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

Abstract

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

Description

[Technical field]

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

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

[0003] Incidentally, semiconductor devices (hereinafter also referred to as "elements") are mounted on printed circuit boards by various methods according to the purpose. Conventional elements were generally fabricated by wire bonding, in which thin wires connect the external terminals (pads) of the element to the lead frame. However, as elements have become faster and the operating frequency has 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 precisely control the length of the mounting wiring, and it has become difficult to meet this requirement using wire bonding.

[0004] Therefore, flip-chip mounting has been proposed, in which a rewiring layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed thereon, and then the chip is flipped over and directly mounted on a printed circuit board (see, for example, Patent Document 1). This flip-chip mounting allows accurate control of wiring distance, and is therefore adopted for high-end devices that handle high-speed signals, and for mobile phones and the like due to its small mounting size, and demand 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 usually formed by roughening the surface of the resin layer by plasma etching, forming a metal layer to be a plating seed layer by sputtering to a thickness of 1 μm or less, and then using the metal layer as an electrode, by electrolytic plating. In this case, Ti is generally used as the metal that becomes the seed layer, and Cu is generally used as the metal for the rewiring layer formed by electrolytic plating.

[0005] For such a metal rewiring layer, it is required that the rewired metal layer and the resin layer have high adhesion after the reliability test. Examples of the reliability test carried out here include a high-temperature storage test in which the rewired metal layer is stored at a high temperature of 125°C or more for 100 hours or more in air, a high-temperature operation test in which the operation is confirmed under the condition of storing at a temperature of about 125°C for 100 hours or more in air while wiring is assembled and voltage is applied, a temperature cycle test in which a low-temperature state of about -65 to -40°C and a high-temperature state of about 125 to 150°C are cycled back and forth in air, a high-temperature and high-humidity storage test in which the rewired metal layer is stored in a water vapor atmosphere at a temperature of 85°C or more and a humidity of 85% or more, a high-temperature and high-humidity bias test in which the same test is carried out while wiring is assembled and voltage is applied, and a solder reflow test in which the rewired metal layer is passed through a solder reflow furnace at 260°C multiple times in air or under nitrogen.

[0006] However, in the past, in the case of a high-temperature storage test among the above reliability tests, there was a problem that voids were generated at the interface between the rewired Cu layer and 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 decreases. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2001-338947 A Summary of the Invention [Problem to be solved by the invention]

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

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

[0010] [1] (A) 100 parts by mass of at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, novolak, polyhydroxystyrene, and phenolic resin, (B) at least one compound selected from the group consisting of cyclic compounds having two or more carbonyl groups, the carbonyl group being directly bonded to the cyclic structure, in which in the case of a monocyclic compound, 1 / 3 or more of the atoms forming the cyclic structure are N atoms, and in the case of a condensed cyclic compound, 1 / 3 or more of the atoms forming the cyclic structure having the carbonyl group are N atoms, in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the (A) resin; and (C) a photosensitizer in an amount of 1 to 50 parts by mass 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 (A) resin 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: 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 at least one radically polymerizable unsaturated bond group having 3 to 20 carbon atoms, and n2 is an integer of 1 to 1000.} 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.} is a polyhydroxyamide, which is a polyoxazole precursor having a structure represented by The following general formula (6) is [ka] In the formula, X5 is a 4-14 valent organic group, Y5 is a 2-12 valent 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 The following general formula (7) is [ka] In the formula, a is an integer of 1 to 3, b is an integer of 0 to 3, and 1≦(a+b)≦4; 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 (I) and a divalent organic group having an aromatic ring having 6 to 12 carbon atoms. [3] The photosensitive resin composition contains a phenol resin having a repeating unit represented by the general formula (7), and 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 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; 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.} 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 are 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; 2. 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]. Effect of the Invention

[0011] According to the present invention, it is possible to provide a photosensitive resin composition which, by combining a specific photosensitive resin with a specific compound, produces a photosensitive resin having high adhesion and no voids are generated at the interface between a Cu layer and a polyimide layer after a high temperature storage test; a method for forming a cured relief pattern using the photosensitive resin composition; and a semiconductor device having the cured relief pattern. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

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

[0014] (A) Resin The resin (A) used in the present invention will be described. The resin (A) of the present invention is mainly 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, novolac, polyhydroxystyrene, and phenolic resin. Here, the term "main component" means that the resin contains 60% by mass or more of the total resin, and preferably 80% by mass or more. In addition, the resin may contain other resins as necessary.

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

[0016] In the present invention, the resin (A) is a photosensitive resin for forming a relief pattern. The photosensitive resin is used together with a photosensitizer (C) described below to form a photosensitive resin composition, and is a resin that causes a phenomenon of dissolving or not dissolving in the subsequent development step.

[0017] As the photosensitive resin, polyamic acid, polyamic acid ester, polyamic acid salt, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, and phenolic resin including novolac and polyhydroxystyrene are preferably used, since the resin after heat treatment has excellent heat resistance and mechanical properties. Moreover, 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 (C) photosensitizer described later.

[0018] [(A) Polyamic acid, polyamic acid ester, polyamic acid salt] In the photosensitive resin composition of the present invention, one example of the most preferable (A) resin from the viewpoint of heat resistance and photosensitive properties is a resin represented by the above 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. 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, a polyamic acid ester or a polyamic acid salt is a precursor of a polyimide represented by the formula (I). The polyimide precursor is converted to a polyimide by heating (for example, at 200° C. or higher) for cyclization. The polyimide precursor is suitable for use in a negative-type photosensitive resin composition.

[0019] In the above general formula (1), the tetravalent organic group represented by X1 is preferably an organic group having 6 to 40 carbon atoms, from the viewpoint of achieving both heat resistance and photosensitive properties, and more preferably an aromatic group in which the -COOR1 group and the -COOR2 group are in the ortho position relative to the -CONH- group, 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 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 fluorine-containing 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 the structure represented by the formula include, but are not limited to, the structure of X1. The structure of X1 may be one type or a combination of two or more types. The X1 group having the structure represented by the formula is particularly preferred in that it has both heat resistance and photosensitive properties.

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

[0021] In the above 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 photosensitive properties. Also, m1 is an integer of 2 to 10, preferably an integer of 2 to 4, from the viewpoint of photosensitive properties.

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

[0023] The ester bond-type polyimide precursor can be obtained by first reacting a tetracarboxylic 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 body), and then subjecting this to amide polycondensation with a diamine containing the above-mentioned divalent organic group Y1.

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

[0025] In the present invention, examples of alcohols having a photopolymerizable unsaturated double bond that are preferably used for preparing 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, and 2-hydroxy-3-t-butoxypropyl acrylate. Examples of the methacryloyloxypropyl acrylate include 1-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

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

[0027] The tetracarboxylic dianhydride suitable for the present invention and the alcohols 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 can be obtained.

[0028] (Preparation of polyimide precursor) The above acid / ester (typically a solution in a solvent described below) is mixed with an appropriate dehydration condensation agent, such as dicyclocarbodiimide (e.g., dicyclohexylcarbodiimide), 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, etc., under ice cooling to convert the acid / ester into a polyacid anhydride, and then a diamine containing a divalent organic group Y1 preferably used in the present invention, dissolved or dispersed in a separate solvent, is added dropwise to the acid / ester to perform amide polycondensation to obtain the desired polyimide precursor. Alternatively, the above acid / ester is converted into an acid chloride by using thionyl chloride or the like, and then reacted with a diamine compound in the presence of a base such as pyridine to obtain the desired polyimide precursor.

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

[0030] 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)benzene, 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, those substituted with a ethyl 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 aryl groups include, but are not limited to, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, and the like, and mixtures thereof.

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

[0032] After the amide polycondensation reaction is completed, the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction solution is filtered off as necessary, 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 operations, and then vacuum drying is performed to isolate the desired polyimide precursor. In order to improve the degree of purification, the polymer solution may be passed through a column packed with an anion and / or cation exchange resin swollen with an appropriate organic solvent to remove ionic impurities.

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

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

[0035] As the (meth)acrylic compound having an amino group, 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, and among them, from the viewpoint of photosensitive properties, dialkylaminoalkyl acrylates or methacrylates in which the alkyl group on the amino group has 1 to 10 carbon atoms and the alkyl chain has 1 to 10 carbon atoms are preferred.

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

[0037] The molecular weight of the ester-bonded and ion-bonded polyimide precursors is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, when measured by gel permeation chromatography in terms of polystyrene equivalent weight average molecular weight. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, and when it is 150,000 or less, the dispersibility in the developer is good, and the resolution performance of the relief pattern is good. As the developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. The weight average molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko KK.

[0038] [(A) Polyamide] Another example of a preferable (A) resin 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 at least one radically polymerizable unsaturated bond group having 3 to 20 carbon atoms, and n2 is an integer of 1 to 1000.} The polyamide has a structure represented by the following formula: This polyamide is suitable for use in a negative-type photosensitive resin composition.

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

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

[0041] In the above general formula (4), the divalent organic group represented by Y2 is preferably an organic group having 6 to 35 carbon atoms, and more preferably a cyclic organic group having 1 to 4 aromatic or aliphatic rings which may be substituted, or an aliphatic group or siloxane group having no cyclic structure. The divalent organic group represented by Y2 includes the following general formula (I) and the following general formulas (34) and (35): [ka] [ka] {where, R 33 and R 34 are each independently one group selected from the group consisting of a hydroxyl group, a methyl group (-CH3), an ethyl group (-C2H5), a propyl group (-C3H7) or a butyl group (-C4H9), and the propyl group and the butyl group include various isomers. [ka] In the formula, m7 represents an integer of 0 to 8, m8 and m9 each independently represent an integer of 0 to 3, and m 10 and m 11 are each independently an integer from 0 to 10, and R 35 and R 36 is a methyl group (-CH3), an ethyl group (-C2H5), a propyl group (-C3H7), a butyl group (-C4H9), or an isomer thereof.

[0042] The aliphatic group or siloxane group having no cyclic structure may be a group represented by the following general formula (36): [ka] {in formula, m 12 is an integer from 2 to 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 a phenyl group which may be substituted.} is mentioned as a preferred example.

[0043] The polyamide resin of the present invention can be synthesized, for example, as follows. (Synthesis of phthalic acid compound-capped compound) First, a compound having a trivalent aromatic group X2, for example, 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 1 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 blocked with a group containing a radically polymerizable unsaturated bond as described below (hereinafter referred to as a "blocked phthalic acid compound"). These may be used alone or in combination.

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

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

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

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

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

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

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

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

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

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

[0054] The chlorinating agent includes thionyl chloride and the like.

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

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

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

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

[0059] Examples of diamine compounds in which the hydrogen atoms on the benzene ring are substituted include 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, and 3,3'-dichloro-4,4'-diaminobiphenyl.

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

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

[0062] Examples of the linear aliphatic diamine compound include hydrocarbon 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 diamines such as 2-(2-aminoethoxy)ethylamine, 2,2'-(ethylenedioxy)diethylamine, and bis[2-(2-aminoethoxy)ethyl]ether.

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

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

[0065] The polyamide preferably has a polystyrene-equivalent weight average molecular weight of 7,000 to 70,000, and more preferably 10,000 to 50,000, as determined by gel permeation chromatography (hereinafter referred to as "GPC"). If the polystyrene-equivalent weight average molecular weight is 7,000 or more, the basic physical properties of the cured relief pattern are ensured. If the polystyrene-equivalent weight average molecular weight is 70,000 or less, the development solubility during the formation of the relief pattern is ensured.

[0066] Tetrahydrofuran or N-methyl-2-pyrrolidone is recommended as the eluent for GPC. The weight average molecular weight value is 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 standard sample STANDARD SM-105.

[0067] [(A) Polyhydroxyamide] Another example of a preferable (A) resin 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 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.} Polyhydroxyamide (polyoxazole precursor (hereinafter, the polyhydroxyamide represented by the above general formula (5) may be simply referred to as "polyoxazole precursor")) having a structure represented by the following formula.

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

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

[0070] The dihydroxydiamide unit can be formed by synthesis from a diaminodihydroxy compound (preferably bisaminophenol) having the structure of Y3(NH2)2(OH)2 and a dicarboxylic acid having the structure of X3(COOH)2. A typical embodiment will be described below using a case where the diaminodihydroxy compound is bisaminophenol as an example. The two pairs of amino groups and hydroxy groups of the bisaminophenol are in the ortho position relative to each other, and the dihydroxydiamide unit is ring-closed by heating at about 250 to 400°C, and changes to a heat-resistant polyoxazole structure. n3 in the general formula (5) is 1 or more for the purpose of obtaining photosensitive properties and 1000 or less for the purpose of obtaining photosensitive properties. n3 is preferably in the range of 2 to 1000, more preferably in the range of 3 to 50, and most preferably in the range of 3 to 20.

[0071] The polyoxazole precursor may have n4 of the diamide units condensed therein as necessary. The diamide units can be formed by synthesis from a diamine having a structure of Y4(NH2)2 and a dicarboxylic acid having a structure of X4(COOH)2. n4 in the general formula (5) is in the range of 0 to 500, and good photosensitive properties can be obtained when n4 is 500 or less. n4 is more preferably in the range of 0 to 10. If the ratio of the diamide units to the dihydroxydiamide units is too high, the solubility in an alkaline aqueous solution used as a developer decreases, so the value of n3 / (n3+n4) in the general formula (5) is more than 0.5, more preferably 0.7 or more, and most preferably 0.8 or more.

[0072] Examples of bisaminophenols as diaminodihydroxy compounds having the structure Y3(NH2)2(OH)2 include 3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis-(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoro ... Examples of the bisaminophenols include bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, and 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenols can be used alone or in combination of two or more. The Y3 group in the bisaminophenol can be represented by the following formula (37): [ka] In terms of photosensitive properties, those represented by the following formula are preferred: {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}.

[0073] Examples of diamines having the structure Y4(NH2)2 include aromatic diamines and silicon diamines. 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'-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane, 3,4'-diaminodiphenyl methane, 4 ... ,4'-Diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4-methyl-2,4-bis(4-aminophenyl)-1-pentene,

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

[0075] Examples of the aromatic diamine include 4,4'-diaminobenzophenone, phenylindane diamine, 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)diphenylsulfone, 4,4'-diaminobenzanilide, and the like, as well as compounds in which the hydrogen atoms of the aromatic nuclei of these aromatic diamines are substituted with at least one group or atom selected from the group consisting of chlorine atoms, fluorine atoms, bromine atoms, methyl groups, methoxy groups, cyano groups, and phenyl groups.

[0076] In addition, silicon diamine can be selected as the diamine to enhance adhesion to the substrate. Examples of silicon diamine 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, bis(γ-aminopropyl)tetraphenyldisiloxane, etc.

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

[0078] The polyoxazole precursor may have a terminal group blocked with a specific organic group. When a polyoxazole precursor blocked with a blocking group is used, it is expected that the mechanical properties (especially elongation) and the cured relief pattern shape of the coating film after heat curing of the photosensitive resin composition of the present invention will be good. A suitable example of such a blocking group is a polyoxazole precursor represented by the following formula (39): [ka] Examples of the above-mentioned are represented by the following formula:

[0079] The polystyrene-equivalent weight average molecular weight of the polyoxazole precursor 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. From the viewpoint of resolution, it is preferably 70,000 or less. As the developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. In addition, the molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from the organic solvent-based standard sample STANDARD SM-105 manufactured by Showa Denko KK.

[0080] [(A) Polyimide] Another example of a preferable (A) resin in the photosensitive resin composition of the present invention is a resin represented by the general formula (6): [ka] In the formula, X5 is a 4-14 valent organic group, Y5 is a 2-12 valent 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.} 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 develop sufficient film properties, and is therefore suitable for treatment at lower temperatures. X5 in the structural unit represented by the above general formula (6) is preferably a 4-14 valent organic group having 4 to 40 carbon atoms, and more preferably an organic group having 5 to 40 carbon atoms and containing an aromatic ring or an aliphatic ring, in order to achieve both heat resistance and photosensitive properties.

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

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

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

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

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

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

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

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

[0089] Among these, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane, 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.} Preferred is a diamine having a structure represented by the following formula:

[0090] Among these, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 1,4-bis(4-aminophenoxy)benzene, and the compound 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 kinds.

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

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

[0093] Furthermore, in order 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 decrease heat resistance.Specific examples of the diamine component include those copolymerized with 1 to 10 mol % of bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc.

[0094] The polyimide can be synthesized by, for example, reacting a tetracarboxylic dianhydride with a diamine compound (partially substituted with a terminal blocking agent that is a monoamine) at low temperature, reacting a tetracarboxylic dianhydride (partially substituted with a terminal blocking agent that is an acid anhydride, a monoacid chloride compound, or a monoactive ester compound) with a diamine compound at low temperature, obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then reacting it with a diamine (partially substituted with a terminal blocking agent that is a monoamine) in the presence of a condensing agent, obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then converting the remaining dicarboxylic acid into an acid chloride and reacting it with a diamine (partially substituted with a terminal blocking agent that is a monoamine), or by using a method in which a polyimide precursor is obtained and then completely imidized by a known imidization reaction method, or by stopping the imidization reaction midway and partially introducing an imide structure (in this case, polyamideimide), or by blending a completely imidized polymer with the polyimide precursor to partially introduce an imide structure.

[0095] The polyimide preferably has an imidization rate of 15% or more relative to the entire 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 entire 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 a thick film.

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

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

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

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

[0100] In this embodiment, the weight average molecular weight of the (A) phenolic resin is preferably 700 to 100,000, more preferably 1,500 to 80,000, and even more preferably 2,000 to 50,000. From the viewpoint of the applicability of the cured film to reflow treatment, 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 from a calibration curve prepared using standard polystyrene.

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

[0102] (Novolac) In this disclosure, novolac refers to any polymer obtained by condensing phenols and formaldehyde in the presence of a catalyst. In general, novolac can be obtained by condensing less than 1 mole of formaldehyde with 1 mole of phenols. 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, β-naphthol, etc. Specific examples of novolak include phenol / formaldehyde condensed novolak resins, cresol / formaldehyde condensed novolak resins, and phenol-naphthol / formaldehyde condensed novolak resins.

[0103] The weight average molecular weight of the novolak is preferably 700 to 100,000, more preferably 1,500 to 80,000, and further 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, the weight average molecular weight is preferably 100,000 or less.

[0104] (Polyhydroxystyrene) In the present disclosure, polyhydroxystyrene means a polymer containing hydroxystyrene as a polymerization unit in general. A preferred example of polyhydroxystyrene is polyparavinylphenol. Polyparavinylphenol means a polymer containing paravinylphenol as a polymerization unit in general. Therefore, to constitute polyhydroxystyrene (for example, polyparavinylphenol), a polymerization unit other than hydroxystyrene (for example, paravinylphenol) can be used as long as it does not go against the object of the present invention. In polyhydroxystyrene, the ratio of the number of moles of hydroxystyrene units based on the number of moles of all polymerization units is preferably 10 mol% to 99 mol%, more preferably 20 to 97 mol%, and even more preferably 30 to 95 mol%. When the ratio is 10 mol% or more, it is advantageous from the viewpoint of the alkali solubility of the photosensitive resin composition, and when it is 99 mol% or less, it is advantageous from the viewpoint of the reflow applicability of the cured film obtained by curing the composition containing the copolymerization component described later. The polymerization unit other than hydroxystyrene (for example, paravinylphenol) can be any polymerization unit copolymerizable with hydroxystyrene (for example, paravinylphenol).Examples of copolymerization components that provide polymerization 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 ... 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, for example, 2-methylstyrene and vinyltoluene; vinyl ester monomers such as, for example, vinyl acrylate and vinyl methacrylate; and o-vinylphenol, m-vinylphenol, and the like.

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

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

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

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

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

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

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

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

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

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

[0115] In this embodiment, in the above general formula (7), X is a divalent organic group selected from the group consisting of a divalent aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic group having 3 to 20 carbon atoms, an alkylene oxide group represented by the above general formula (8), and a divalent organic group having an aromatic ring having 6 to 12 carbon atoms, from the viewpoint of the shape of the cured relief pattern and the elongation of the cured film. Among these divalent organic groups, X is preferably a divalent organic group represented by the following general formula (9): [ka] {where, R 13 , R 14 , R 15 and R 16 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; 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.} 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 are 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 number of carbon atoms in the divalent organic group X having an aromatic ring with 6 to 12 carbon atoms is preferably 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 a divalent organic group selected from the group consisting of divalent groups represented by the general formula (7) above, in which an OH group and any R 12 This is different from the structure in which the group is bonded to an aromatic ring.

[0116] Furthermore, from the viewpoints 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) is preferably a divalent organic group represented by the following formula (12): [ka] It is more preferable that the divalent organic group is represented by the following formula (13): [ka] It is particularly preferable that the divalent organic group is represented by the following formula:

[0117] In the structure represented by the general formula (7), X is particularly preferably a structure represented by the formula (12) or (13), and the proportion of the portion represented by the structure represented by the 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 the alkali solubility of the composition, the above proportion is preferably 80% by mass or less, more preferably 70% by mass or less.

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

[0119] m5 in the general formula (14) and m6 in the general formula (15) represent the total number of repeating units in the main chain of the phenol resin. That is, in the (A) phenol resin, for example, the repeating unit in the parentheses in the structure represented by the general formula (14) and the repeating unit in the parentheses in the structure represented by the general formula (15) can be arranged randomly, in blocks, or in a combination thereof. m5 and m6 are each independently an integer of 1 to 500, 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 more from the viewpoint of the toughness of the film after curing, 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 more, more preferably 4 or more, and even more preferably 6 or more from the viewpoint of the toughness of the film after curing, and is preferably 200 or less, more preferably 175 or less, and even more preferably 150 or less from the viewpoint of solubility in an alkaline aqueous solution.

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

[0121] The phenolic resin having a repeating unit represented by the general formula (7) typically contains a phenolic compound and a copolymerization component (specifically, one or more compounds selected from the group consisting of a compound having an aldehyde group (including a compound that decomposes to produce an aldehyde compound, such as trioxane), a compound having a ketone group, a compound having two methylol groups in the molecule, a compound having two alkoxymethyl groups in the molecule, and a compound having two haloalkyl groups in the molecule), and more typically can be synthesized by polymerizing a monomer component consisting of 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 a 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), an 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 stability of the obtained (A) phenolic resin and photosensitive resin composition, the molar ratio of the phenol compound to the copolymerization component (phenol compound):(copolymerization component) is preferably 5:1 to 1.01:1, and more preferably 2.5:1 to 1.1:1.

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

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

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

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

[0126] Examples of the methylol compound include 2,6-bis(hydroxymethyl)-p-cresol, 2,6-bis(hydroxymethyl)-4-ethylphenol, 2,6-bis(hydroxymethyl)-4-propylphenol, 2,6-bis(hydroxymethyl)-4-n-butylphenol, 2,6-bis(hydroxymethyl)-4-t-butylphenol, 2,6-bis(hydroxymethyl)-4-methoxyphenol, 2,6-bis(hydroxymethyl)-4-ethoxyphenol, 2,6-bis(hydroxymethyl)-4-hydroxy ... 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 ethers include 4'-bis(hydroxymethyl)benzophenone, 4'-hydroxymethylphenyl 4-hydroxymethylbenzoate, 4'-hydroxymethylanilide 4-hydroxymethylbenzoate, 4,4'-bis(hydroxymethyl)phenylurea, 4,4'-bis(hydroxymethyl)phenylurethane, 1,8-bis(hydroxymethyl)anthracene, 4,4'-bis(hydroxymethyl)biphenyl, 2,2'-dimethyl-4,4'-bis(hydroxymethyl)biphenyl, 2,2-bis(4-hydroxymethylphenyl)propane, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and tetrapropylene glycol.

[0127] Examples of the alkoxymethyl compound include 2,6-bis(methoxymethyl)-p-cresol, 2,6-bis(methoxymethyl)-4-ethylphenol, 2,6-bis(methoxymethyl)-4-propylphenol, 2,6-bis(methoxymethyl)-4-n-butylphenol, 2,6-bis(methoxymethyl)-4-t-butylphenol, 2,6-bis(methoxymethyl)-4-methoxyphenol, 2,6-bis(methoxymethyl)-4-ethoxyphenol, 2,6-bis(methoxymethyl)-4-ethoxyphenol, 2,6-bis(methoxymethyl)-4-methoxy ... 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) Diphenylthioether, 4,4'-bis(methoxymethyl)benzophenone, 4-methoxymethylbenzoic acid-4'-methoxymethylphenyl, 4-methoxymethylbenzoic acid-4'-methoxymethylanilide, 4,4'-bis(methoxymethyl)phenylurea, 4,4'-bis(methoxymethyl)phenylurethane, 1,8-bis(methoxymethyl)anthracene, 4,4'-bis(methoxymethyl)biphenyl, 2,2'-dimethyl-4,4'-bis(methoxymethyl)biphenyl, 2,Examples of the dimethyl ether include 2-bis(4-methoxymethylphenyl)propane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, and tetrapropylene glycol dimethyl ether.

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

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

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

[0131] The amount of the 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 the phenolic compound), preferably the total number of moles of the aldehyde compound, ketone compound, methylol compound, alkoxymethyl compound, diene compound, and haloalkyl compound, 100 mol %.

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

[0133] The phenolic resin having the repeating structure represented by the general formula (7) may be obtained by further polymerizing a phenolic compound that is not a raw material for the structure of the 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 mole number of the phenolic compounds that are raw materials for the (A) phenolic resin.

[0134] (Phenol resin modified with a compound having an unsaturated hydrocarbon group with 4 to 100 carbon atoms) The phenol 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 phenol resin and an unsaturated hydrocarbon group-containing compound.

[0135] The phenol derivative that can be used is the same as that described above as a raw material for the phenol resin having a repeating unit represented by the general formula (7).

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

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

[0138] The vegetable oil usually contains an ester of glycerin and an unsaturated fatty acid, and is a non-drying oil having an iodine value of 100 or less, a semi-drying oil having an iodine value of more than 100 and less than 130, or a drying oil having an iodine value of 130 or more. Examples of non-drying oils include olive oil, morning glory seed oil, cashew seed oil, camellia oil, camellia oil, castor oil, and peanut oil. Examples of semi-drying oils include corn oil, cottonseed oil, and sesame oil. Examples of drying oils include tung oil, linseed oil, soybean oil, walnut oil, safflower oil, sunflower oil, perilla oil, and mustard oil. Processed vegetable oils obtained by processing these vegetable oils may also be used.

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

[0140] The reaction between phenol or its derivative and the unsaturated hydrocarbon group-containing compound is preferably carried out at 50 to 130°C. The reaction ratio between phenol or its derivative and the 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 its derivative, from the viewpoint of reducing the residual stress of the cured film. 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, and if it exceeds 100 parts by mass, the heat resistance of the cured film tends to decrease. In the above reaction, p-toluenesulfonic acid, trifluoromethanesulfonic acid, or the like may be used as a catalyst as necessary.

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

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

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

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

[0145] The phenolic resin modified with an unsaturated hydrocarbon group-containing compound can also be obtained by reacting the phenolic resin with the 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 phenolic derivative) and an aldehyde. In this case, the phenolic derivative and the aldehyde can be the same as the phenolic derivative and the aldehyde described above, and the phenolic resin can be synthesized under the conventionally known conditions as described above.

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

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

[0148] The reaction between the phenolic resin and the unsaturated hydrocarbon group-containing compound is preferably carried out at 50 to 130°C. In addition, 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, more preferably 2 to 70 parts by mass, and even more preferably 5 to 50 parts by mass, per 100 parts by mass of the phenolic resin, from the viewpoint of improving the flexibility of the cured film (resist pattern). 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, and if it 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 with each other, p-toluenesulfonic acid, trifluoromethanesulfonic acid, or the like may be used as a catalyst as necessary. In addition, for example, a solvent such as toluene, xylene, methanol, or tetrahydrofuran can be used for the reaction, which will be described in detail later.

[0149] A phenolic resin modified with an unsaturated hydrocarbon group-containing compound produced by the above-mentioned method can be used by further reacting a polybasic acid anhydride with the phenolic hydroxyl group remaining in the phenolic resin modified with the unsaturated hydrocarbon group-containing compound. By acid-modifying with a polybasic acid anhydride, a carboxyl group is introduced, and the solubility in an alkaline aqueous solution (used as a developer) is further improved.

[0150] The polybasic acid anhydride is not particularly limited as long as it has an acid anhydride group formed by dehydration condensation of the carboxyl groups of a polybasic acid having a plurality of carboxyl 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 having a better shape can be formed.

[0151] The reaction between the phenolic hydroxyl group and the polybasic acid anhydride can be carried out at 50 to 130° C. In this reaction, it is preferable to react 0.10 to 0.80 mol of the polybasic acid anhydride 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, the developability tends to decrease, and if it exceeds 0.80 mol, the alkali resistance of the unexposed area tends to decrease.

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

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

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

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

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

[0157] Specific examples of the (B) compound include 5-membered ring compounds such as hydantoin, allantoin, and parabanic acid; 6-membered ring compounds such as barbituric acid, 1,3-dimethylbarbituric acid, 1,3-dicyclohexylbarbituric acid, uramil, alloxan, cyanuric acid, and tris(2-hydroxyethyl) isocyanurate; 5-membered ring and 5-membered ring condensed ring compounds such as glycoluril; and 6-membered ring and 5-membered ring condensed ring compounds such as cyclohexyl ether. Examples of the condensed ring compounds of six-membered rings include lumazine, 7,8-dimethylaloxazine, 1,4-dihydro-6-methylquinoxaline-2,3-dione, and mixtures thereof. Among these, it is preferable to use the condensed ring compounds.

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

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

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

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

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

[0163] [(C) Negative photosensitizer: photopolymerization initiator and / or photoacid generator] First, the case where a negative type 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, o-benzoylbenzoic acid methyl, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone and other benzophenone derivatives, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone and other acetophenone derivatives, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone and other thioxanthone derivatives, benzil, benzil dimethyl ketal, benzyl-β-methoxyethyl acetal and other benzyl derivatives,

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

[0165] When a photoacid generator is used as a photosensitizer (C) in a negative photosensitive resin composition, it becomes acidic when exposed to active light such as ultraviolet light, and by its action, it crosslinks the crosslinking agent described below with the resin, which is the component (A), or polymerizes the crosslinking agents themselves. Examples of this photoacid generator include diaryl sulfonium salts, triaryl sulfonium salts, dialkyl phenacylsulfonium salts, diaryliodonium salts, aryl diazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, nitrobenzyl esters, oximesulfonic acid esters, aromatic N-oxyimidosulfonates, aromatic sulfamides, haloalkyl group-containing hydrocarbon compounds, haloalkyl group-containing heterocyclic compounds, and naphthoquinone diazide-4-sulfonic acid esters. Two or more of these compounds can be used in combination as necessary, or can be used in combination with other sensitizers. Among the above photoacid generators, aromatic oximesulfonic acid esters and aromatic N-oxyimidosulfonates are more preferable, especially in terms of photosensitivity.

[0166] The amount of these photosensitizers is 1 to 50 parts by mass relative to 100 parts by mass of the (A) resin, and from the viewpoint of photosensitivity characteristics, it is preferably 2 to 15 parts by mass. By adding 1 part by mass or more of the (C) photosensitizer relative to 100 parts by mass of the (A) resin, excellent photosensitivity is achieved, and by adding 50 parts by mass or less, excellent thick-film curing properties are achieved.

[0167] Furthermore, as described above, when the (A) resin represented by general formula (1) is of 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, a (meth)acrylic compound having an amino group is used as the (C) photosensitizer, and as described above, for example, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, diethylaminopropyl methacrylate, dimethylaminobutyl acrylate, dimethylaminobutyl methacrylate, diethylaminobutyl acrylate, diethylaminobutyl methacrylate, and other dialkylaminoalkyl acrylates or methacrylates are preferred, and among them, 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.

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

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

[0170] [(C) Positive-type photosensitizer: Compound having a quinone diazide group] Examples of compounds having a quinone diazide group (C) (hereinafter also referred to as "quinone diazide compound (C)") 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 quinone diazide compound (C) 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 below in detail, and 1,2-naphthoquinone diazide-5-sulfonic acid esters of the polyhydroxy compounds (hereinafter also referred to as "NQD compounds").

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

[0172] In this embodiment, from the viewpoint of sensitivity and resolution when forming a resist pattern, it is preferable that the (C) compound having a quinonediazide group is a 1,2-naphthoquinonediazide-4-sulfonic acid ester and / or a 1,2-naphthoquinonediazide-5-sulfonic acid ester of a hydroxy compound represented by the following general formulas (70) to (74). The general formula (70) is [ka] {where, X 11 and X 12 each independently represents a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms (preferably, 1 to 30 carbon atoms); 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 represents 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) T 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] In the formula, 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] It represents a divalent group selected from the three groups represented by the following formula: Furthermore, the general formula (74) is [ka] In the formula, r17, r18, r19, and r20 each independently represent an integer of 0 to 2, and at least one of r17, r18, r19, and r20 is 1 or 2; 20 ~X 29 each independently represents a monovalent group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group, and an acyl group, and Y 10 , Y 11 and Y 12 each independently represents a divalent group selected from the group consisting of a single bond, -O-, -S-, -SO-, -SO2-, -CO-, -CO2-, cyclopentylidene, cyclohexylidene, phenylene, and a divalent organic group having 1 to 20 carbon atoms.

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

[0174] Examples of the compound represented by the above general formula (70) include hydroxy compounds represented by the following formulae (75) to (79). Here, the general formula (75) is [ka] In the formula, 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, and X 40 is represented by the following general formula:

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

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

[0177] [ka] In the formula, each r19 is independently an integer of 0 to 2; 43 each independently represents a hydrogen atom or the following general formula:

[0178] [ka] (In the formula, 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 44 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 1 to 20 carbon atoms.}, and formulas (78) and (79) have the following structures.

[0179] [ka]

[0180] [ka]

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

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

[0183] [ka]

[0184] [ka]

[0185] The compound represented by the above general formula (76) is represented by the following formula (83): [ka] Hydroxy compounds represented by the following formula are preferred because they have high sensitivity when converted into NQDs and low precipitation tendency in the photosensitive resin composition.

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

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

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

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

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

[0191] Specific examples of the compound represented by the above general formula (74) include compounds represented by the following formula (94): [ka] The NQD product of a polyhydroxy compound represented by the following formula is preferred because it has high sensitivity and low precipitation in a photosensitive resin composition.

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

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

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

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

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

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

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

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

[0199] The halogen-containing compound includes haloalkyl group-containing hydrocarbon compounds, and is preferably trichloromethyltriazine.

[0200] The amount of the photoacid generator is 1 to 50 parts by mass, and preferably 5 to 30 parts by mass, relative to 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 property of the photosensitive resin composition is 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 development residue (scum) in the exposed area is small.

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

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

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

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

[0205] Examples of the solvent include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and alcohols. Examples of the solvent include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyroacetone, ethyl acetate, butyl lactate ... 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. can be used. Among them, from the viewpoints of the solubility of the resin, the stability of the resin composition, and the adhesion to the substrate, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenyl glycol, and tetrahydrofurfuryl alcohol are preferred.

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

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

[0208] In the photosensitive resin composition of the present invention, the amount of the solvent used is preferably 100 to 1,000 parts by mass, more preferably 120 to 700 parts by mass, and even more preferably 125 to 500 parts by mass, relative to 100 parts by mass of the resin (A).

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

[0210] Examples of the 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, triazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, and the like.

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

[0212] Specific examples of purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-aminopurine, and the like. 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 the like, and derivatives thereof.

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

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

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

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

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

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

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

[0220] Examples of the crosslinking agent 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, 1174; UFR65, 300; Mycoat 102, 105 (all manufactured by Mitsui Cytec Co., Ltd.), and Nikalac (registered trademark) MX-270, -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 tertiary esters include ML-BisOC-P, DMOM-PTBT, TMOM-BP, TMOM-BPA, TML-BPAF-MF (all manufactured by Honshu Chemical Industry Co., Ltd.), benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, and dimethylbis(methoxymethyl)biphenyl.

[0221] In addition, 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, 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), Epolight (registered trademark) 70P, Epolight 100MF (all trade names, manufactured by Kyoeisha Chemical Co., Ltd.), etc.

[0222] Further examples of isocyanate group-containing compounds include 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.), Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, and E402-B80T (all trade names, manufactured by Asahi Kasei Chemicals Corporation).

[0223] In addition, the following bismaleimide compounds are available: 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 disulfone 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 Kasei Kogyo Co., Ltd.), but are not limited to these as long as they are compounds that can be thermally crosslinked as described above.

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

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

[0226] Organotitanium compounds that can be used include those in which an organic chemical is bonded to a titanium atom via a covalent or ionic bond.

[0227] Specific examples of the organotitanium compound are shown below in I) to VII): I) Titanium chelate compounds: Among these, titanium chelates having two or more alkoxy groups are more preferred since they provide good storage stability for the negative photosensitive resin composition 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), and the like.

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

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

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

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

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

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

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

[0235] When an organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the (A) resin. When the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited, while when it is 10 parts by mass or less, excellent storage stability is exhibited.

[0236] Furthermore, an adhesive aid can be optionally blended to improve adhesion between a film formed using the photosensitive resin composition of the present invention and a substrate. Examples of the adhesive aid 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)propane, 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, 3-(trialkoxysilyl)propylsuccinic anhydride, and aluminum-based adhesion aids such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

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

[0238] Examples of silane coupling agents include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM803, manufactured by Chisso Corporation: trade name Sila-Ace S810), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Corporation: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS1375, manufactured by Azmax Corporation: trade name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Corporation: trade name SIM6473.5C), and mercaptomethylmethyldimethoxysilane (manufactured by Azmax Corporation: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethyl triethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name) LS3610, Azmax Corporation: Trade name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (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 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, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butyldiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, 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 thereto. These may be used alone or in combination.

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

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

[0241] The photosensitive resin composition of the present invention may further contain components other than those described above. The preferred components vary depending on whether the (A) resin 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.

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

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

[0244] In order to improve the resolution of the relief pattern, a monomer having a photopolymerizable unsaturated bond can be optionally blended. As such a monomer, a (meth)acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferable, and examples thereof include, but are not limited to, mono- or diacrylates and methacrylates of ethylene glycol or polyethylene glycol, such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, mono- or diacrylates and methacrylates of propylene glycol or polypropylene glycol, mono-, di- or triacrylates and methacrylates of glycerol, cyclohexane diacrylate and dimethacrylate, diacrylates and dimethacrylates of 1,4-butanediol, and 1,6-hexane diacrylate and dimethacrylate. 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 its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, di- or triacrylates and methacrylates of glycerol, di-, tri-, or tetraacrylates and methacrylates of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds.

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

[0246] In the case of a negative type using a polyimide precursor or the like as the (A) resin, a thermal polymerization inhibitor can be optionally blended in order to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition during storage, particularly in the form of a solution containing a solvent. As the thermal polymerization inhibitor, 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, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, etc. can be used.

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

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

[0249] <Dyes, surfactants, adhesives> More specifically, the above additives include dyes such as methyl violet, crystal violet, and malachite green. Examples of surfactants include nonionic surfactants made of polyglycols such as polypropylene glycol or polyoxyethylene lauryl ether or derivatives thereof, fluorine-based surfactants such as Fluorad (trade name, manufactured by Sumitomo 3M), Megafac (trade name, manufactured by Dainippon Ink and Chemicals), and Lumiflon (trade name, manufactured by Asahi Glass), and organic siloxane surfactants such as KP341 (trade name, manufactured by Shin-Etsu Chemical), DBE (trade name, manufactured by Chisso), and Granol (trade name, manufactured by Kyoeisha Chemical). Examples of adhesion promoters include alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy silane, epoxy polymer, and various silane coupling agents.

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

[0251] 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 thermal acid generator is preferably added from the viewpoint of providing a cured product with good thermal and mechanical properties even when the curing temperature is lowered.

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

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

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

[0255] In addition to the above-mentioned onium salts, the salts formed from the strong acid and base may also be pyridinium salts. Examples of the strong acid 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 the base include alkylpyridines such as pyridine and 2,4,6-trimethylpyridine, N-alkylpyridines such as 2-chloro-N-methylpyridine, and halogenated N-alkylpyridines.

[0256] As the imide sulfonate, for example, naphthoyl imide sulfonate, phthalimide sulfonate, etc. can be used, but there is no limitation thereto so long as it is a compound that generates an acid by heat.

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

[0258] In the case of a positive-type photosensitive resin composition, a dissolution promoter can be used to promote the removal of resin that is no longer needed after exposure. For example, a compound having a hydroxyl group or a carboxyl group is preferable. 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, and 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.), 2-5 phenol-substituted diphenylmethane, 1-5 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, N-hydroxy5-norbornene-2,3-dicarboxylic anhydride, etc. Examples of the compound 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, itaconic acid, etc.

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

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

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

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

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

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

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

[0266] The amount of the sulfur-containing compound (B) is 0.01 to 10 parts by mass, and preferably 0.05 to 2 parts by mass, based on 100 parts by mass of the resin (A). From the viewpoint of migration resistance, it is desirable to add 0.01 parts by mass or more, and from the viewpoint of solubility, it is desirable to add less than 10 parts by mass. Sulfur-containing compounds, especially thiourea, can coordinate with copper through sulfur atoms, which changes the state of the copper surface and suppresses copper migration during high-temperature storage tests.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[0285] [ka] [ka]

[0286] Specific examples of the triazole derivative represented by the general formula (III) include (4-((1H-1,2,4-triazol-1-ylmethyl)phenyl)methanol, tricyclazole, 1,2,4-1H-triazole, triapentenol, bitertanol, 4-(1H-1,2,4-triazol-1-yl)benzaldehyde, 4-(1H-1,2,4-triazol-1-yl)benzoic acid, 3-(1H-1,2,4-triazol-1-ylmethyl)benzoic acid, 4-[(1H-1,2,4 -triazol-1-ylmethyl)phenyl]methanol, 3-(1H-1,2,4-triazol-1-yl)benzaldehyde, 3-(1H-1,2,4-triazol-1-ylmethyl)benzaldehyde, 3-(1H-1,2,4-triazol-1-yl)benzoic acid, and 2-(1H-1,2,4-triazol-1-yl)aniline are preferably used. Among them, (4-((1H-1,2,4-triazol-1-ylmethyl)phenyl)methanol ((B)-7) is particularly preferably used.

[0287] [ka]

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

[0289] The content of the aromatic amine compound (B) is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 1 to 8 parts by mass, relative to 100 parts by mass of the resin (A). A content higher than this range is undesirable because the storage stability decreases, while a content lower than this range is likely to cause voids to occur between the copper surface.

[0290] <Method for Producing Cured Relief Pattern and Semiconductor Device> The present invention also provides a method for producing a cured relief pattern, comprising the steps of: (1) forming a resin layer on a substrate by applying the above-mentioned 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) subjecting the relief pattern to a heat treatment to form a cured relief pattern. Typical aspects of each step are described below.

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

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

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

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

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

[0296] The developer used for development is preferably a good solvent for the photosensitive resin composition, or a combination of the good solvent and a poor solvent. For example, in the case of a photosensitive resin composition that is not soluble in an alkaline aqueous solution, the good solvent is preferably N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc., and the poor solvent is preferably toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water, etc. When a good solvent and a poor solvent are used in combination, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the photosensitive resin composition. In addition, two or more types of each solvent, for example, several types, can be used in combination.

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

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

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

[0300] Furthermore, if necessary, suitable amounts of a water-soluble organic solvent such as methanol, ethanol, propanol, or ethylene glycol, a surfactant, a storage stabilizer, and a resin dissolution inhibitor may be added to the alkaline aqueous solution. In this manner, a relief pattern can be formed.

[0301] (4) A step of forming a hardened relief pattern by heat treating the relief pattern. In this step, the relief pattern obtained by the above development is heated to convert it into a hardened relief pattern. As the heat hardening method, various methods can be selected, such as using a hot plate, an oven, or a temperature-elevating oven in which a temperature program can be set. Heating can be performed, for example, under conditions of 180°C to 400°C for 30 minutes to 5 hours. As the atmospheric gas during heat hardening, air may be used, or an inert gas such as nitrogen or argon may also be used.

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

[0303] The photosensitive resin composition of the present invention is useful not only for application to the above-mentioned semiconductor devices, but also for applications such as interlayer insulation in multilayer circuits, cover coats for flexible copper-clad boards, solder resist films, and liquid crystal alignment films. In addition, although the above description has been given separately for Aspects A to D, combinations of the respective aspects are also included in the present invention. EXAMPLES

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

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

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

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

[0308] (3) High temperature storage test and subsequent evaluation of hardened relief patterns on Cu The wafer with the cured relief pattern formed on Cu was heated in air at 150°C for 168 hours using a temperature-programmable curing furnace (VF-2000, manufactured by Koyo Lindberg). Then, 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 / flow rate: O2: 40ml / min + CF4: 1ml / min Gas pressure: 50Pa Mode: Hard Mode Etching time: 1800 seconds

[0309] The Cu surface from which all the resin layers had been removed was observed using a FE-SEM (S-4800 model, 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, Asahi Kasei Corporation).

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

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

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

[0313] Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while 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 while stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

[0314] The reaction solution obtained was added to 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered off and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and 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) to find that the weight average molecular weight (Mw) was 20,000.

[0315] The weight average molecular weight of the resin obtained in each production example was measured by gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight was calculated in terms of standard polystyrene. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Column: Shodex KD-806M, 2 in series Mobile phase: 0.1mol / l LiBr / NMP Flow rate: 1ml / min.

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

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

[0318] <Production Example A4> ((A) Synthesis of Polymer D as Polyamide) (Synthesis of phthalic acid compound-capped AIPA-MO) In a 5-liter separable flask, 543.5 g of 5-aminoisophthalic acid (hereafter abbreviated as AIPA) and 1,700 g of N-methyl-2-pyrrolidone were added, 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 using a dropping funnel, and the mixture was stirred at 50°C for about 2 hours.

[0319] After confirming the completion of the reaction (disappearance of 5-aminoisophthalic acid) by low molecular weight gel permeation chromatography {hereinafter referred to as low molecular weight GPC}, the reaction solution was poured into 15 liters of ion-exchanged water, stirred, and left to stand. After waiting for the reaction product to crystallize and precipitate, it was filtered off, 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 obtained AIPA-MO was about 100%.

[0320] (Synthesis of Polymer D) In a 2L separable flask, 100.89g (0.3mol) of the obtained AIPA-MO, 71.2g (0.9mol) of pyridine, and 400g of GBL were put, mixed, and cooled to 5°C in an ice bath. Dicyclohexylcarbodiimide (DCC) 125.0g (0.606mol) dissolved and diluted in GBL 125g was added dropwise to the mixture over about 20 minutes under ice cooling, followed by 4,4'-bis(4-aminophenoxy)biphenyl {hereinafter referred to as BAPB.} 103.16g (0.28mol) dissolved in NMP 168g, which was added dropwise over about 20 minutes, and 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 stirred at room temperature for 5 hours. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

[0321] A mixture of 840 g of water and 560 g of isopropanol was added dropwise to the reaction solution, and the precipitated polymer was separated and redissolved in 650 g of NMP. The crude polymer solution was added dropwise to 5 liters of water to precipitate the polymer, and the 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) to find that the weight average molecular weight (Mw) was 34,700.

[0322] <Production Example A5> ((A) Synthesis of Polymer E as Polyoxazole Precursor) In a 3-liter 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 obtain a homogeneous solution. A solution of 118.0 g of 4,4'-diphenyletherdicarbonyl chloride dissolved in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise from a dropping funnel. At this time, the separable flask was cooled in a water bath at 15 to 20°C. The time required for the dropwise addition was 40 minutes, and the reaction liquid temperature was a maximum of 30°C.

[0323] Three hours after the end of the dropwise addition, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic anhydride was added to the reaction solution, and the mixture was left to stir at room temperature for 15 hours, so that 99% of the total amine end groups of the polymer chain were blocked with carboxycyclohexylamide groups. The reaction rate at this time can be easily calculated by tracking the remaining amount of 1,2-cyclohexyldicarboxylic anhydride added by high performance liquid chromatography (HPLC). The reaction solution was then dropped into 2 L of water under high speed stirring to disperse and precipitate the polymer, which was then recovered, appropriately washed with water, dehydrated, and vacuum dried to obtain a crude polybenzoxazole precursor with a weight average molecular weight of 9,000 (polystyrene equivalent) measured by gel permeation chromatography (GPC).

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

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

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

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

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

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

[0330] The reaction vessel was then cooled in the air, and 100 g of tetrahydrofuran was added and stirred. The above reaction dilution was dropped into 4 L of water under high speed stirring to disperse and precipitate the resin, which was then recovered, washed with water as appropriate, dehydrated, and vacuum dried to obtain a copolymer (polymer G) consisting of 3,5-dihydroxybenzoic acid methyl ester / BMMB in a yield of 70%. The weight average molecular weight of this polymer G, calculated as standard polystyrene by the GPC method, was 21,000.

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

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

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

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

[0335] <Example A1> Negative 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 0.2 g of xanthine (corresponding to (B) cyclic compound having a carbonyl group), 4 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (described 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 obtained solution was adjusted to about 35 poise by further adding a small amount of the mixed solvent, and a negative photosensitive resin composition was obtained. 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 5.2%. <Example A2> A negative photosensitive resin composition solution was prepared in the same manner as in Example A1, except that in Example A1, the amount of xanthine added as component (B) was changed to 0.05 g. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, resulting in 6.4%. <Example A3> A negative photosensitive resin composition solution was prepared in the same manner as in Example A1, except that in Example A1, the amount of xanthine added as component (B) was changed to 5 g. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in 4.9%. <Example A4> A negative photosensitive resin composition solution was prepared in the same manner as in Example A1, except that in Example A1, 8-azaxanthine was used as the component (B) instead of xanthine. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, resulting in 5.1%. <Example A5> A negative photosensitive resin composition solution was prepared in the same manner as in Example A1, except that in Example A1, uric acid was used instead of xanthine as the component (B). This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, resulting in 5.4%. <Example A6> A negative photosensitive resin composition solution was prepared in the same manner as in Example A1, except that lumazine was used instead of xanthine as the component (B) in Example A1. 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 5.5%. <Example A7> A negative photosensitive resin composition solution was prepared in the same manner as in Example A1, except that barbituric acid was used instead of xanthine as the component (B). This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in 7.3%. <Example A8> A negative photosensitive resin composition solution was prepared in the same manner as in Example A1 above, and this composition was cured at 350°C 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, resulting in 4.5%. <Example A9> A negative type photosensitive resin composition solution was prepared in the same manner as in Example A1, except that in Example A1, 50 g of Polymer A and 50 g of Polymer B were changed to 100 g of Polymer A as the (A) resin, and 4 g of PDO was changed to 2.5 g of 1,2-octanedione, 1-{4-(phenylthio)-, 2-(O-benzoyloxime)} (Irgacure OXE01 (BASF, product name)) as the (C) component. This composition was cured at 230°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated, resulting in 5.1%. <Example A10> A negative photosensitive resin composition solution was prepared in the same manner as in Example A1 above, except that in Example A1, 50 g of Polymer A and 50 g of Polymer B were replaced with 100 g of Polymer A as the (A) resin, 4 g of PDO was replaced with 2.5 g of 1,2-octanedione, 1-{4-(phenylthio)-, 2-(O-benzoyloxime)} (Irgacure OXE01 (BASF, product name)) as the (C) component, and the solvent was replaced with 85 g of γ-butyrolactone and 15 g of dimethylsulfoxide. 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 5.2%. <Example A11> A negative photosensitive resin composition solution was prepared in the same manner as in Example A1, except that 50 g of Polymer A and 50 g of Polymer B were replaced with 100 g of Polymer C as the resin (A). This composition was cured at 350°C using the method described above to create a hardened relief pattern on the Cu layer. After a high-temperature storage test, the area percentage of voids on the surface of the Cu layer was evaluated, resulting in 4.9%. <Example A12> A negative photosensitive resin composition solution was prepared in the same manner as in Example A1, except that 50 g of Polymer A and 50 g of Polymer B were changed to 100 g of Polymer D as the resin (A) in Example A1. 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 5.0%. <Example A13> A positive-type 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 reacted with a compound represented by the following formula (96): [ka] The compound (C1) (20 g) in which 77% of the phenolic hydroxyl groups are converted to naphthoquinone diazide-4-sulfonic acid ester (manufactured by Toyo Gosei Co., Ltd., corresponds to (C) photosensitizer), 0.2 g of xanthine (corresponding to (B) cyclic compound having a carbonyl group), and 6 g of 3-t-butoxycarbonylaminopropyltriethoxysilane were dissolved in 100 g of γ-butyrolactone (as a solvent). The viscosity of the obtained 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 5.5%. <Example A14> A positive photosensitive resin composition solution was prepared in the same manner as in Example A13, except that 100 g of Polymer E was replaced with 100 g of Polymer F as the (A) resin in Example A13. 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 5.7%. <Example A15> A positive photosensitive resin composition solution was prepared in the same manner as in Example A13, except that 100 g of Polymer E was replaced with 100 g of Polymer G as the (A) resin in Example A13. 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 ratio of voids on the surface of the Cu layer was evaluated, resulting in 5.3%. <Example A16> A positive photosensitive resin composition solution was prepared in the same manner as in Example A13, except that 100 g of Polymer E was changed to 100 g of Polymer H as the (A) resin in Example A13. 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 5.2%. <Comparative Example A1> A negative photosensitive resin composition was prepared in the same manner as in Example A1, except that 0.2 g of benzotriazole was added instead of 0.2 g of xanthine in the composition of Example A1, and the composition was evaluated in the same manner as in Example A1. The evaluation result was 15.2% because the compound (B) of the present invention was not included. <Comparative example A2> A negative photosensitive resin composition was prepared in the same manner as in Example A1, except that xanthine was not added to the composition of Example A1, and the composition was evaluated in the same manner as in Example A1. The evaluation result was 14.3% because the compound (B) of the present invention was not included. <Comparative example A3> A negative photosensitive resin composition was prepared in the same manner as in Example A10, except that xanthine was not added to the composition of Example A10, and the same evaluation was carried out as in Example A10. The evaluation result was 15.7% because the compound (B) of the present invention was not included. <Comparative example A4> A negative photosensitive resin composition was prepared in the same manner as in Example A11, except that xanthine was not added to the composition of Example A11, and the same evaluation was performed as in Example A11. The evaluation result was 14.9% because the compound (B) of the present invention was not included. The results of Examples A1 to A16 and Comparative Examples A1 to A4 are shown in Table 1.

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

[0337] Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while 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 while stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

[0338] The reaction solution obtained was added to 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered off and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and 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) to find that the weight average molecular weight (Mw) was 20,000.

[0339] The weight average molecular weight of the resin obtained in each Production Example B was measured by gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight was calculated in terms of standard polystyrene. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Column: Shodex KD-806M, 2 in series Mobile phase: 0.1mol / l LiBr / NMP Flow rate: 1ml / min.

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

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

[0342] <Production Example B4> ((A) Synthesis of Polymer D as Polyamide) (Synthesis of phthalic acid compound-capped AIPA-MO) In a 5-liter separable flask, 543.5 g of 5-aminoisophthalic acid (hereafter abbreviated as AIPA) and 1,700 g of N-methyl-2-pyrrolidone were added, 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 using a dropping funnel, and the mixture was stirred at 50°C for about 2 hours.

[0343] After confirming the completion of the reaction (disappearance of 5-aminoisophthalic acid) by low molecular weight gel permeation chromatography {hereinafter referred to as low molecular weight GPC}, the reaction solution was poured into 15 liters of ion-exchanged water, stirred, and left to stand. After waiting for the reaction product to crystallize and precipitate, it was filtered off, 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 obtained AIPA-MO was about 100%.

[0344] (Synthesis of Polymer D) In a 2L separable flask, 100.89g (0.3mol) of the obtained AIPA-MO, 71.2g (0.9mol) of pyridine, and 400g of GBL were put, mixed, and cooled to 5°C in an ice bath. Dicyclohexylcarbodiimide (DCC) 125.0g (0.606mol) dissolved and diluted in GBL 125g was added dropwise to the mixture over about 20 minutes under ice cooling, followed by 4,4'-bis(4-aminophenoxy)biphenyl {hereinafter referred to as BAPB.} 103.16g (0.28mol) dissolved in NMP 168g, which was added dropwise over about 20 minutes, and 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 stirred at room temperature for 5 hours. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

[0345] A mixture of 840 g of water and 560 g of isopropanol was added dropwise to the reaction solution, and the precipitated polymer was separated and redissolved in 650 g of NMP. The crude polymer solution was added dropwise to 5 liters of water to precipitate the polymer, and the 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) to find that the weight average molecular weight (Mw) was 34,700.

[0346] <Production Example B5> ((A) Synthesis of Polymer E as Polyoxazole Precursor) In a 3-liter 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 obtain a homogeneous solution. A solution of 118.0 g of 4,4'-diphenyletherdicarbonyl chloride dissolved in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise from a dropping funnel. At this time, the separable flask was cooled in a water bath at 15 to 20°C. The time required for the dropwise addition was 40 minutes, and the reaction liquid temperature was a maximum of 30°C.

[0347] Three hours after the end of the dropwise addition, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic anhydride was added to the reaction solution, and the mixture was left to stir at room temperature for 15 hours, so that 99% of the total amine end groups of the polymer chain were blocked with carboxycyclohexylamide groups. The reaction rate at this time can be easily calculated by tracking the remaining amount of 1,2-cyclohexyldicarboxylic anhydride added by high performance liquid chromatography (HPLC). The reaction solution was then dropped into 2 L of water under high speed stirring to disperse and precipitate the polymer, which was then recovered, appropriately washed with water, dehydrated, and vacuum dried to obtain a crude polybenzoxazole precursor with a weight average molecular weight of 9,000 (polystyrene equivalent) measured by gel permeation chromatography (GPC).

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

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

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

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

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

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

[0354] The reaction vessel was then cooled in the air, and 100 g of tetrahydrofuran was added and stirred. The above reaction dilution was dropped into 4 L of water under high speed stirring to disperse and precipitate the resin, which was then recovered, washed with water as appropriate, dehydrated, and vacuum dried to obtain a copolymer (polymer G) consisting of 3,5-dihydroxybenzoic acid methyl ester / BMMB in a yield of 70%. The weight average molecular weight of this polymer G, calculated as standard polystyrene by the GPC method, was 21,000.

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

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

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

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

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

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

[0361] Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while 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 while stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

[0362] The reaction solution obtained was added to 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered off and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and 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) to find that the weight average molecular weight (Mw) was 20,000.

[0363] The weight average molecular weight of the resin obtained in each Production Example C was measured by gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight was calculated in terms of standard polystyrene. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Column: Shodex KD-806M, 2 in series Mobile phase: 0.1mol / l LiBr / NMP Flow rate: 1ml / min.

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

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

[0366] <Production Example C4> ((A) Synthesis of Polymer D as Polyamide) (Synthesis of phthalic acid compound-capped AIPA-MO) In a 5-liter separable flask, 543.5 g of 5-aminoisophthalic acid (hereafter abbreviated as AIPA) and 1,700 g of N-methyl-2-pyrrolidone were added, 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 using a dropping funnel, and the mixture was stirred at 50°C for about 2 hours.

[0367] After confirming the completion of the reaction (disappearance of 5-aminoisophthalic acid) by low molecular weight gel permeation chromatography {hereinafter referred to as low molecular weight GPC}, the reaction solution was poured into 15 liters of ion-exchanged water, stirred, and left to stand. After waiting for the reaction product to crystallize and precipitate, it was filtered off, 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 obtained AIPA-MO was about 100%.

[0368] (Synthesis of Polymer D) In a 2L separable flask, 100.89g (0.3mol) of the obtained AIPA-MO, 71.2g (0.9mol) of pyridine, and 400g of GBL were put, mixed, and cooled to 5°C in an ice bath. Dicyclohexylcarbodiimide (DCC) 125.0g (0.606mol) dissolved and diluted in GBL 125g was added dropwise to the mixture over about 20 minutes under ice cooling, followed by 4,4'-bis(4-aminophenoxy)biphenyl {hereinafter referred to as BAPB.} 103.16g (0.28mol) dissolved in NMP 168g, which was added dropwise over about 20 minutes, and 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 stirred at room temperature for 5 hours. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

[0369] A mixture of 840 g of water and 560 g of isopropanol was added dropwise to the reaction solution, and the precipitated polymer was separated and redissolved in 650 g of NMP. The crude polymer solution was added dropwise to 5 liters of water to precipitate the polymer, and the 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) to find that the weight average molecular weight (Mw) was 34,700.

[0370] <Production Example C5> ((A) Synthesis of Polymer E as a Polyoxazole Precursor) In a 3-liter 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 obtain a homogeneous solution. A solution of 118.0 g of 4,4'-diphenyletherdicarbonyl chloride dissolved in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise from a dropping funnel. At this time, the separable flask was cooled in a water bath at 15 to 20°C. The time required for the dropwise addition was 40 minutes, and the reaction liquid temperature was a maximum of 30°C.

[0371] Three hours after the end of the dropwise addition, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic anhydride was added to the reaction solution, and the mixture was left to stir at room temperature for 15 hours, so that 99% of the total amine end groups of the polymer chain were blocked with carboxycyclohexylamide groups. The reaction rate at this time can be easily calculated by tracking the remaining amount of 1,2-cyclohexyldicarboxylic anhydride added by high performance liquid chromatography (HPLC). The reaction solution was then dropped into 2 L of water under high speed stirring to disperse and precipitate the polymer, which was then recovered, appropriately washed with water, dehydrated, and vacuum dried to obtain a crude polybenzoxazole precursor with a weight average molecular weight of 9,000 (polystyrene equivalent) measured by gel permeation chromatography (GPC).

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

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

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

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

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

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

[0378] The reaction vessel was then cooled in the air, and 100 g of tetrahydrofuran was added and stirred. The above reaction dilution was dropped into 4 L of water under high speed stirring to disperse and precipitate the resin, which was then recovered, washed with water as appropriate, dehydrated, and vacuum dried to obtain a copolymer (polymer G) consisting of 3,5-dihydroxybenzoic acid methyl ester / BMMB in a yield of 70%. The weight average molecular weight of this polymer G, calculated as standard polystyrene by the GPC method, was 21,000.

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

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

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

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

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

[0384] Example D <Production Example D1> ((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 stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generation due to the reaction had ceased, the mixture was allowed to cool to room temperature and left to stand for 16 hours.

[0385] Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while 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 while stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

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

[0387] The weight average molecular weight of the resin obtained in each Production Example D was measured by gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight was calculated in terms of standard polystyrene. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Column: Shodex KD-806M, 2 in series Mobile phase: 0.1mol / l LiBr / NMP Flow rate: 1ml / min.

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

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

[0390] <Production Example D4> (Synthesis of polymer (A)-4 as polyamide (A)) (Synthesis of phthalic acid compound-capped AIPA-MO) In a 5-liter separable flask, 543.5 g of 5-aminoisophthalic acid (hereafter abbreviated as AIPA) and 1,700 g of N-methyl-2-pyrrolidone were added, 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 using a dropping funnel, and the mixture was stirred at 50°C for about 2 hours.

[0391] After confirming the completion of the reaction (disappearance of 5-aminoisophthalic acid) by low molecular weight gel permeation chromatography {hereinafter referred to as low molecular weight GPC}, the reaction solution was poured into 15 liters of ion-exchanged water, stirred, and left to stand. After waiting for the reaction product to crystallize and precipitate, it was filtered off, 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 obtained AIPA-MO was about 100%.

[0392] (Synthesis of Polymer (A)-4) In a 2L separable flask, 100.89g (0.3mol) of the obtained AIPA-MO, 71.2g (0.9mol) of pyridine, and 400g of GBL were put, mixed, and cooled to 5°C in an ice bath. Dicyclohexylcarbodiimide (DCC) 125.0g (0.606mol) dissolved and diluted in GBL 125g was added dropwise to the mixture over about 20 minutes under ice cooling, followed by 4,4'-bis(4-aminophenoxy)biphenyl {hereinafter referred to as BAPB.} 103.16g (0.28mol) dissolved in NMP 168g, which was added dropwise over about 20 minutes, and 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 stirred at room temperature for 5 hours. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

[0393] A mixture of 840 g of water and 560 g of isopropanol was added dropwise to the reaction solution, and the precipitated polymer was separated and redissolved in 650 g of NMP. The crude polymer solution was added dropwise to 5 L of water to precipitate the polymer, and the 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) to find that the weight average molecular weight (Mw) was 34,700.

[0394] <Production Example D5> (Synthesis of polymer (A)-5 as polyoxazole precursor (A)) In a 3-liter 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 obtain a homogeneous solution. A solution of 118.0 g of 4,4'-diphenyletherdicarbonyl chloride dissolved in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise from a dropping funnel. At this time, the separable flask was cooled in a water bath at 15 to 20°C. The time required for the dropwise addition was 40 minutes, and the reaction liquid temperature was a maximum of 30°C.

[0395] Three hours after the end of the dropwise addition, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic anhydride was added to the reaction solution, and the mixture was left to stir at room temperature for 15 hours, so that 99% of the total amine end groups of the polymer chain were blocked with carboxycyclohexylamide groups. The reaction rate at this time can be easily calculated by tracking the remaining amount of 1,2-cyclohexyldicarboxylic anhydride added by high performance liquid chromatography (HPLC). The reaction solution was then dropped into 2 L of water under high speed stirring to disperse and precipitate the polymer, which was then recovered, appropriately washed with water, dehydrated, and vacuum dried to obtain a crude polybenzoxazole precursor with a weight average molecular weight of 9,000 (polystyrene equivalent) measured by gel permeation chromatography (GPC).

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

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

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

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

[0400] <Example D1> Negative 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 polymer (A)-1 and 50 g of (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 together with 3 g of N-phenylbenzylamine (manufactured by Tokyo Chemical Industry Co., Ltd., corresponding to (B)-1), 4 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (described as "PDO" in Table 4) (corresponding to (C) photosensitizer), 8 g of tetraethylene glycol dimethacrylate, and 1.5 g of N-[3-(triethoxysilyl)propyl]phthalamic acid. The viscosity of the obtained 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 by the above-mentioned method to create a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated and found to be 4.5%. In addition, the viscosity change rate of the obtained varnish after the storage stability test was within 10%. <Example D2> A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 above, except that in Example D1, the component (B) was changed to N,N'-diphenylethane-1,2-diamine (manufactured by Tokyo Chemical Industry Co., Ltd.). This composition was cured at 230°C by the above-mentioned method to create a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated and found to be 4.2%. In addition, the viscosity change rate of the obtained varnish after the storage stability test was within 10%. <Example D3> A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 above, except that in Example D1, the component (B) was changed to tert-butylphenyl carbamate (manufactured by Tokyo Chemical Industry Co., Ltd.). This composition was cured at 230°C by the above-mentioned method to create a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated and found to be 5.1%. In addition, the viscosity change rate of the obtained varnish after the storage stability test was within 10%. <Example D4> A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 above, except that in Example D1, the component (B) was changed to tert-butyl(3-hydroxyphenyl)carbamate (manufactured by Tokyo Chemical Industry Co., Ltd.). This composition was cured at 230°C by the above-mentioned method to create a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated and found to be 5.8%. In addition, the viscosity change rate of the obtained varnish after the storage stability test was within 10%. <Example D5> A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 above, except that in Example D1, the component (B) was changed to 2-hydroxy-N-(1H-1,2,4-triazol-3-yl)benzamide (ADEKA CORPORATION, Adeka STAB CDA-1). This composition was cured at 230°C by the above-mentioned method to create a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated and found to be 4.8%. In addition, the viscosity change rate of the obtained varnish after the storage stability test was within 10%. <Example D6> A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 above, except that in Example D1, the (B) component was changed to 2-(2H-benzo[d][1,2,3]triazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol (ADEKA CORPORATION, Adeka STAB LA-29). This composition was cured at 230°C by the above-mentioned method to create a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated and found to be 4.2%. In addition, the viscosity change rate of the obtained varnish after the storage stability test was within 10%. <Example D7> A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 above, except that in Example D1, the component (B) was changed to (4-((1H-1,2,4-triazol-1-yl)methyl)phenyl)methanol (manufactured by Tokyo Chemical Industry Co., Ltd.). This composition was cured at 230°C by the above-mentioned method to create a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated and found to be 6.1%. In addition, the viscosity change rate of the obtained varnish after the storage stability test was within 10%. <Example D8> A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 above, except that the amount of the (B)-1 component added was changed to 1 g. This composition was cured at 230°C by the above-mentioned method to create a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated and found to be 8.5%. In addition, the viscosity change rate of the obtained varnish after the storage stability test was within 10%. <Example D9> A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 above, except that the amount of the (B)-1 component added was changed to 6 g. This composition was cured at 230°C by the above-mentioned method to create a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated and found to be 4.9%. In addition, the viscosity change rate of the resulting varnish after a storage stability test was within 10%. <Example D10> A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 above, except that the amount of the (B)-1 component added was changed to 10 g. This composition was cured at 230°C by the above-mentioned method to create a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated and found to be 5.0%. In addition, the viscosity change rate of the obtained varnish after the storage stability test was within 10%. <Example D11> A negative photosensitive resin composition solution was prepared in the same manner as in Example D1, except that the curing temperature was changed from 230° C. to 350° C. in Example D1. A cured relief pattern was created on the Cu layer of this composition, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated and found to be 6.1%. In addition, the viscosity change rate of the obtained varnish after the storage stability test was within 10%. <Example D12> A negative photosensitive resin composition solution was prepared in the same manner as in Example D1 above, except that in Example D1, 50 g of polymer (A)-1 and 50 g of polymer (A)-2 were used as the (A) resin, but 100 g of polymer (A)-1 was used, and 2.5 g of 1,2-octanedione, 1-{4-(phenylthio)-, 2-(O-benzoyloxime)} (Irgacure OXE01 (BASF, product name)) was used as the (C) component instead of PDO. A cured relief pattern was created on the Cu layer of this composition, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated and found to be 5.8%. In addition, the viscosity change rate of the obtained varnish after the storage stability test was within 10%. <Example D13> A negative photosensitive resin composition solution was prepared in the same manner as in Example D12, except that the solvent in Example D12 was changed to 85 g of γ-butyrolactone and 15 g of dimethyl sulfoxide. A cured relief pattern was created on the Cu layer of this composition, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated and found to be 5.4%. In addition, the viscosity change rate of the obtained varnish after the storage stability test was within 10%. <Example D14> A negative type photosensitive resin composition solution was prepared in the same manner as in Example D1, except that in Example D1, 50 g of polymer (A)-1 and 50 g of polymer (A)-2 were replaced with 100 g of polymer (A)-3 as the (A) resin, and the curing temperature was changed from 230°C to 350°C. A cured relief pattern was created on the Cu layer of this composition, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated and found to be 7.2%. In addition, the viscosity change rate of the obtained varnish after the storage stability test was within 10%. <Example D15> A negative photosensitive resin composition solution was prepared in the same manner as in Example D1, except that in Example D1, 50 g of polymer (A)-1 and 50 g of polymer (A)-2 were replaced with 100 g of polymer (A)-4 as the (A) resin. A cured relief pattern was created on the Cu layer of this composition, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated and found to be 4.9%. In addition, the viscosity change rate of the obtained varnish after the storage stability test was within 10%. <Example D16> A positive-type 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 (corresponding to resin (A)), which is a polyoxazole precursor, was added to the following 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 are 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 obtained 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 by the above-mentioned method to create a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of voids on the surface of the Cu layer was evaluated and found to be 6.9%. In addition, the viscosity change rate of the obtained varnish after a storage stability test was within 10%. <Example D17> A positive photosensitive resin composition solution was prepared in the same manner as in Example D12, except that in Example D16, 100 g of polymer (A)-5 was changed to 100 g of polymer (A)-6 as the (A) resin. This composition was cured at 250°C by the above-mentioned method to create a cured relief pattern on the Cu layer, and after a high-temperature storage test, the area ratio of the voids on the surface of the Cu layer was evaluated and found to be 6.0%. In addition, the viscosity change rate of the obtained varnish after the storage stability test was within 10%. <Comparative Example D1> A negative photosensitive resin composition was prepared in the same manner as in Example D1, except that the (B)-1 component was not added to the composition of Example D1, and the same evaluation as in Example D1 was performed. The evaluation result was 15.2% because the (B) component of the present invention was not included. In addition, the viscosity change rate of the obtained varnish after the storage stability test was within 10%. <Comparative example D2> A negative photosensitive resin composition was prepared in the same manner as in Example D15, except that the (B)-1 component was not added to the composition of Example D15, and the same evaluation as in Example D15 was performed. The evaluation result was 14.3% because the (B) component of the present invention was not included. In addition, the viscosity change rate of the obtained varnish after the storage stability test was within 10%. <Comparative Example D3> A negative photosensitive resin composition was prepared in the same manner as in Example D13, except that the (B)-1 component was not added to the composition of Example D13, and the same evaluation as in Example D13 was performed. The evaluation result was 15.7% because the (B) component of the present invention was not included. In addition, the viscosity change rate of the obtained varnish after the storage stability test was within 10%. <Comparative Example D4> A positive photosensitive resin composition was prepared in the same manner as in Example D17, except that the (B)-1 component was not added to the composition of Example D17, and the same evaluation as in Example D17 was performed. The evaluation result was 16.3% because the (B) component of the present invention was not included. In addition, the viscosity change rate of the obtained varnish after the storage stability test was within 10%. <Comparative Example D5> A negative photosensitive resin composition was prepared in the same manner as in Example D1, except that the amount of the (B)-1 component added was changed to 25 g in the composition of Example D1, and the same evaluation as in Example D1 was performed. The evaluation result was 7.2%. In addition, the viscosity change rate of the obtained varnish after the storage stability test was 10% or more. The results of Examples D1 to D17 and Comparative Examples D1 to D5 are shown in Table 4.

[0401] [Table 1]

[0402] [Table 2]

[0403] [Table 3]

[0404] [Table 4] [Industrial Applicability]

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

Claims

1. (A) 100 parts by mass of at least one resin selected from the group consisting of polyamic acid esters, polyamic acid salts, and polyimides, (B) a sulfur-containing compound in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the (A) resin; and (C) a photosensitizer, in an amount of 1 to 50 parts by mass based on 100 parts by mass of the (A) resin; Including, The photosensitive resin composition, wherein the sulfur-containing compound (B) contains nitrogen, and the sulfur in the sulfur-containing compound (B) is contained as one atom forming a ring structure.

2. The resin (A) is at least one selected from the group consisting of a polyimide precursor having the following general formula (1) and a polyimide having the following general formula (6), The following general formula (1) is 【Chemistry 1】 {In the formula, X １ is a tetravalent organic group, Y １ is a divalent organic group, n １ is an integer from 2 to 150, and R １ and R ２ each independently represents a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, an aromatic group, or a group represented by the following general formula (2): 【Chemistry 2】 (In the formula, R ３ , R ４ and R ５ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m １ is an integer of 2 to 10; or a saturated aliphatic group having 1 to 4 carbon atoms, or a monovalent organic group represented by the following general formula (3): 【Chemistry 3】 (In the formula, R 6 , R ７ and R 8 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m 2 is an integer from 2 to 10. A polyimide precursor, which is a polyamic acid, a polyamic acid ester, or a polyamic acid salt, is represented by the formula (I), The following general formula (6) is 【Chemistry 6】 {In the formula, X ５ is a 4-14 valent organic group; Y ５ is a divalent to dodecavalent organic group, 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; n ５ is an integer from 3 to 200, and m ３ and m ４ represents an integer from 0 to 10. A polyimide having a structure represented by the formula: The photosensitive resin composition according to claim 1 .

3. 3. The photosensitive resin composition according to claim 1, wherein the sulfur-containing compound (B) is at least one selected from the group consisting of thiazole, 2-aminothiazole, 2-(4-thiazolyl)benzimidazole, 1,3,4-thiadiazole, 2-amino-1,3,4-thiadiazole, 5-amino-1,2,3-thiadiazole, 2,4-thiazolidinedione, benzothiazole, 2-aminobenzothiazole, phenothiazine, N-methylphenothiazine, rhodanine, and N-allylrhodanine.

4. An interlayer insulating film obtained by using the photosensitive resin composition according to any one of claims 1 to 3.

5. (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; 2. A method for producing a cured relief pattern comprising:

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

7. 1. A method for manufacturing a semiconductor device including a cured relief pattern, comprising: A method for manufacturing a semiconductor device, comprising producing a cured relief pattern by the method according to claim 5 or 6.

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