Photosensitive resin composition and method for producing cured relief pattern

Abstract

To provide a photosensitive resin composition capable of obtaining a resin layer of high adhesion, without causing a void at a boundary face of a Cu layer abutting on the cured photosensitive resin layer after a high temperature storage test, and also to provide a formation method of a cured relief pattern using the photosensitive resin composition.SOLUTION: In a photosensitive resin composition, a photosensitive resin and a specific plasticizer are combined to achieve a photosensitive resin of high adhesion, without causing a void at a boundary face of a Cu layer and a resin layer after a high temperature storage test. A cured relief pattern uses the photosensitive resin composition.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, and a method for forming a cured relief pattern using the same. [Background technology]

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

[0003] 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 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 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 discovered that by combining a specific photosensitive resin with a specific plasticizer, a photosensitive resin composition can be obtained that provides a cured film that does not generate voids at the interface where the Cu layer contacts the resin layer after a high-temperature storage test, and that provides a resin layer with high adhesion, and have thus completed the present invention.

[0010] [1] (A) 100 parts by mass of resin, (B) 2 to 16 parts by mass of a plasticizer 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, Including, The (A) resin is represented by the following 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, 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). A polyamic acid, polyamic acid ester, or polyamic acid salt polyimide precursor is a polyimide precursor represented by the formula: The (B) plasticizer is represented by the following general formula (7): [ka] {wherein X is a structure containing a saturated hydrocarbon, an unsaturated hydrocarbon, or an aromatic hydrocarbon having 1 to 15 carbon atoms, n is an integer from 1 to 4, and when n is 2 or more, R may be the same or different and are saturated hydrocarbons, unsaturated hydrocarbons, or aromatic hydrocarbons having 2 to 15 carbon atoms.} The following general formula (8): [ka] {wherein m is an integer of 1 to 4, and when m is 2 or greater, each R may be the same or different and is a saturated hydrocarbon, unsaturated hydrocarbon, or aromatic hydrocarbon having 2 to 15 carbon atoms.}, and The following general formula (9): [ka] {wherein Y is a structure containing a saturated hydrocarbon, an unsaturated hydrocarbon, or an aromatic hydrocarbon having from 1 to 10 carbon atoms, and R may be the same or different and are each represented by a saturated hydrocarbon, an unsaturated hydrocarbon, or an aromatic hydrocarbon having from 2 to 15 carbon atoms.} [2] The (B) plasticizer is The following general formula (8): [ka] {wherein m is an integer of 1 to 4, and when m is 2 or more, R may be the same or different and represent a saturated hydrocarbon, an unsaturated hydrocarbon, or an aromatic hydrocarbon having from 2 to 15 carbon atoms.}. [3] (1) A step of forming a photosensitive resin layer on a substrate by applying the photosensitive resin composition according to [1] or [2] 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: [4] The method according to [3], wherein the substrate is made of copper or a copper alloy.

[0011] The present inventors have also found that by incorporating nanoparticles into a photosensitive resin composition, it is possible to obtain a photosensitive resin composition that provides a cured film in which the generation of voids at the interface in contact with a Cu layer is suppressed after a high-temperature storage test. The present invention can also be applied to the following aspects. [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-1) nanoparticles 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) 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:}, wherein the polyimide precursor is a polyamic acid, a polyamic acid ester, or a polyamic acid salt, 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, multiple R1s may be the same or different from each other, 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].

[0012] The present inventors have also found that by combining a photosensitive resin with a specific thermal crosslinking agent, it is possible to obtain a negative-type photosensitive resin composition that provides a cured film in which the generation of voids at the interface in contact with a Cu layer is suppressed after a high-temperature storage test. The present invention can also be applied to the following aspects. [1] (A) 100 parts by mass of at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, and polyamic acid salt, (B-2) a thermal crosslinking agent in an amount of 0.01 to 50 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 negative photosensitive resin composition comprising: [2] The photosensitive resin composition according to [1], wherein the (A) resin is at least one selected from the group consisting of a polyimide precursor having the following general formula (1) and a polyamide having the following general formula (4): 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) is [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 polyimide having a structure represented by the following formula: [3] The photosensitive resin composition according to [1], wherein the (B-2) thermal crosslinking agent is at least one selected from the group consisting of (B-2-1) a compound containing at least one of a methylol group and an alkoxyalkyl group, (B-2-2) an oxirane ring-containing compound, (B-2-3) an isocyanate group-containing compound, (B-2-4) a bismaleimide group-containing compound, (B-2-5) an aldehyde group-containing compound, (B-2-6) an oxetane ring-containing compound, (B-2-7) a benzoxazine ring-containing compound, (B-2-8) an oxazoline ring-containing compound, (B-2-9) a carbodiimide group-containing compound, (B-2-10) an allyl compound, (B-2-11) a triazine thiol compound, and (B-2-12) a metal chelate compound. [4] The photosensitive resin composition according to [1] or [3], wherein the (B-2) thermal crosslinking agent is (B-2-1) a compound containing at least one of a methylol group and an alkoxyalkyl group. [5] The (B-2) thermal crosslinking agent is represented by the following general formula (TS1): [ka] {In the formula, Rs1 is a monovalent group selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group; Rs2 is a group selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an ester group having 1 to 10 carbon atoms, and a urethane group; mm1 is an integer of 1 to 5; and mm2 is an integer of 0 to 4. Here, 1≦(mm1+mm2)≦5, nn1 is an integer of 1 to 4, and V1 is CH2ORs1 when nn1=1, and is a single bond or a divalent to tetravalent organic group when nn1=2 to 4. CH2ORs1 and R 10 When there are multiple, they may be the same or different. The photosensitive resin composition according to [1] or [3], having a structure represented by the following formula: [6] (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 [5] 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: [7] [6] The method according to [6], wherein the substrate is made of copper or a copper alloy.

[0013] The present inventors have also found that by combining a specific photosensitive resin with a specific fluorine-containing hydrophobic compound, a photosensitive resin composition can be obtained that provides a cured film that does not generate voids at the interface where the Cu layer contacts the resin layer after a high-temperature storage test, and that provides a resin layer with high adhesion. The present invention can also be applied to the following aspects. [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, novolac, polyhydroxystyrene, and phenolic resin, (B-3) 0.01 to 50 parts by mass of a fluorine-containing hydrophobic compound 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) is [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.} 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, multiple R1s may be the same or different from each other, 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] X in the general formula (7) is 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, at least one R6 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, R18 , 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] The photosensitive resin composition according to any one of [1] to [3], wherein the weight ratio of fluorine atoms in the molecules of the fluorine-containing hydrophobic compound (B-3) is 30 mass % or more and 80 mass % or less. [5] The photosensitive resin composition according to any one of [1] to [4], wherein the (B-3) fluorine-containing hydrophobic compound has at least one unsaturated double bond in the molecule. [6] The photosensitive resin composition according to any one of [1] to [5], wherein the fluorine-containing hydrophobic compound (B-3) is an acrylate or methacrylate compound having a perfluoro group. [7] (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 [6] 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: [8] [7] The method according to [7], wherein the substrate is made of copper or a copper alloy. [Effects of the Invention]

[0014] According to the present invention, it is possible to provide a photosensitive resin composition that produces a photosensitive resin having high adhesion and that does not generate voids at the interface between a Cu layer and a resin 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

[0015] Hereinafter, an embodiment of the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. Note that the present embodiment is an example for explaining the present invention, and is not intended to limit the present invention. The present invention can be practiced by appropriately modifying it within the scope of its gist. 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 one another.

[0016] <Photosensitive resin composition> In this embodiment, the essential components are 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, and novolak, polyhydroxystyrene, and phenolic resin, (B) 0.1 to 50 parts by mass of plasticizer based on 100 parts by mass of the (A) resin, and (C) 1 to 50 parts by mass of photosensitizer based on 100 parts by mass of the (A) resin.

[0017] <Photosensitive resin composition> In another embodiment, the essential components are 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, and novolak, polyhydroxystyrene, and phenolic resin; (B-1) nanoparticles: 0.01 to 10 parts by mass based on 100 parts by mass of the (A) resin; and (C) photosensitizer: 1 to 50 parts by mass based on 100 parts by mass of the (A) resin.

[0018] <Photosensitive resin composition> Another embodiment is a negative-type photosensitive resin composition comprising, as essential components, 100 parts by mass of (A) at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, and polyamic acid salt, (B-2) a thermal crosslinking agent in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the (A) resin, and (C) a photosensitizer in an amount of 1 to 50 parts by mass based on 100 parts by mass of the (A) resin.

[0019] <Photosensitive resin composition> In another embodiment, the essential components are 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, and novolak, polyhydroxystyrene, and phenolic resin, 0.01 to 50 parts by mass of (B-3) a fluorine-containing hydrophobic compound based on 100 parts by mass of the (A) resin, and 1 to 50 parts by mass of (C) a photosensitizer based on 100 parts by mass of the (A) resin.

[0020] (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, 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.

[0021] 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. It is preferably 1,000 or more, more preferably 1,000 or more. The upper limit is preferably 500,000 or less, and when used as a photosensitive resin composition, it is more preferably 20,000 or less from the viewpoint of solubility in a developer.

[0022] In the present invention, the resin (A) is preferably a photosensitive resin in order to form 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.

[0023] Examples of photosensitive resins that can be used include polyamic acids, polyamic acid esters, polyamic acid salts, polyhydroxyamides, polyaminoamides, polyamides, polyamideimides, polyimides, polybenzoxazoles, and phenolic resins including novolacs and polyhydroxystyrenes. Among these, polyimide precursors (polyamic acids, polyamic acid esters, polyamic acid salts), polyamides, polyhydroxyamides, polyimides, and phenolic resins are preferred because the resins obtained after heat treatment have excellent heat resistance and mechanical properties. 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.

[0024] [(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.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] (Preparation of Acid / Ester Forms) In the present invention, the tetracarboxylic acid dianhydride containing a tetravalent organic group X1 that is suitably used for preparing an ester bond type polyimide precursor includes a tetracarboxylic acid dianhydride having a structure 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, diphenylsulfone-3,3',4,4'-tetracarboxylic acid dianhydride, Examples of suitable dianhydrides include, but are not limited to, 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 pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, and biphenyl-3,3',4,4'-tetracarboxylic dianhydride. These dianhydrides may be used alone or in combination of two or more.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] (Preparation of Polyimide Precursor) The acid / ester compound (typically a solution in a solvent described below) is mixed with an appropriate dehydration condensation agent, such as dicyclocarbodiimide, 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.

[0035] 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,

[0036] 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 suitable fluorocarbons 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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] [(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.

[0045] 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:

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] When a phthalic acid compound is blocked with a group containing the radically polymerizable unsaturated bond, negative photosensitivity (photocurability) can be imparted to the polyamide resin.

[0051] 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.

[0052] The above-mentioned phthalic acid compound-terminated 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.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] (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.

[0058] 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.

[0059] 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.

[0060] The chlorinating agent includes thionyl chloride.

[0061] 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.

[0062] 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.

[0063] 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,

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] [(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.}

[0074] 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).

[0075] 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.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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,

[0080] 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,

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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:

[0085] 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.

[0086] [(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.

[0087] 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.

[0088] 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,

[0089] 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.

[0090] 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,

[0091] 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.

[0092] 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.

[0093] 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,

[0094] 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.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] 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.

[0105] [(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.

[0106] 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.

[0107] 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 26 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.

[0108] (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.

[0109] 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.

[0110] (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.

[0111] The novolak and polyhydroxystyrene described above may each be used alone or in combination of two or more.

[0112] 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.

[0113] (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.

[0114] 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.

[0115] 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.

[0116] 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).

[0117] 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.

[0118] As the novolac and polyhydroxystyrene as the (a2) resin, the same resins as those listed in the above (novolac) and (polyhydroxystyrene) sections can be used.

[0119] 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.

[0120] Furthermore, in this embodiment, in the general formula (7), a and b satisfy the relationship 1≦(a+b)≦4.

[0121] 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.

[0122] 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:

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] 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.

[0128] 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.

[0129] 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.

[0130] 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.

[0131] 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.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] 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.

[0136] 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.

[0137] 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 %).

[0138] In the synthesis reaction of (A) phenolic resin, the reaction temperature is usually preferably 40°C to 250°C, more preferably in the range of 100°C to 200°C, and the reaction time is preferably about 1 hour to 10 hours. If necessary, a solvent capable of sufficiently dissolving the resin can be used.

[0139] 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.

[0140] (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.

[0141] 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).

[0142] 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.

[0143] 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.

[0144] 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.

[0145] 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.

[0146] 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.

[0147] 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.

[0148] 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.

[0149] 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.

[0150] 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.

[0151] 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.

[0152] 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.

[0153] 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.

[0154] 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, p-toluenesulfonic acid, trifluoromethanesulfonic acid, or the like may be used as a catalyst, if necessary. As will be described in detail later, solvents such as toluene, xylene, methanol, and tetrahydrofuran can be used for the reaction.

[0155] 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).

[0156] 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.

[0157] 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.

[0158] 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.

[0159] 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.

[0160] 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.

[0161] 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.

[0162] (B) Plasticizer The (B) plasticizer in this embodiment will be described in detail below. The (B) plasticizer is a compound that improves the fluidity of the (A) resin and improves the packing properties of the polymer in the (A) resin when a relief pattern formed using the photosensitive resin composition of this embodiment is heat-cured. By improving the packing properties, it is possible to suppress the generation of voids during a high-temperature storage test and to suppress a decrease in adhesion at the interface between the Cu layer and the resin layer. The (B) plasticizer is not particularly limited as long as it satisfies the above conditions.

[0163] (B) The compound functioning as a plasticizer is represented by the following general formula (7): [ka] In the formula, X is a structure containing a saturated hydrocarbon, an unsaturated hydrocarbon, or an aromatic hydrocarbon having 1 to 15 carbon atoms, n is an integer from 1 to 4, and when n is 2 or more, R may be the same or different and are each a saturated hydrocarbon, an unsaturated hydrocarbon, or an aromatic hydrocarbon having 2 to 15 carbon atoms.) is particularly preferably used.

[0164] Among them, the following general formula (8): [ka] {wherein m is an integer of 1 to 4, and when m is 2 or more, R may be the same or different and are represented by a saturated hydrocarbon, an unsaturated hydrocarbon, or an aromatic hydrocarbon having 2 or more and 15 or less carbon atoms.}, or The following general formula (9): [ka] {wherein Y is a structure containing a saturated hydrocarbon, an unsaturated hydrocarbon, or an aromatic hydrocarbon having 1 to 10 carbon atoms, and R may be the same or different and are each represented by a saturated hydrocarbon, an unsaturated hydrocarbon, or an aromatic hydrocarbon having 2 to 15 carbon atoms.} is preferred as the plasticizer of the present invention.

[0165] Examples of the plasticizer represented by the general formula (7) include benzoate esters, phthalate esters, isophthalate esters, terephthalate esters, trimellitate esters, pyromellitate esters, and tetrahydrofurfuryl aliphatic acid, etc. Specific examples of the benzoate ester compound include methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, pentyl benzoate, heptyl benzoate, n-octyl benzoate, nonyl benzoate, isononyl benzoate, isodecyl benzoate, 2-ethylhexyl benzoate, isodecyl benzoate, butylbenzyl benzoate, cyclopropyl benzoate, cyclobutyl benzoate, cyclopentyl benzoate, cyclohexyl benzoate, cycloheptyl benzoate, allyl benzoate, butylbenzyl benzoate, and phenyl benzoate. Among these, 2-ethylhexyl benzoate, cyclohexyl benzoate, and phenyl benzoate are particularly preferred.

[0166] Specific examples of phthalate ester compounds include dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dipentyl phthalate, diheptyl phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, bis(2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate, dicyclopropyl phthalate, dicyclobutyl phthalate, dicyclopentyl phthalate, dicyclohexyl phthalate, dicycloheptyl phthalate, diallyl phthalate, bisbutyl benzyl phthalate, and diphenyl phthalate. Among these, bis(2-ethylhexyl) phthalate, dicyclohexyl phthalate, and diphenyl phthalate are particularly preferred.

[0167] Specific examples of isophthalic acid ester compounds include dimethyl isophthalate, diethyl isophthalate, dipropyl isophthalate, dibutyl isophthalate, dipentyl isophthalate, diheptyl isophthalate, di-normal-octyl isophthalate, dinonyl isophthalate, diisononyl isophthalate, diisodecyl isophthalate, bis(2-ethylhexyl) isophthalate, diisodecyl isophthalate, butyl benzyl isophthalate, dicyclopropyl isophthalate, dicyclobutyl isophthalate, dicyclopentyl isophthalate, dicyclohexyl isophthalate, dicycloheptyl isophthalate, diallyl isophthalate, bisbutyl benzyl isophthalate, and diphenyl isophthalate. Among these, bis(2-ethylhexyl) isophthalate, dicyclohexyl isophthalate, and diphenyl isophthalate are particularly preferred.

[0168] Specific examples of terephthalic acid ester compounds include dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, dipentyl terephthalate, diheptyl terephthalate, di-normal-octyl terephthalate, dinonyl terephthalate, diisononyl terephthalate, diisodecyl terephthalate, bis(2-ethylhexyl) terephthalate, diisodecyl terephthalate, butyl benzyl terephthalate, dicyclopropyl terephthalate, dicyclobutyl terephthalate, dicyclopentyl terephthalate, dicyclohexyl terephthalate, dicycloheptyl terephthalate, diallyl terephthalate, bisbutyl benzyl terephthalate, and diphenyl terephthalate. Among these, bis(2-ethylhexyl) terephthalate, dicyclohexyl terephthalate, and diphenyl terephthalate are particularly preferred.

[0169] Specific examples of trimellitic acid ester compounds include trimethyl trimellitate, triethyl trimellitate, tripropyl trimellitate, tributyl trimellitate, tripentyl trimellitate, triheptyl trimellitate, tri-normal-octyl trimellitate, trinonyl trimellitate, triisononyl trimellitate, triisodecyl trimellitate, tris(2-ethylhexyl) trimellitate, triisodecyl trimellitate, trisbutylbenzyl trimellitate, tricyclopropyl trimellitate, tricyclobutyl trimellitate, tricyclopentyl trimellitate, tricyclohexyl trimellitate, tricycloheptyl trimellitate, triallyl trimellitate, trisbutylbenzyl trimellitate, and triphenyl trimellitate. Among these, tris(2-ethylhexyl) trimellitate, tricyclohexyl trimellitate, and triphenyl trimellitate are particularly preferred.

[0170] Specific examples of pyromellitic acid ester compounds include tetramethyl pyromellitic acid, tetraethyl pyromellitic acid, tetrapropyl pyromellitic acid, tetrabutyl pyromellitic acid, tetrapentyl pyromellitic acid, tetraheptyl pyromellitic acid, tetra-normal-octyl pyromellitic acid, tetranonyl pyromellitic acid, tetraisononyl pyromellitic acid, tetraisodecyl pyromellitic acid, tetrakis(2-ethylhexyl) pyromellitic acid, tetraisodecyl pyromellitic acid, tetrakisbutylbenzyl pyromellitic acid, tetracyclopropyl pyromellitic acid, tetracyclobutyl pyromellitic acid, tetracyclopentyl pyromellitic acid, tetracyclohexyl pyromellitic acid, tetracycloheptyl pyromellitic acid, tetraallyl pyromellitic acid, tetrakisbutylbenzyl pyromellitic acid, and tetraphenyl pyromellitic acid. Among these, tetrakis(2-ethylhexyl) pyromellitic acid, tetracyclohexyl pyromellitic acid, and tetraphenyl pyromellitic acid are particularly preferred.

[0171] Suitable plasticizers represented by the general formula (8) include malonic acid esters, succinic acid esters, glutaric acid esters, adipic acid esters, pimelic acid esters, suberic acid esters, azelaic acid esters, and sebacate esters. Specific examples of malonic acid esters include dimethyl malonate, diethyl malonate, dipropyl malonate, dibutyl malonate, dipentyl malonate, diheptyl malonate, di-n-octyl malonate, dinonyl malonate, diisononyl malonate, diisodecyl malonate, bis(2-ethylhexyl) malonate, diisodecyl malonate, butylbenzyl malonate, dicyclopropyl malonate, dicyclobutyl malonate, dicyclopentyl malonate, dicyclohexyl malonate, dicycloheptyl malonate, diallyl malonate, bisbutylbenzyl malonate, and diphenyl malonate. Among these, bis(2-ethylhexyl) malonate, dicyclohexyl malonate, and diphenyl malonate are particularly preferred.

[0172] Specific examples of succinate esters include dimethyl succinate, diethyl succinate, dipropyl succinate, dibutyl succinate, dipentyl succinate, diheptyl succinate, di-normal-octyl succinate, dinonyl succinate, diisononyl succinate, diisodecyl succinate, bis(2-ethylhexyl) succinate, diisodecyl succinate, butylbenzyl succinate, dicyclopropyl succinate, dicyclobutyl succinate, dicyclopentyl succinate, dicyclohexyl succinate, dicycloheptyl succinate, diallyl succinate, bisbutylbenzyl succinate, and diphenyl succinate. Among these, bis(2-ethylhexyl) succinate, dicyclohexyl succinate, and diphenyl succinate are particularly preferred.

[0173] Specific examples of glutaric acid ester compounds include dimethyl glutarate, diethyl glutarate, dipropyl glutarate, dibutyl glutarate, dipentyl glutarate, diheptyl glutarate, di-n-octyl glutarate, dinonyl glutarate, diisononyl glutarate, diisodecyl glutarate, bis(2-ethylhexyl) glutarate, diisodecyl glutarate, butylbenzyl glutarate, dicyclopropyl glutarate, dicyclobutyl glutarate, dicyclopentyl glutarate, dicyclohexyl glutarate, dicycloheptyl glutarate, diallyl glutarate, bisbutylbenzyl glutarate, and diphenyl glutarate. Among these, bis(2-ethylhexyl) glutarate, dicyclohexyl glutarate, and diphenyl glutarate are particularly preferred.

[0174] Specific examples of adipate esters include dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, dipentyl adipate, diheptyl adipate, di-n-octyl adipate, dinonyl adipate, diisononyl adipate, diisodecyl adipate, bis(2-ethylhexyl) adipate, diisodecyl adipate, butylbenzyl adipate, dicyclopropyl adipate, dicyclobutyl adipate, dicyclopentyl adipate, dicyclohexyl adipate, dicycloheptyl adipate, diallyl adipate, bisbutylbenzyl adipate, and diphenyl adipate. Among these, bis(2-ethylhexyl) adipate, dicyclohexyl adipate, and diphenyl adipate are particularly preferred.

[0175] Specific examples of pimelic acid esters include dimethyl pimelate, diethyl pimelate, dipropyl pimelate, dibutyl pimelate, dipentyl pimelate, diheptyl pimelate, di-n-octyl pimelate, dinonyl pimelate, diisononyl pimelate, diisodecyl pimelate, bis(2-ethylhexyl) pimelate, diisodecyl pimelate, butylbenzyl pimelate, dicyclopropyl pimelate, dicyclobutyl pimelate, dicyclopentyl pimelate, dicyclohexyl pimelate, dicycloheptyl pimelate, diallyl pimelate, bisbutylbenzyl pimelate, and diphenyl pimelate. Among these, bis(2-ethylhexyl) pimelate, dicyclohexyl pimelate, and diphenyl pimelate are particularly preferred.

[0176] Specific examples of suberate compounds include dimethyl suberate, diethyl suberate, dipropyl suberate, dibutyl suberate, dipentyl suberate, diheptyl suberate, di-n-octyl suberate, dinonyl suberate, diisononyl suberate, diisodecyl suberate, bis(2-ethylhexyl) suberate, diisodecyl suberate, butylbenzyl suberate, dicyclopropyl suberate, dicyclobutyl suberate, dicyclopentyl suberate, dicyclohexyl suberate, dicycloheptyl suberate, diallyl suberate, bisbutylbenzyl suberate, and diphenyl suberate. Among these, bis(2-ethylhexyl) suberate, dicyclohexyl suberate, and diphenyl suberate are particularly preferred.

[0177] Specific examples of azelaic acid ester compounds include dimethyl azelate, diethyl azelate, dipropyl azelate, dibutyl azelate, dipentyl azelate, diheptyl azelate, di-normal-octyl azelate, dinonyl azelate, diisononyl azelate, diisodecyl azelate, bis(2-ethylhexyl) azelate, diisodecyl azelate, butylbenzyl azelate, dicyclopropyl azelate, dicyclobutyl azelate, dicyclopentyl azelate, dicyclohexyl azelate, dicycloheptyl azelate, diallyl azelate, bisbutylbenzyl azelate, and diphenyl azelate. Among these, bis(2-ethylhexyl) azelate, dicyclohexyl azelate, and diphenyl azelate are particularly preferred.

[0178] Specific examples of sebacate ester compounds include dimethyl sebacate, diethyl sebacate, dipropyl sebacate, dibutyl sebacate, dipentyl sebacate, diheptyl sebacate, di-n-octyl sebacate, dinonyl sebacate, diisononyl sebacate, diisodecyl sebacate, bis(2-ethylhexyl) sebacate, diisodecyl sebacate, butyl benzyl sebacate, dicyclopropyl sebacate, dicyclobutyl sebacate, dicyclopentyl sebacate, dicyclohexyl sebacate, dicycloheptyl sebacate, diallyl sebacate, bisbutyl benzyl sebacate, and diphenyl sebacate. Among these, bis(2-ethylhexyl) sebacate, dicyclohexyl sebacate, and diphenyl sebacate are particularly preferred.

[0179] Specific examples of the aliphatic acid tetrahydrofurfuryl compound include tetrahydrofurfuryl formate, tetrahydrofurfuryl acetate, tetrahydrofurfuryl propionate, tetrahydrofurfuryl butyrate, tetrahydrofurfuryl isobutyrate, tetrahydrofurfuryl valerate, tetrahydrofurfuryl isovalerate, tetrahydrofurfuryl caproate, etc. Among these, tetrahydrofurfuryl propionate, tetrahydrofurfuryl butyrate, and tetrahydrofurfuryl isobutyrate are particularly preferred.

[0180] The content of the plasticizer (B) is preferably 0.1 to 50 parts by mass, more preferably 1 to 40 parts by mass, and even more preferably 1 to 30 parts by mass, relative to 100 parts by mass of the resin (A). A content higher than this range is undesirable because it reduces the glass transition temperature, while a content lower than this range does not provide sufficient plasticity, making it more likely that voids will occur between the resin and the copper surface.

[0181] The role of the plasticizer (B) in this embodiment is to improve the fluidity of the (A) resin and the packing of the polymer in the (A) resin when the relief pattern formed using the photosensitive resin composition of this embodiment is cured by heating, thereby obtaining a robust cured film, suppressing the generation of voids during high-temperature storage tests, and suppressing a decrease in adhesion at the interface between the Cu layer and the resin layer.

[0182] The photosensitive resin composition of the present embodiment can contain any of (B-1) nanoparticles, (B-2) a thermal crosslinking agent, and (B-3) a fluorine-containing hydrophobic compound, instead of or in combination with the above-mentioned (B) plasticizer. By combining a photosensitive resin with specific (B-1) nanoparticles, (B-2) a thermal crosslinking agent, or (B-3) a fluorine-containing hydrophobic compound, it is possible to provide a photosensitive resin composition that produces a photosensitive resin with high adhesion and no voids at the interface between the Cu layer and the resin layer after a high-temperature storage test, and a method for forming a cured relief pattern using the photosensitive resin composition.

[0183] (B-1) Nanoparticles The (B-1) nanoparticles are solid at room temperature and have an average primary particle size of 1 μm or less, preferably 300 nm or less, from the viewpoint of optical transparency. The primary particle size can be determined by SEM observation or laser diffraction. Furthermore, from the viewpoint of Cu migration resistance during HTS, plate-like, scale-like, needle-like, or fibrous particles with an aspect ratio of 5 or more are preferred. From the viewpoint of compatibility with the (A) resin, the nanoparticles are preferably surface-treated with a silane coupling agent or the like. Furthermore, from the viewpoint of water resistance, these nanoparticles preferably contain an oxide, composite oxide, doped oxide, oxoacid, oxoacid salt, nitride, carbide, or sulfide.

[0184] Examples of the (B-1) nanoparticles that can be used in the present invention include SiO2, Al2O3, TiO2, ZrO2, HfO2, V2O5, WO3, In2O3, SnO2, Sb2O3, Nb2O5, MoO3, Fe2O3, CuO, ZnO, CaO, MgO, aerosil, silica alumina, mica, montmorillonite, talc, clay, boehmite, kaolin, (poly)zirconium phosphate, barium titanate, calcium carbonate, (poly)zirconium tungstate, PZT, glass, aluminum borate, aluminum nitride, titanium nitride, silicon nitride, boron nitride, and mixtures thereof. The addition of nanoparticles can reduce the thermal expansion coefficient of the photosensitive resin. This reduction in the thermal expansion coefficient suppresses the thermal expansion of the resin during high-temperature storage tests, thereby suppressing copper migration. Nanoparticles with a high aspect ratio are preferred because they can reduce the thermal expansion coefficient with a smaller amount. Furthermore, nanoparticles with a high aspect ratio tend to reduce the number of voids on the copper surface, improving developability and chemical resistance, making them more preferable.

[0185] The aspect ratio of the nanoparticles is preferably greater than 1 from the viewpoints of the number of voids on the copper surface, developability, and chemical resistance, and the aspect ratio is preferably 2 or greater, more preferably 3 or greater, and even more preferably 4 or greater. Furthermore, the aspect ratio is more preferably 5 or greater, more preferably 8 or greater, more preferably 10 or greater, more preferably 12 or greater, more preferably 15 or greater, and particularly preferably 20 or greater. The aspect ratio is a value expressed as the length of the nanoparticle's major axis divided by the length of its minor axis. If the nanoparticle is a perfect sphere, the aspect ratio is 1. If the nanoparticle is not a perfect sphere or a perfect ellipsoid, the major axis of the nanoparticle is the diameter of the smallest sphere large enough to completely contain the nanoparticle, and the minor axis of the nanoparticle is the diameter of the largest sphere large enough to completely contain the nanoparticle.

[0186] The blending amount of (B-1) nanoparticles is 0.1 to 50 parts by mass, preferably 0.05 to 10 parts by mass, per 100 parts by mass of (A) resin. From the viewpoint of migration resistance, it is desirable to blend 0.1 parts by mass or more, and from the viewpoint of solubility, it is desirable to blend less than 50 parts by mass.

[0187] (B-2) Thermal crosslinking agent The (B-2) thermal crosslinking agent used in the present invention will now be described. The (B-2) thermal crosslinking agent refers to a compound that can crosslink with the (A) resin or that itself forms a crosslinked network when a relief pattern formed using the photosensitive resin composition of this embodiment is heat-cured. The (B) thermal crosslinking agent is not particularly limited as long as it satisfies the above conditions, but is preferably any of the following (B-2-1) to (B-2-12). (B-2-1) Compounds containing methylol groups and / or alkoxymethyl groups The compound containing a methylol group and / or an alkoxymethyl group is a compound represented by the following general formula (TS2): [ka] {wherein Rs3 is a monovalent organic group or a hydrogen atom.} Specifically, the following general formula (TS1): [ka] {In the formula, Rs1 is a monovalent group selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group; Rs2 is a group selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an ester group having 1 to 10 carbon atoms, and a urethane group; mm1 is an integer of 1 to 5; and mm2 is an integer of 0 to 4. Here, 1≦(mm1+mm2)≦5, nn1 is an integer of 1 to 4, and V1 is CH2ORs1 when nn1=1, and is a single bond or a divalent to tetravalent organic group when nn1=2 to 4. CH2ORs1 and R 10 When there are a plurality of, they may be the same or different.}, and General formulas (TS3) and (TS4): [ka] {wherein Rs3 and Rs4 each independently represent a monovalent organic group selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 10 carbon atoms.} [ka] {wherein each Rs5 is independently a hydrogen atom or a monovalent organic group selected from the group consisting of hydrocarbon groups having 1 to 10 carbon atoms.}, but are not limited to these.

[0188] Preferred specific examples include Cymel (registered trademark) 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300, Mycoat 102, 105 (all manufactured by Mitsui Cytec Co., Ltd.), Nikalac (registered trademark) MX-270, -280, -290, Nikalac MS-11, Nikalac MW-30, -10 0, -300, -390, -750 (manufactured by Sanwa Chemical Co., Ltd.), DML-OCHP, DML-MBPC, DML-BPC, DML-PEP, DML-34X, DML-PSBP, DML-PTBP, DML-PC HP, DML-POP, DML-PFP, DML-MBOC, BisCMP-F, DML-BisOC-Z, DML-BisOCHP-Z, DML-BisOC-P, DMOM-PTBT, TMOM-BP, TMO Examples of such methylol compounds include M-BPA, TML-BPAFMF, TM-BIP-A, HMOM-TP-HAP (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, dimethylbis(methoxymethyl)biphenyl, and methylolated novolac.

[0189] Among these, those having the structure represented by the above general formula (12) are more preferred, and specific examples thereof include 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, DML-BisOC-P, DMOM-PTBT, TMOM-BP, TMOM-BPA, TML-BPAFMF, TM-BIP-A, HMOM-TP-HAP (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, dimethylbis(methoxymethyl)biphenyl, and methylolated novolaks. Of these, TMOM-BP, TMOM-BPA, TML-BPAFMF, TM-BIP-A, and HMOM-TP-HAP are particularly preferred.

[0190] (B-2-2) Oxirane Compounds The oxirane (epoxy) compound is not particularly limited as long as it is a compound containing an epoxy group in the molecule, and specific examples thereof include phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol type epoxy resins, trisphenol type epoxy resins, tetraphenol type epoxy resins, phenol-xylylene type epoxy resins, naphthol-xylylene type epoxy resins, phenol-naphthol type epoxy resins, phenol-dicyclopentadiene type epoxy resins, alicyclic epoxy resins, linear 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, and YDB. -340, YDB-412, YDF-2001, YDF-2004 (trade names, manufactured by Nippon Steel Chemical Co., Ltd.), GAN, GOT, NC-3000-H, EPPN-501H, EPPN-502H, EOCN-1020, NC-6000, NC-7000L, EPPN-201L, XD-1000, EOCN-4600 (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 (trade names, manufactured by Japan Epoxy Resins Co., Ltd.), EHPE3150, Plaxel G402, PUE101, PUE105 (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-850CRP, 860, EXA-4701, EXA-4850-1000 (trade names, manufactured by DIC Corporation), Denacol® EX-201, EX-212L, EX-214L, EX-216L, 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-850L, EX-911, EM-1 50 (trade name, manufactured by Nagase ChemteX Corporation), Epolite (registered trademark) 70P, 40E, 100E, 100MF, 200E, 400E, 200P, 400P, 1500NP, 80MF, 4000, 3002 (trade name, manufactured by Kyoeisha Chemical), jER (registered trademark) 828, 834, 1001, 1002, 1003, 1004, 1005, 1007, 1010, 1100 L, 630, ESCN-220L, 220F, 220H, 220HH, 180H65, 1032H60, YX4000H, 152, 157S70, 1031 (manufactured by Mitsubishi Chemical), Adeka Resin (registered trademark) EP-4000s, EP-4003s (manufactured by Adeka), and the like.

[0191] Among these, from the viewpoint of reliability after HTS testing, triglycidyl isocyanurate, Epiclon 830, 850, 1050, N-680, N-690, N-695, N-770, HP-7200, HP-820, EXA-4850-1000, Denacol EX-201, EX-313, EX-314, EX-321, EX-411, EX-511, EX-512, EX-612, EX-614, EX-614B, EX-731, EX-810, EX-911, and EM-150 epoxy compounds are particularly preferred.

[0192] (B-2-3) Isocyanate group-containing compound The isocyanate group-containing compound is not particularly limited as long as it contains an isocyanate group in the molecule, but from the viewpoint of reliability after HTS testing, 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, ND (trade names, manufactured by Mitsui Chemicals, Inc.), Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T (trade names, manufactured by Asahi Kasei Chemicals Corporation), and the like are preferred.

[0193] (B-2-4) Bismaleimide compounds The bismaleimide compound is not particularly limited as long as it contains a maleimide group in the molecule. From the viewpoint of reliability after HTS testing, however, 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 ... Preferred are 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone 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 (trade names, manufactured by Daiwa Chemical Industry Co., Ltd.). (B-2-5) Aldehyde group-containing compounds The aldehyde group-containing compound is not particularly limited as long as it contains an aldehyde group in the molecule, and from the viewpoint of reliability after HTS testing, formaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, furfural, glyoxal, glutaraldehyde, terephthalaldehyde, isophthalaldehyde, hexamethylenetetramine, trioxane, malondialdehyde, succindialdehyde, and the like are preferred.

[0194] (B-2-6) Oxetane ring-containing compounds The oxetane ring-containing compound is a compound represented by the following formula: [ka] It is a compound containing a divalent group represented by the following formula: The oxetane ring-containing compound is not particularly limited as long as it contains an oxetanyl group in the molecule, and examples thereof include 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, bis[1-ethyl(3-oxetanyl)]methyl ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl, 4,4'-bis(3-ethyl-3-oxetanylmethoxy)biphenyl, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, diethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, bis(3-ethyl-3-oxetanylmethyl)diphenoate, trimethylene glycol bis(3-ethyl-3-oxetanylmethyl)diphenoate, and methyl ether. Tyrolpropane tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, 3-ethyl-3{[(3-ethyloxetanyl)methoxy]methyl}oxetane, 3-ethyl-3-hydroxymethyloxetane (OXT-101), 2-ethylhexyloxetane (OXT-212), xylylene bisoxetane (OXT-121), 3-ethyl-3-{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane (OXT-221), OX-SQ-H, OXT-191, PNOX-1009, RSOX, all manufactured by Toagosei Co., Ltd. below: [ka] and Ethanacol EHO, OXBP, OXMA, OXIPA, HBOX, and OXTP manufactured by Ube Industries, Ltd. Among these, OXBP, OXIPA, OXT-121, and OXT-221 are preferred from the viewpoints of solubility in a developer and elongation of the resulting cured film. (B-2-7) Benzoxazine ring-containing compounds The benzoxazine ring-containing compound is not particularly limited as long as it contains a benzoxazine ring in the molecule. From the viewpoint of reliability after HTS testing, however, the compounds disclosed in JP 2006-335671 A, as well as bisphenol F-type benzoxazine BF-BXZ, bisphenol A-type benzoxazine BA-BXZ, bisphenol S-type benzoxazine BS-BXZ (trade names, manufactured by Konishi Chemical Industry Co., Ltd.), and the like are preferred.

[0195] (B-2-8) Oxazoline ring-containing compounds The oxazoline ring-containing compound is not particularly limited as long as it is a compound containing an oxazoline ring in the molecule, and examples thereof include 2-oxazoline, 2-amino-2-oxazoline, 2,2'-bis(2-oxazoline), 1,3-bis(4,5-dihydro-2-oxazolyl)benzene, 1,4-bis(4,5-dihydro-2-oxazolyl)benzene, 1,3,5-tris(4,5-dihydro-2-oxazolyl)benzene, 2,2'-(2,6-pyridinediyl)bis(4-isopropyl-2-oxazoline), 2,2'-(2,6-pyridinediyl)bis(4-phenyl-2-oxazoline), 2-phenyl(2-oxazoline), 4,4-dimethyl-2-oxazoline, 2,2'-isopropylidenebis(4-phenyl-2-oxazoline), and the like. Examples of suitable oxazoline include 4-tert-butyl-2-oxazoline, 2-ethyl-2-oxazoline, 2,2'-isopropylidenebis(4-t-butyl-2-oxazoline), 2-isopropyl-2-oxazoline, 4-methoxymethyl-2-methyl-5-phenyl-2-oxazoline, 2-methyl-2-oxazoline, 2,4,4-trimethyl-2-oxazoline, and Nippon Shokubai Co., Ltd.'s Epocross series K-1010E, K-2010E, K-1020E, K-2020E, K-1030E, K-2030E, WS-500, WS-700, RPS-1005, and RAS-1005. From the viewpoint of reliability after HTS testing, for example, 2,2'-bis(2-oxazoline), 1,3-bis(4,5-dihydro-2-oxazolyl)benzene, 1,4-bis(4,5-dihydro-2-oxazolyl)benzene, 1,3,5-tris(4,5-dihydro-2-oxazolyl)benzene, 2-phenyl(2-oxazoline), Epocross WS-500, etc. are preferred.

[0196] The oxazoline ring-containing compound is represented by the following general formula (TS5): [ka] {In the formula, Rs6 is an organic group having 1 to 10 carbon atoms, and nn2 is an integer of 0 to 4.} More preferred are compounds represented by the following formula: and most preferred are 1,3-bis(4,5-dihydro-2-oxazolyl)benzene and 1,3,5-tris(4,5-dihydro-2-oxazolyl)benzene. (B-2-9) Carbodiimide group-containing compound The carbodiimide group-containing compound is not particularly limited as long as it contains a carbodiimide group in the molecule. From the viewpoint of reliability after HTS testing, however, bis(2,6-diisopropylphenyl)carbodiimide, Carbodilite SV-02, V-01, V-02, V-03, V-04, V-05, V-07, V-09, E-01, E-02, LA-1 (trade names, manufactured by Nisshinbo Chemical Inc.), and the like are preferred.

[0197] (B-2-10) Allyl compounds The allyl compound is not particularly limited as long as it contains an allyl group in the molecule, and examples thereof include trimethylolpropane trimethacrylate, 1,3,5-benzenetricarboxylic acid triallyl, trimellitic acid triallyl, pyromellitic acid tetraallyl ester, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, NK Ester 1G, 2G, 3G, 4G, 9G, 14G, NPG, BPE-100, BPE-200, BPE-500, BPE-1400, A-200, A-400, A-600, TMPT, A-TMM-3 (trade names, manufactured by Shin-Nakamura Chemical Co., Ltd.), BANI-M, BANI-X (trade names, manufactured by Maruzen Petrochemical Co., Ltd.), and the like.

[0198] Among these, from the viewpoint of reliability after HTS testing, vinyl acetate, trimethylolpropane trimethacrylate, 1,3,5-benzenetricarboxylic acid triallyl, trimellitic acid triallyl, pyromellitic acid tetraallyl ester, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, BANIM, and BANI-X are particularly preferred.

[0199] (B-2-11) Triazine thiol compounds The triazine thiol compound is not particularly limited as long as it contains a thiocyanuric acid group in the molecule. From the viewpoint of reliability after the HTS test, however, 2,4,6-trithiol-1,3,5-triazine, 2-dimethylamino-4,6-dithiol-1,3,5-triazine, 2-dibutylamino-4,6-dithiol-1,3,5-triazine, 2-phenylamino-4,6-dithiol-1,3,5-triazine, and the like are preferred.

[0200] (B-2-12) Metal chelate compounds Examples of metal chelate compounds include aluminum chelate compounds, titanium chelate compounds, zirconium chelate compounds, chromium chelate compounds, magnesium chelate compounds, and nickel chelate compounds. However, from the viewpoint of reliability after HTS testing, acetylacetone aluminum (III) salt, acetylacetone titanium (IV) salt, acetylacetone chromium (III) salt, acetylacetone magnesium (II) salt, acetylacetone nickel (II) salt, acetylacetone zirconium (IV) salt, trifluoroacetylacetone aluminum (III) salt, trifluoroacetylacetone titanium (IV) salt, trifluoroacetylacetone chromium (III) salt, trifluoroacetylacetone magnesium (II) salt, trifluoroacetylacetone nickel (II) salt, trifluoroacetylacetone zirconium (IV) salt, titanium diisopropoxybis(acetylacetonate), titanium tetraacetylacetonate, titanium di-2-ethylhexoxybis(2-ethyl-3-hydroxyhexoxide), titanium diisopropoxybis(ethylacetoacetate), and the like are preferred.

[0201] Among these compounds, from the viewpoint of reliability after HTS testing, acetylacetone aluminum (III) salt, acetylacetone titanium (IV) salt, acetylacetone zirconium (IV) salt, acetylacetone nickel (II) salt, trifluoroacetylacetone aluminum (III) salt, trifluoroacetylacetone titanium (IV) salt, trifluoroacetylacetone nickel (II) salt, trifluoroacetylacetone zirconium (IV) salt, titanium diisopropoxybis(acetylacetonate), titanium tetraacetylacetonate, titanium di-2-ethylhexoxybis(2-ethyl-3-hydroxyhexoxide), and titanium diisopropoxybis(ethylacetoacetate) are preferred, and from the viewpoint of adhesion on silicon wafers, acetylacetone aluminum (III) salt, acetylacetone titanium (IV) salt, acetylacetone zirconium (IV) salt, trifluoroacetylacetone aluminum (III) salt, trifluoroacetylacetone titanium (IV) salt, trifluoroacetylacetone zirconium (IV) salt, and titanium diisopropoxybis(acetylacetonate) are preferred. Among these crosslinking agents described in (B-2-1) to (B-2-12), from the viewpoint of reliability after HTS testing, (B-2-1) methylol group and / or alkoxymethyl group-containing compounds, (B-2-2) oxirane compounds, (B-2-3) isocyanate group-containing compounds, (B-2-4) bismaleimide group-containing compounds, (B-2-5) aldehyde group-containing compounds, (B-2-6) oxetane ring-containing compounds, (B-2-7) benzoxazine ring-containing compounds, and (B-2-8) oxazoline (B-2-1) methylol group- and / or alkoxymethyl group-containing compounds, (B-2-3) isocyanate group-containing compounds, (B-2-4) bismaleimide group-containing compounds, (B-2-6) oxetane ring-containing compounds, (B-2-7) benzoxazine ring-containing compounds, and (B-2-10) allyl compounds are preferred, and (B-2-1) methylol group- and / or alkoxymethyl group-containing compounds are most preferred.

[0202] These crosslinking agents (B-2) can be used either individually or in combination of two or more. Among the above (B-2) crosslinking agents, those preferably used in the present invention are (B-2-1) methylol group and / or alkoxymethyl group-containing compounds, and those more preferably used are compounds represented by the following general formula (12): [ka] {In the formula, Rs1 is a monovalent group selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group; Rs2 is a group selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an ester group having 1 to 10 carbon atoms, and a urethane group; mm1 is an integer of 1 to 5; and mm2 is an integer of 0 to 4. Here, 1≦(mm1+mm2)≦5, nn1 is an integer of 1 to 4, and V1 is CH2ORs1 when nn1=1, and is a single bond or a divalent to tetravalent organic group when nn1=2 to 4. CH2ORs1 and R 10 When a plurality of groups are present, they may be the same or different. By adding a crosslinking agent, the glass transition temperature of the resin can be increased at the same curing temperature. Increasing the glass transition temperature of the resin suppresses migration of copper into the resin.

[0203] The amount of the crosslinking agent (B-2) added is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and even more preferably 5 to 20 parts by mass, per 100 parts by mass of the resin (A).

[0204] (B-3) Fluorine-containing hydrophobic compound The fluorine-containing hydrophobic compound (B-3) in this embodiment will be described in detail below. The fluorine-containing hydrophobic compound (B) is not particularly limited as long as it contains a fluorine atom in the molecule and has hydrophobicity.

[0205] Compounds that can be suitably used as the fluorine-containing hydrophobic compound (B-3) in this embodiment include fluorinated acids, fluorinated acrylates, fluorinated methacrylates, fluorinated alcohols, fluorinated alkanes, fluorinated esters, and fluorinated ethers. <Fluorinated Acid> Specific examples of the fluorinated acid (B-3), which is a fluorine-containing hydrophobic compound, include perfluoropentanoyl fluoride, perfluorohexanoyl fluoride, perfluoroheptanoyl fluoride, perfluorooctanoyl fluoride, perfluorosuccinoyl fluoride, hexafluoroglutaryl fluoride, octafluoroadipoyl fluoride, perfluoromethoxypropionoyl fluoride, perfluorobutoxyethoxyacetyl fluoride, perfluoropolyether diacryl fluoride (n=1), perfluoropolyether diacryl fluoride (n=2), perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, perfluoro Preferred examples of the present invention include perfluorododecanoic acid, perfluorotetradecanoic acid, perfluorohexadecanoic acid, perfluoro-3,5,5-trimethylhexanoic acid, perfluoro-3,7-dimethyloctanoic acid, perfluorosuccinic acid, perfluoroglutaric acid, perfluoroadipic acid, perfluorosuberic acid, perfluoroazelaic acid, perfluorosebacic acid, perfluorododecanedioic acid, perfluoro-3,6-dioxaheptanoic acid, perfluoro-3,6,9-trioxadecanoic acid, perfluoro-3,6-dioxadecanoic acid, perfluoro-3,6,9-trioxatridecanoic acid, perfluoro-3,6-dioxaoctane-1,8-dioic acid, and perfluoro-3,6,9-trioxaundecane-1,11-dioic acid. <Fluorinated acrylate> Specific examples of the fluorinated acrylate (B-3), which is a fluorine-containing hydrophobic compound, include 1H,1H-perfluoro-n-butyl acrylate, 1H,1H-perfluoro-n-octyl acrylate, 1H,1H-perfluoro-n-decyl acrylate, 1H,1H,6H,6H-perfluoro-1,6-hexanediol diacrylate, 1H,1H,8H,8H-perfluorotetraethylene glycol diacrylate, 1H,1H,6H,6H-perfluorotriethylene glycol diacrylate, 1H,1H,4H,4H- Preferred examples of such compounds include perfluorodiethylene glycol diacrylate, 1H,1H,10H,10H-pentaethylene glycol diacrylate, 1H,1H,18H,18H-nonaethylene glycol diacrylate, perfluoro-1,6-hexanediol diacrylate, perfluorotetraethylene glycol diacrylate, perfluorotriethylene glycol diacrylate, perfluorodiethylene glycol diacrylate, pentaethylene glycol diacrylate, and nonaethylene glycol diacrylate. Among these, 1H,1H,6H,6H-perfluoro-1,6-hexanediol diacrylate and 1H,1H,8H,8H-perfluorotetraethylene glycol diacrylate are particularly preferred, and are available from Exfluor under the product names C6DIACRY and DA-F4EO, respectively. <Fluorinated methacrylate> Specific examples of the fluorinated methacrylate compound (B-3) that is a fluorine-containing hydrophobic compound include 1H,1H-perfluoro-n-butyl methacrylate, 1H,1H-perfluoro-n-octyl methacrylate, 1H,1H-perfluoro-n-decyl methacrylate, 1H,1H,6H,6H-perfluoro-1,6-hexanediol dimethacrylate, 1H,1H,8H,8H-perfluorotetraethylene glycol dimethacrylate, 1H,1H,6H,6H-perfluorotriethylene glycol dimethacrylate, 1H,1H,4 ... Perfluorodiethylene glycol dimethacrylate, 1H,1H,10H,10H-pentaethylene glycol dimethacrylate, 1H,1H,18H,18H-nonaethylene glycol dimethacrylate, perfluoro-1,6-hexanediol dimethacrylate, perfluorotetraethylene glycol dimethacrylate, perfluorotriethylene glycol dimethacrylate, perfluorodiethylene glycol dimethacrylate, pentaethylene glycol dimethacrylate, nonaethylene glycol dimethacrylate, and the like are preferably used. <Fluorinated alcohol> Specific examples of the fluorinated alcohol (B-3) which is a fluorine-containing hydrophobic compound include 1H,1H-perfluoro-1-hexanol, 1H,1H-perfluoro-1-heptanol, 1H,1H-perfluoro-1-octanol, 1H,1H-perfluoro-1-nonanol, 1H,1H-perfluoro-1-decanol, 1H,1H-perfluoro-1-undecanol, 1H,1H-perfluoro-1-dodecanol, 1H,1H-perfluoro-1-tetradecanol, 1H,1H-perfluoro-1-hexadecanol, perfluoro-3,5,5-trimethylhexane-1-ol, perfluoro-3,7-dimethyloctan-1-ol, 1H,1H,4H,4H-perfluoro-1,4-butanediol, and 1H,1H,5H,5H-perfluoro-1,5-pentanediol. 1H,1H,5H,5H-perfluoro-1,5-pentanediol, 1H,1H,6H,6H-perfluoro-1,6-hexanediol, 1H,1H,8H,8H-perfluoro-1,8-octanediol, 1H,1H,9H,9H-perfluoro-1,9-nonanediol, 1H,1H,10H,10H-perfluoro-1,10-decanediol, 1H,1H,12H,12H-perfluoro-1,12-dodecanediol, perfluoro-tert-butanol, fluorinated diethylene glycol monomethyl ether, fluorinated triethylene glycol monomethyl ether, fluorinated diethylene glycol monobutyl ether, fluorinated triethylene glycol monobutyl ether, fluorinated triethylene glycol, fluorinated tetraethylene glycol, and the like are preferably used. <Fluorinated Alkanes> Specific examples of the fluorinated alkane that is the fluorine-containing hydrophobic compound (B-3) that are preferably used include perfluoroheptane, perfluorooctane, perfluorononane, perfluorotridecane, perfluoropentadecane, 1H-perfluoropentane, 1H-perfluorohexane, 1H-perfluoroheptane, 1H-perfluorooctane, 1H-perfluorononane, 1H-perfluorodecane, 1H-perfluoroundecane, 1H-perfluorotridecane, 1H-perfluoropentadecane, 1H-perfluoro-2,4,4-trimethylpentane, 1H-perfluoro-2,6-dimethylheptane, 1H,4H-perfluorobutane, 1H,6H-perfluorohexane, 1H,7H-perfluoroheptane, 1H,8H-perfluorooctane, and 1H,10H-perfluorodecane. <Fluorinated ester> Specific examples of the fluorinated ester (B-3), which is a fluorine-containing hydrophobic compound, include methyl perfluoropentanoate, methyl perfluorohexanoate, methyl perfluoroheptanoate, methyl perfluorooctanoate, methyl perfluorononanoate, methyl perfluorodecanoate, methyl perfluoroundecanoate, methyl perfluorododecanoate, methyl perfluorotetradecanoate, methyl perfluorohexadecanoate, dimethyl perfluorosuccinate, dimethyl perfluoroglutarate, dimethyl perfluoroadipate, and dimethyl perfluorosubetanoate. Dimethyl phosphate, dimethyl perfluoroazelate, dimethyl perfluorosebacate, dimethyl perfluoro-1,12-decanedioate, methyl perfluoro-3,6-dioxaheptanoate, methyl perfluoro-3,6,9-trioxadecanoate, methyl perfluoro-3,6-dioxadecanoate, methyl perfluoro-3,6,9-trioxatridecanoate, dimethyl perfluoro-3,6-dioxaoctane-1,8-dioate, dimethyl perfluoro-3,6,9-trioxaundecane-1,11-dioate, and the like are preferably used. <Fluorinated ether> Specific examples of the fluorinated ether (B-3), which is a fluorine-containing hydrophobic compound, that are preferably used include perfluoro(diethylene glycol dimethyl ether), perfluoro(triethylene glycol dimethyl ether), and perfluoro(triethylene glycol dimethyl ether).

[0206] The weight percentage of fluorine atoms in the molecules of the (B-3) fluorine-containing hydrophobic compound is preferably 30% by mass or more and 80% by mass or less. If the weight percentage of fluorine is lower than this range, sufficient hydrophobicity cannot be obtained. On the other hand, if the fluorine content is higher than this range, compatibility with the solvent decreases, making it difficult to obtain a coating film with uniform surface flatness, which is not preferable. A more preferable range of the fluorine content by weight is 35% by mass or more and 75% by mass or less.

[0207] In this embodiment, the fluorine-containing hydrophobic compound (B-3) preferably has at least one unsaturated double bond in the molecule. The presence of an unsaturated double bond allows crosslinking reactions to occur between the fluorine-containing hydrophobic compound (B-3) molecules and between the fluorine-containing hydrophobic compound (B-3) and the resin (A) during the exposure process. This makes the fluorine-containing hydrophobic compound (B-3) less likely to volatilize during heat treatment, allowing the hydrophobic effect to be fully exerted. Suitable examples of unsaturated double bonds include acrylate and methacrylate.

[0208] The content of the fluorine-containing hydrophobic compound (B-3) is preferably 0.01 to 50 parts by mass, more preferably 0.02 to 30 parts by mass, and even more preferably 0.05 to 20 parts by mass, relative to 100 parts by mass of the resin (A). A content higher than this range is undesirable because it reduces compatibility with the solvent and makes it difficult to obtain a coating film with uniform surface flatness, while a content lower than this range does not provide a sufficient hydrophobic effect and is prone to voids occurring between the copper surface.

[0209] (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 polyamide as the resin (A), or a positive type that mainly uses, for example, at least one of a polyoxazole precursor, a soluble polyimide, a novolak, a polyhydroxystyrene, and a phenolic resin as the resin (A).

[0210] 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) photosensitive 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 photosensitive resin layer after curing.

[0211] [(C) Negative-type photosensitizer: polymerization initiator, 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,

[0212] 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.

[0213] 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.

[0214] In the case of a negative type, the blending amount of these photosensitizers is 1 to 50 parts by mass per 100 parts by mass of the (A) resin, and from the viewpoint of photosensitivity characteristics, 2 to 15 parts by mass is preferable. Blending 1 part by mass or more of the (C) photosensitizer per 100 parts by mass of the (A) resin provides excellent photosensitivity, and blending 50 parts by mass or less provides excellent thick-film curing properties.

[0215] 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.

[0216] 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.

[0217] 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.

[0218] [(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").

[0219] 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.

[0220] 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.

[0221] 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:

[0222] 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:

[0223] [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

[0224] [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

[0225] [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:

[0226] [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.

[0227] [ka]

[0228] [ka]

[0229] 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.

[0230] The structures of formulas (80) to (82) are as follows: [ka]

[0231] [ka]

[0232] [ka]

[0233] 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.

[0234] 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]

[0235] 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:

[0236] 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]

[0237] 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 is less prone to precipitation in a photosensitive resin composition.

[0238] As the compound represented by the 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 the photosensitive resin composition. The structures of formulas (92) and (93) are as follows: [ka] [ka]

[0239] 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.

[0240] (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.

[0241] 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.

[0242] 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.

[0243] 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 of the following formulae: [ka] However, all Qs cannot be hydrogen atoms at the same time.

[0244] 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.

[0245] Among the naphthoquinone diazide sulfonate ester groups described in paragraph

[0243] above, those having the following general formula (95): [ka] Particularly preferred are those represented by the following formula:

[0246] 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.

[0247] Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds, and trichloromethyltriazine is preferred.

[0248] In the case of a positive-tone composition, the amount of the photoacid generator is 1 to 50 parts by mass, preferably 5 to 30 parts by mass, per 100 parts by mass of the (A) resin. When the amount of the photoacid generator 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.

[0249] The above NQD compounds may be used alone or in combination of two or more.

[0250] 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.

[0251] The photosensitive resin composition of the present invention may further contain components other than the above components (A) to (C). The preferred components differ depending on whether the resin (A) is a negative type using, for example, a polyimide precursor and a polyamide, or a positive type using, for example, a polyoxazole precursor, a soluble polyimide and a phenolic resin.

[0252] 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.

[0253] <Solvent>

[0254] 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.

[0255] 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.

[0256] Suitable solvents for the above phenolic resins include, but are not limited to, 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.

[0257] 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).

[0258] The photosensitive resin composition of the present invention may further contain components other than the above components (A) to (C).

[0259] 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, a nitrogen-containing heterocyclic compound such as an azole compound or a purine derivative can be optionally blended in order to suppress discoloration on the copper.

[0260] 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.

[0261] 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.

[0262] 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.

[0263] When the photosensitive resin composition 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.

[0264] 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),

[0265] 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,

[0266] 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,

[0267] 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.

[0268] 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.

[0269] 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.

[0270] 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.

[0271] 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.

[0272] 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).

[0273] 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.

[0274] 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.

[0275] 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 the (B) compound and the organotitanium compound in the photosensitive resin composition, the cured resin layer has the effect of having excellent substrate adhesion and chemical resistance. In particular, by incorporating both the (B-1) nanoparticles and the organotitanium compound in the photosensitive resin composition, the resin layer after curing has excellent chemical resistance in addition to excellent substrate adhesion. In particular, by incorporating both the thermal crosslinking agent (B-2) and the organotitanium compound in the photosensitive resin composition, the resin layer after curing has excellent chemical resistance in addition to excellent substrate adhesion. In particular, by incorporating both the (B-3) compound and the organotitanium compound in the photosensitive resin composition, the resin layer after curing has excellent chemical resistance in addition to excellent substrate adhesion.

[0276] Usable organotitanium compounds include those in which an organic chemical is bonded to a titanium atom via a covalent or ionic bond.

[0277] 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.

[0278] 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.

[0279] 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.

[0280] IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.

[0281] V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.

[0282] VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate.

[0283] VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate.

[0284] 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.

[0285] 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.

[0286] 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.

[0287] 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.

[0288] 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.

[0289] 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]

[0290] 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.

[0291] The photosensitive resin composition of the present invention may further contain components other than those described above, and the preferred components 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.

[0292] 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.

[0293] 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.

[0294] 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.

[0295] 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.

[0296] In the case of negative-tone photosensitive resin compositions using a polyimide precursor or polyamide as the (A) resin, a thermal polymerization inhibitor can be optionally added to improve the viscosity and photosensitivity stability of the photosensitive resin composition, particularly during storage in a solvent-containing solution. Examples of thermal polymerization inhibitors that can be used include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

[0297] When the thermal polymerization inhibitor is added to the photosensitive resin composition, the amount of the thermal polymerization inhibitor added is preferably in the range of 0.005 to 12 parts by mass per 100 parts by mass of the (A) resin.

[0298] On the other hand, in the photosensitive resin composition of the present invention, when a polyoxazole precursor, a soluble polyimide, a phenolic resin, or the like is used as the resin (A), 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 appropriately added as needed.

[0299] 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.

[0300] 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.

[0301] 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.

[0302] 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.

[0303] 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.

[0304] 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.

[0305] 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.

[0306] 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.

[0307] 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.

[0308] 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.

[0309] 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.

[0310] <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.

[0311] (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.

[0312] As a method for forming a relief pattern using the photosensitive resin composition of the present invention, not only can the photosensitive resin composition be applied to a substrate to form a resin layer on the substrate, but also the photosensitive resin composition can be formed into a film and the layer of the photosensitive resin composition can be laminated on a substrate to form a resin layer. Alternatively, a film of the photosensitive resin composition of the present invention can be formed on a supporting substrate, and the supporting substrate can be removed after lamination when using the film, or before lamination.

[0313] 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.

[0314] (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.

[0315] 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.

[0316] (3) A step of developing the exposed resin layer to form a relief pattern. In this step, the exposed or unexposed portions of the photosensitive resin layer after exposure are 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 portions are 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 portions are 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.

[0317] 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.

[0318] 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.

[0319] 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.

[0320] 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.

[0321] 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.

[0322] (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.

[0323] <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.

[0324] 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. [Example]

[0325] 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.

[0326] (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.

[0327] (2) Creation of hardened relief patterns on Cu A 6-inch silicon wafer (manufactured by 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 (Model L-440S-FHL, manufactured by Canon Anelva Corporation). Subsequently, a photosensitive resin composition prepared by the method described below was spin-coated onto the wafer using a coater developer (Model D-Spin60A, manufactured by SOKUDO Co., Ltd.) and dried to form a 10 μm thick coating film (in the second example, a 6-10 μm thick coating film was formed). A test patterned mask was used to apply 300 mJ / cm to this coating film using a parallel light mask aligner (Model PLA-501FA, manufactured by 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.

[0328] 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.

[0329] (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

[0330] 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).

[0331] <First Example> As a first example, the following experiment was carried out.

[0332] <Production Example 1> ((A) Synthesis of Polymer (A)-1 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.

[0333] 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.

[0334] 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 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.

[0335] 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.

[0336] <Production Example 2> (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 the above-described Production Example 1, 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 1. 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.

[0337] <Production Example 3> (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 the above-described Production Example 1, 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 1. 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.

[0338] <Production Example 4> (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.

[0339] 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%.

[0340] (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.

[0341] 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.

[0342] <Production Example 5> (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.

[0343] 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).

[0344] 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).

[0345] <Production Example 6> (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.

[0346] 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.

[0347] 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).

[0348] <Production Example 7> (Synthesis of Polymer (A)-8 as (A) 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.

[0349] 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.

[0350] 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.

[0351] After the reaction was completed, the same treatment as in Production Example 7 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.

[0352] Example 1 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 4 g of dicyclohexyl phthalate (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 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 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 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 4.1%. <Example 2> A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 above, except that the component (B) in Example 1 was changed to diphenyl phthalate (manufactured by Tokyo Chemical Industry Co., Ltd.). 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 3 A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 above, except that component (B) was changed to di-2-ethylhexyl phthalate (manufactured by Tokyo Chemical Industry Co., Ltd.). 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 4 A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 above, except that the component (B) in Example 1 was changed to dicyclohexyl trimellitate (manufactured by Tokyo Chemical Industry Co., Ltd.). 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 4.3%. <Example 5> A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 above, except that component (B) was changed to dicyclohexyl pyromellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.). 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 4.2%. Example 6 A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 above, except that component (B) was changed to dicyclohexyl adipate (manufactured by Tokyo Chemical Industry Co., Ltd.). 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 5.9%. Example 7 A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 above, except that component (B) was changed to dicyclohexyl sebacate (manufactured by Tokyo Chemical Industry Co., Ltd.). 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 5.8%. Example 8 A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 above, except that the component (B) in Example 1 was changed to tetrahydrofurfuryl butyrate (manufactured by Tokyo Chemical Industry Co., Ltd.). 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 9 A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 above, except that the amount of component (B)-1 added was changed to 2 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 7.6%. Example 10 A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 above, except that the amount of component (B)-1 added was changed to 8 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 11 A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 above, except that the amount of component (B)-1 added was changed to 16 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 10.5%. Example 12 A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 above, 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 area ratio of voids on the surface of the Cu layer was evaluated, resulting in a result of 4.5%. Example 13 A negative photosensitive resin composition solution was prepared in the same manner as in Example 1, except that in Example 1, 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 area ratio of voids on the surface of the Cu layer was evaluated, resulting in a result of 4.3%. Example 14 A negative photosensitive resin composition solution was prepared in the same manner as in Example 12, except that the solvent in Example 12 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 area ratio of voids on the surface of the Cu layer was evaluated, resulting in a result of 4.5%. Example 15 A negative photosensitive resin composition solution was prepared in the same manner as in Example 1, except that in Example 1, 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 area ratio of voids on the surface of the Cu layer was evaluated, resulting in a result of 4.8%. Example 16 A negative photosensitive resin composition solution was prepared in the same manner as in Example 1, except that the (A) resin in Example 1 was changed from 50 g of polymer (A)-1 and 50 g of polymer (A)-2 to 100 g of polymer (A)-4. A cured relief pattern was created on a Cu layer using this composition, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, resulting in a result of 4.9%. Example 17 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 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 18 A positive photosensitive resin composition solution was prepared in the same manner as in Example 17, except that 100 g of polymer (A)-6 was used as the (A) resin instead of 100 g of polymer (A)-5. 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 6.2%. Example 19 A positive photosensitive resin composition solution was prepared in the same manner as in Example 17, except that in Example 17, 100 g of polymer (A)-6 was replaced with 100 g of polymer (A)-7 (novolak resin, polystyrene-equivalent weight average molecular weight (Mw) = 10,600 (manufactured by Asahi Organic Chemicals Co., Ltd., product name EP-4080G)). 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 5.2%. Example 20 A positive photosensitive resin composition solution was prepared in the same manner as in Example 17, except that in Example 17, 100 g of polymer (A)-6 was replaced with 100 g of polymer (A)-7 (novolak resin, polystyrene-equivalent weight average molecular weight (Mw) = 10,600 (manufactured by Asahi Organic Chemicals Co., Ltd., product name EP-4080G)) as the (A) resin, and the (B) component was replaced with tetrahydrofurfuryl butyrate (manufactured by Tokyo Chemical Industry Co., Ltd.). 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 5.6%. <Example 21> A positive photosensitive resin composition solution was prepared in the same manner as in Example 17, except that 100 g of polymer (A)-8 was used as the (A) resin instead of 100 g of polymer (A)-6. 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 4.6%. <Example 22> A positive photosensitive resin composition solution was prepared in the same manner as in Example 17, except that in Example 17, 100 g of polymer (A)-6 was replaced with 100 g of polymer (A)-8 as the (A) resin, and tetrahydrofurfuryl butyrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the (B) component. 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 4.3%. <Comparative Example 1> A negative photosensitive resin composition was prepared in the same manner as in Example 1, except that the (B)-1 component was not added to the composition of Example 1, and the composition was evaluated in the same manner as in Example 1. The evaluation result was 15.2% because the (B) plasticizer of the present invention was not included. <Comparative Example 2> A negative photosensitive resin composition was prepared in the same manner as in Example 15, except that the (B)-1 component was not added to the composition of Example 16, and the composition was evaluated in the same manner as in Example 15. The evaluation result was 14.3% because the composition did not contain the (B) plasticizer of the present invention. <Comparative Example 3> A negative photosensitive resin composition was prepared in the same manner as in Example 13, except that the (B)-1 component was not added to the composition of Example 14, and the composition was evaluated in the same manner as in Example 13. The evaluation result was 15.7% because the composition did not contain the (B) plasticizer of the present invention. <Comparative Example 4> A positive photosensitive resin composition was prepared in the same manner as in Example 17, except that the (B)-1 component was not added to the composition of Example 18, and the composition was evaluated in the same manner as in Example 17. The evaluation result was 16.3% because the composition did not contain the (B) plasticizer of the present invention. <Comparative Example 5> A negative photosensitive resin composition was prepared in the same manner as in Example 1, except that the amount of component (B)-1 added was changed to 0.05 g in the composition of Example 1, and the composition was evaluated in the same manner as in Example 1. The evaluation result was 13.1%. <Comparative Example 6> A negative photosensitive resin composition was prepared in the same manner as in Example 1, except that the amount of component (B)-1 added was changed to 60 g in the composition of Example 1, and the composition was evaluated in the same manner as in Example 1. The evaluation result was 15.2%. The results of Examples 1 to 22 and Comparative Examples 1 to 6 are summarized in Table 1. [Table 1]

[0353] <Second Example> As a second example, the following experiment was carried out.

[0354] <Production Example 1> ((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.

[0355] 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.

[0356] 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.

[0357] 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.

[0358] <Production Example 2> ((A) Synthesis of Polymer B as Polyimide Precursor) A reaction was carried out in the same manner as in the above-described Production Example 1, 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 1, 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.

[0359] <Production Example 3> (A) Synthesis of Polymer C as Polyimide Precursor) A reaction was carried out in the same manner as in the above-described Production Example 1, 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 1, 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.

[0360] <Production Example 4> ((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.

[0361] 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%.

[0362] (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.

[0363] 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 found to have a weight average molecular weight (Mw) of 34,700.

[0364] <Production Example 5> ((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.

[0365] 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).

[0366] 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).

[0367] <Production Example 6> ((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.

[0368] 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.

[0369] 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).

[0370] <Production Example 7> (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.

[0371] 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.

[0372] 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.

[0373] <Production Example 8> (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.

[0374] 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.

[0375] 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.

[0376] After the reaction was completed, the same treatment as in Production Example 7 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.

[0377] Example 1 Negative-tone photosensitive resin compositions were prepared using polymers A and B by the following method, and the prepared photosensitive resin compositions were evaluated. 50 g of polymers A and B (corresponding to (A) resin), which are polyimide precursors, 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 together with 5 g of zirconium phosphate (plate-like particles with a major axis of 100 nm and a minor axis of 5 nm, corresponding to (B-1) nanoparticles with an aspect ratio of 20), 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 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 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 2> A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 above, except that the amount of zirconium phosphate added as component (B-1) was changed to 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 6.6%. Example 3 A negative photosensitive resin composition solution was prepared in the same manner as in Example 1, except that montmorillonite (plate-like particles with a major axis of 100 nm, a minor axis of 10 nm, and an aspect ratio of 10) was used as the component (B-1) instead of zirconium phosphate. 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 5.8%. Example 4 A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 above, except that 1 g of Aerosil (spherical particles with a particle size of 12 nm, aspect ratio of 1) was used as the component (B-1) instead of 5 g of zirconium phosphate. 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 5> A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 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 4.5%. Example 6 A negative photosensitive resin composition solution was prepared in the same manner as in Example 1, except that in Example 1, 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 5.3%. Example 7 A negative photosensitive resin composition solution was prepared in the same manner as in Example 1, except that in Example 1, 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 5.3%. Example 8 A negative photosensitive resin composition solution was prepared in the same manner as in Example 1, except that 50 g of polymer A and 50 g of polymer B in Example 1 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 4.8%. Example 9 A negative photosensitive resin composition solution was prepared in the same manner as in Example 1, except that 50 g of polymer A and 50 g of polymer B in Example 1 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 5.6%. Example 10 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), 5 g of zirconium phosphate (plate-like particles with a major axis of 100 nm and a thickness of 5 nm, corresponding to (B) nanoparticles), 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-tone 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 5.7%. Example 11 A positive photosensitive resin composition solution was prepared in the same manner as in Example 10, 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 12 A positive photosensitive resin composition solution was prepared in the same manner as in Example 10, except that 100 g of polymer E was changed to 100 g of polymer G 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%. Example 13 A positive photosensitive resin composition solution was prepared in the same manner as in Example 10, 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 5.5%. <Comparative Example 1> A negative photosensitive resin composition was prepared in the same manner as in Example 1, except that zirconium phosphate was not added to the composition of Example 1, and the composition was evaluated in the same manner as in Example 1. The evaluation result was 14.3% because the compound (B) of the present invention was not contained. <Comparative Example 2> A negative photosensitive resin composition was prepared in the same manner as in Example 8, except that zirconium phosphate was not added to the composition of Example 8, and the composition was evaluated in the same manner as in Example 10. The evaluation result was 14.9% because the composition did not contain the compound (B) of the present invention. <Comparative Example 3> A positive photosensitive resin composition was prepared in the same manner as in Example 10, except that zirconium phosphate was not added to the composition of Example 10, and the composition was evaluated in the same manner as in Example 10. The evaluation result was 14.6% because the composition did not contain the compound (B) of the present invention. These results are summarized in Table 1.

[0378] [Table 2]

[0379] <Third Example> As a third example, the following experiment was carried out.

[0380] <Production Example 1> ((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.

[0381] 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.

[0382] 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.

[0383] 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.

[0384] <Production Example 2> ((A) Synthesis of Polymer B as Polyimide Precursor) A reaction was carried out in the same manner as in the above-described Production Example 1, 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 1, 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.

[0385] <Production Example 3> (A) Synthesis of Polymer C as Polyimide Precursor) A reaction was carried out in the same manner as in the above-described Production Example 1, 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 1, 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.

[0386] <Production Example 4> ((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.

[0387] 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%.

[0388] (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.

[0389] 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 found to have a weight average molecular weight (Mw) of 34,700.

[0390] Example 1 Negative-tone photosensitive resin compositions were prepared using polymers A and B using 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 10 g of TMOM-BP (trade name, Honshu Chemical, corresponding to (B-2) thermal crosslinker), 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 5.7%. <Example 2> A negative photosensitive resin composition solution was prepared in the same manner as in Example 1 above, except that the amount of TMOM-BP added as component (B-2) was changed to 20 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...

Claims

1. (A) 100 parts by mass of at least one resin selected from the group consisting of polyamic acid esters represented by the following general formula (1), polyamic acid salts, polyamides having a structure represented by the following general formula (4), and polybenzoxazole precursors, (B-1) 0.01 to 10 parts by mass of nanoparticles having an average primary particle diameter of 1 μm or less, 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; Including, 【Chemistry 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 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.) is a monovalent organic group represented by the formula: 【Transformation 3】 {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. The photosensitive resin composition, wherein the nanoparticles are any component selected from the group consisting of montmorillonite and zirconium phosphate.

2. The photosensitive resin composition according to claim 1 , wherein the nanoparticles are spherical, plate-like, scale-like, needle-like, or fibrous.

3. 2. The photosensitive resin composition according to claim 1, wherein in the resin (A), the polybenzoxazole precursor has a structure represented by the following general formula (5): 【Chemistry 4】 {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.

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 formed using the photosensitive resin composition according to any one of claims 1 to 3.

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