using the method described above to create a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated and found to be 6.9%. Furthermore, the viscosity change rate of the resulting varnish after a storage stability test was within 10%. <Example D17> A positive photosensitive resin composition solution was prepared in the same manner as in Example D12, except that in Example D16, 100 g of polymer (A)-5 was changed to 100 g of polymer (A)-6 as the (A) resin. This composition was cured at 250°C using the method described above to create a cured relief pattern on the Cu layer, and after a high-temperature storage test, the void area ratio on the surface of the Cu layer was evaluated and found to be 6.0%. Furthermore, the viscosity change rate of the resulting varnish after a storage stability test was within 10%. <Comparative Example D1> A negative photosensitive resin composition was prepared in the same manner as in Example D1, except that the component (B)-1 was not added to the composition of Example D1, and the same evaluations were carried out as in Example D1. The evaluation result was 15.2% because the component (B) of the present invention was not included. Furthermore, the viscosity change rate of the obtained varnish after the storage stability test was within 10%. <Comparative example D2> A negative photosensitive resin composition was prepared in the same manner as in Example D15, except that the component (B)-1 was not added to the composition of Example D15, and the same evaluations were carried out as in Example D15. The evaluation result was 14.3% because the component (B) of the present invention was not included. Furthermore, the viscosity change rate of the obtained varnish after the storage stability test was within 10%. <Comparative Example D3> A negative photosensitive resin composition was prepared in the same manner as in Example D13, except that the (B)-1 component was not added to the composition of Example D13, and the same evaluations were carried out as in Example D13. The evaluation result was 15.7% because the component (B) of the present invention was not included. Furthermore, the viscosity change rate of the obtained varnish after the storage stability test was within 10%. <Comparative Example D4> A positive photosensitive resin composition was prepared in the same manner as in Example D17, except that the (B)-1 component was not added to the composition of Example D17, and the same evaluations were carried out as in Example D17. The evaluation result was 16.3% because the component (B) of the present invention was not included. Furthermore, the viscosity change rate of the obtained varnish after the storage stability test was within 10%. <Comparative Example D5> A negative photosensitive resin composition was prepared in the same manner as in Example D1, except that the amount of component (B)-1 added was changed to 25 g, and the same evaluations were carried out as in Example D1. The evaluation result was 7.2%. Furthermore, the viscosity change rate of the obtained varnish after the storage stability test was 10% or more. The results of Examples D1 to D17 and Comparative Examples D1 to D5 are summarized in Table 4.

[0401] [Table 1]

[0402] [Table 2]

[0403] [Table 3]

[0404] [Table 4] [Industrial Applicability]

[0405] The photosensitive resin composition of the present invention can be suitably used in the field of photosensitive materials useful for producing electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

1. (A) 100 parts by mass of at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, novolak, polyhydroxystyrene, and phenolic resin, (B) at least one compound selected from the group consisting of cyclic compounds having two or more carbonyl groups, wherein the carbonyl groups are directly bonded to the cyclic structure, and in the case of a monocyclic compound, one-third or more of the atoms forming the cyclic structure are nitrogen atoms, and in the case of a fused ring compound, one-third or more of the atoms forming the cyclic structure having the carbonyl group are nitrogen atoms, in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the (A) resin; and (C) 1 to 50 parts by mass of a photosensitizer based on 100 parts by mass of the (A) resin; A photosensitive resin composition comprising:

2. 2. The photosensitive resin composition according to claim 1, wherein the resin (A) is at least one selected from the group consisting of a polyimide precursor having the following general formula (1), a polyamide having the following general formula (4), a polyoxazole precursor having the following general formula (5), a polyimide having the following general formula (6), and a novolak, a polyhydroxystyrene, and a phenolic resin having the following general formula (7): The following general formula (1) 【Chemical 1】 {In the formula, X 1 is a tetravalent organic group, and Y 1 is a divalent organic group, and n 1 is an integer from 2 to 150, and R 1 and R 2 are each independently a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, an aromatic group, or a group represented by the following general formula (2): 【Chemistry 2】 (In the formula, R 3 , R 4 and R 5 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m 1 is an integer of 2 to 10, or a saturated aliphatic group having 1 to 4 carbon atoms, or a monovalent organic group represented by the following general formula (3): 【Chemistry 3】 (In the formula, R 6 , R 7 and R 8 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m 2 is an integer of 2 to 10. A monovalent ammonium ion represented by the formula: The following general formula (4) 【Chemistry 4】 {In the formula, X 2 is a trivalent organic group having 6 to 15 carbon atoms, and Y 2 is a divalent organic group having 6 to 35 carbon atoms, and may have the same structure or multiple structures; R 9 is an organic group having at least one radically polymerizable unsaturated bond group having 3 to 20 carbon atoms, and n 2 is an integer from 1 to 1000. It is a polyamide having a structure represented by The following general formula (5) 【Chemistry 5】 {In the formula, Y 3 is a tetravalent organic group having a carbon atom, and Y 4 , X 3 and X 4 are each independently a divalent organic group having two or more carbon atoms, and n 3 is an integer from 1 to 1000, and n 4 is an integer from 0 to 500, and n 3 / (n 3 +n 4 ) > 0.5, and X 3 and Y 3 n including 3 dihydroxydiamide units and X 4 and Y 4 n including 4 The arrangement order of the diamide units does not matter. and a polyhydroxyamide, which is a polyoxazole precursor, having a structure represented by the formula: The following general formula (6) is 【Chemistry 6】 {In the formula, X 5 is a tetravalent to tetratetravalent organic group, and Y 5 is a divalent to dodecavalent organic group, and R 10 and R 11 each independently represents an organic group having at least one group selected from a phenolic hydroxyl group, a sulfonic acid group, or a thiol group, and n 5 is an integer from 3 to 200, and m 3 and m 4 represents an integer from 0 to 10. and a polyimide having a structure represented by The following general formula (7) 【Chemistry 7】 {wherein a is an integer of 1 to 3, b is an integer of 0 to 3, 1≦(a+b)≦4, and R 12 represents a monovalent substituent selected from the group consisting of a monovalent organic group having 1 to 20 carbon atoms, a halogen atom, a nitro group, and a cyano group, and when b is 2 or 3, a plurality of R 12 may be the same or different, and X represents a divalent aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic group having 3 to 20 carbon atoms, or a group represented by the following general formula (8): 【Chemistry 8】 (wherein p is an integer of 1 to 10), and a divalent organic group selected from the group consisting of a divalent alkylene oxide group represented by the formula (I), and a divalent organic group having an aromatic ring and having 6 to 12 carbon atoms.

3. The photosensitive resin composition contains a phenolic resin having a repeating unit represented by the general formula (7), and X in the general formula (7) is a repeating unit represented by the following general formula (9): 【Chemistry 9】 {In the formula, R 13 , R 14 , R 15 and R 16 are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a monovalent aliphatic group having 1 to 10 carbon atoms in which some or all of the hydrogen atoms have been substituted with fluorine atoms, n 6 is an integer from 0 to 4, and n 6 is an integer from 1 to 4, 17 is a halogen atom, a hydroxyl group, or a monovalent organic group having 1 to 12 carbon atoms, and at least one R 17 is a hydroxyl group, and n 6 is an integer from 2 to 4, 17 may be the same or different from each other.}, and a divalent group represented by the following general formula (10): 【Chemistry 10】 {In the formula, R 18 , R 19 , R 20 and R 21 each independently represents a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a monovalent aliphatic group having 1 to 10 carbon atoms in which some or all of the hydrogen atoms have been substituted with fluorine atoms; W represents a single bond, an aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, an alicyclic group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, or a group represented by the following general formula (8): 【Chemistry 11】 (wherein p is an integer of 1 to 10), and a divalent alkylene oxide group represented by the following formula (11): 【Chemistry 12】 3. The photosensitive resin composition according to claim 1, wherein the divalent organic group is a divalent group selected from the group consisting of divalent groups represented by the following formula:

4. (1) forming a photosensitive resin layer on a substrate by applying the photosensitive resin composition according to any one of claims 1 to 3 onto the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) forming a hardened relief pattern by heat-treating the relief pattern; 1. A method for producing a cured relief pattern, comprising:

5. The method of claim 4 , wherein the substrate is formed from copper or a copper alloy.

6. A semiconductor device comprising a cured relief pattern obtained by the method of claim 4 or 5.

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