resin composition

Abstract

A resin composition comprising at least one resin selected from the group consisting of polyimides, polybenzoxazole, and precursors of these, a compound represented by formula (A), and a solvent. [In formula (A), Ra represents a hydrogen atom, a hydroxyl group, a methylol group, or a C1-C30 alkyl group, Rb represents a C1-C30 alkyl group, m indicates an integer of 0-3, n indicates an integer of 1-4, and the sum of m and n is four at most.]

Description

Technical Field

[0001] The present invention relates to a resin composition, a resin film obtained from the resin composition, a photosensitive resist film using the photosensitive resin composition, a method for producing a substrate with a cured relief pattern, and a semiconductor device.

Background Art

[0002] Conventionally, polyimide resins, polybenzoxazole resins and the like, which have excellent heat resistance, electrical properties and mechanical properties in combination, have been used for insulating materials for electronic components, passivation films for semiconductor devices, surface protective films, interlayer insulating films and the like (see Patent Document 1).

[0003] When forming an insulating film or the like from a resin composition containing a polyimide-based resin, if the insulating film or the like is formed on a metal wiring (for example, copper wiring, copper alloy wiring, etc.), adhesion may be deteriorated. Therefore, in order to suppress a decrease in adhesion, it has been proposed to incorporate triazole or a derivative thereof into a photosensitive polyimide-based resin composition (Patent Document 2).

[0004] Further, when forming an insulating film or the like from a resin composition containing a polyimide-based resin, if the insulating film or the like is formed on a metal wiring (for example, copper or copper alloy wiring), the metal wiring may be oxidized. Therefore, in order to suppress oxidation of the metal wiring, it has been proposed to incorporate an antioxidant such as a phenolic antioxidant into the polyimide resin composition (Patent Document 3).

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

[0006] In recent years, semiconductor devices have increasingly used higher frequencies of electrical signals due to the need to transmit and process large amounts of information at high speeds. Since high-frequency electrical signals are prone to attenuation, it is necessary to minimize transmission loss. Therefore, resins used in semiconductor devices require a low dielectric loss tangent.

[0007] Therefore, there is a need for a resin composition that can produce a film on a substrate having metal wiring on its surface that possesses excellent adhesion, excellent oxidation resistance, and a low dielectric loss tangent. However, the resin compositions described in Patent Documents 1 to 3 do not satisfy all of those properties.

[0008] In view of the above circumstances, the object of the present invention is to provide a resin composition that can be obtained on a substrate having metal wiring on its surface that has excellent adhesion, excellent oxidation resistance, and low dielectric loss tangent, a resin film obtained from the resin composition, a photosensitive resist film using the resin composition, a method for manufacturing a substrate with a cured relief pattern, and a semiconductor device. [Means for solving the problem]

[0009] As a result of diligent research to achieve the above objectives, the present inventors have discovered that by incorporating a compound represented by the following formula (A) into a resin composition containing polyimide or the like, a resin composition can be obtained that provides a film with excellent adhesion, excellent oxidation resistance, and low dielectric loss tangent on a substrate having metal wiring on its surface, thereby completing the present invention.

[0010] [1] A resin composition comprising at least one resin selected from the group consisting of polyimides, polybenzoxazoles and their precursors, a compound represented by the following formula (A), and a solvent. [ka] [In formula (A), Ra R represents a hydrogen atom, a hydroxyl group, a methylol group, or an alkyl group having 1 to 30 carbon atoms. b 'm' represents an alkyl group with 1 to 30 carbon atoms. 'm' represents an integer from 0 to 3, and 'n' represents an integer from 1 to 4. The maximum sum of m and n is 4. [2] The resin composition according to [1], wherein the resin is at least one resin selected from the group consisting of polyimides and their precursors. [3] The resin composition according to [1] or [2], wherein the resin is a polyimide having structural units represented by the following formula (1-a) and the following formula (1-b-1), or a polyimide precursor having structural units represented by the following formula (3) and the following formula (1-b-2). [ka] [In formulas (1-a) and (1-b-1), Ar1 represents a tetravalent organic group, X 11 This represents a divalent organic group that has a photopolymerizable group. In formulas (3) and (1-b-2), Ar3 represents a tetravalent organic group, L1 and L2 each independently represent a monovalent organic group, and X 12 The symbols represent a divalent organic group, L1, L2, and X. 12 At least one of them has a photopolymerizable group. [4] The resin composition according to any one of [1] to [3], wherein the resin has a divalent organic group represented by the following formula (9-a). [ka] [In formula (9-a), V1 represents a direct bond, ether bond, ester bond, amide bond, urethane bond, or urea bond, W1 represents an oxygen atom or an NH group, R 15 R represents an alkylene group having 2 to 6 carbon atoms, which may be directly bonded or substituted with a hydroxyl group. 16 * represents a hydrogen atom or a methyl group, and * represents a bonding bond. [5] The resin composition according to [4], wherein V1 in formula (9-a) represents an ester bond and W1 represents an oxygen atom. [6] R in formula (9-a)15 The resin composition according to [4] or [5], wherein represents a 1,2-ethylene group. [7] R in the formula (A) a The resin composition according to any one of [1] to [6], wherein represents a hydrogen atom. [8] The resin composition according to any one of [1] to [7], wherein m in the formula (A) represents 0. [9] The resin composition according to any one of [1] to [8], wherein the compound represented by the formula (A) comprises at least one of 1H-benzotriazole-5-carboxylic acid and 1H-benzotriazole-4-carboxylic acid.

[10] The resin composition according to any one of [1] to [9], further comprising a photo-radical polymerization initiator.

[11] The resin composition according to any one of [1] to

[10] , further comprising a crosslinkable compound.

[12] The resin composition according to any one of [1] to

[11] , which is for forming an insulating film.

[13] The resin composition according to any one of [1] to

[12] , which is a photosensitive resin composition.

[14] The resin composition according to any one of [1] to

[13] , which is a negative photosensitive resin composition.

[15] A resin film which is a fired product of a coating film of the resin composition according to any one of [1] to

[14] .

[16] The resin film according to

[15] , which is an insulating film.

[17] A photosensitive resist film comprising a base film, a photosensitive resin layer formed from the resin composition according to

[13] or

[14] , and a cover film.

[18] (1) a step of applying the resin composition according to

[13] or

[14] onto a substrate to form a photosensitive resin layer on the substrate; (2) a step of exposing the photosensitive resin layer; (3) a step of developing the exposed photosensitive resin layer to form a relief pattern; (4) a step of heat-treating the relief pattern to form a cured relief pattern; and A method for producing a substrate with a cured relief pattern, comprising

[19] A method for manufacturing a substrate with a cured relief pattern according to

[18] , wherein in step (1), the resin composition is applied to the substrate having metal wiring on its surface.

[20] The method for manufacturing a substrate with a cured relief pattern according to

[18] or

[19] , wherein the developer used for development is an organic solvent. A substrate with a cured relief pattern manufactured by any of the methods described in

[21]

[18] to

[20] .

[22] A semiconductor device comprising a semiconductor element and a cured film provided on the upper or lower part of the semiconductor element, wherein the cured film is a cured film formed from any of the resin compositions described in [1] to

[14] .

[23] The resin composition is a photosensitive resin composition, The semiconductor device according to

[22] , wherein the cured film is a cured relief pattern formed from the photosensitive resin composition. [Effects of the Invention]

[0011] According to the present invention, a resin composition is obtained that provides a film on a substrate having metal wiring on its surface that exhibits excellent adhesion, excellent oxidation resistance, and low dielectric loss tangent; a resin film obtained from the resin composition; a photosensitive resist film using the resin composition; a method for manufacturing a substrate with a cured relief pattern; and a semiconductor device. [Modes for carrying out the invention]

[0012] (Resin composition) The resin composition of the present invention comprises at least one resin selected from the group consisting of polyimides, polybenzoxazoles, and their precursors, a compound represented by formula (A), and a solvent.

[0013] <Polyimide, etc.> The resin composition comprises at least one resin selected from the group consisting of polyimides, polybenzoxazoles, and their precursors (hereinafter sometimes referred to as "polyimides, etc.").

[0014] Polyimides and the like are preferably photopolymerizable groups, more preferably polymerizable unsaturated groups, even more preferably (meth)acryloyl groups, and particularly preferably have a divalent organic group represented by the following formula (9-a), in terms of imparting photosensitivity when the resin composition is used as a photosensitive resin composition. [ka] [In formula (9-a), V1 represents a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-), or a urea bond (-NHCONH-), W1 represents an oxygen atom or an NH group, R 15 R represents an alkylene group having 2 to 6 carbon atoms, which may be directly bonded or substituted with a hydroxyl group. 16 * represents a hydrogen atom or a methyl group, and * represents a bonding bond.

[0015] <<Polyimides and their precursors>> Examples of polyimides and their precursors include polyimides, polyamic acids, and polyamic acid esters.

[0016] Examples of polyimides include the following polyimide (1). Examples of polyamic acids include the following polyamic acid (2). Examples of polyamic acid esters include the following polyamic acid ester (3). Polyimide (1) is a polyimide having structural units represented by the following formulas (1-a) and (1-b). Polyamic acid (2) is a polyamic acid having structural units represented by the following formula (2) and the following formula (1-b). Polyamic acid ester (3) is a polyamic acid ester having structural units represented by the following formula (3) and formula (1-b).

[0017] [ka] [In formula (1-a), Ar1 represents a tetravalent organic group. In formula (1-b), X represents a divalent organic group.]

[0018] Chemical Formula [In formula (2), Ar2 represents a tetravalent organic group.]

[0019] Chemical Formula [In formula (3), Ar3 represents a tetravalent organic group, and L1 and L2 each independently represent a monovalent organic group.]

[0020] An example of polyimide is a polyimide having a structural unit represented by formula (1-a) and the following formula (1-b-1). An example of a polyimide precursor is a polyimide precursor having a structural unit represented by formula (3) and the following formula (1-b-2), provided that in the polyimide precursor, L1, L2 and X 12 at least one of which has a photopolymerizable group. Chemical Formula [In formula (1-b-1), X 11 represents a divalent organic group having a photopolymerizable group. In formula (1-b-2), X 12 represents a divalent organic group.]

[0021] <<<Ar1, Ar2, and Ar3>>> Ar1, Ar2, and Ar3 each represent a tetravalent organic group. There are no particular restrictions on the tetravalent organic group, and examples thereof include a tetravalent organic group derived from an aliphatic tetracarboxylic dianhydride, a tetravalent organic group derived from an alicyclic tetracarboxylic dianhydride, and a tetravalent organic group derived from an aromatic tetracarboxylic dianhydride. As the tetravalent organic group, a tetravalent organic group having three or more aromatic rings is preferable from the viewpoint that a film having a lower dielectric loss tangent can be obtained.

[0022] The number of aromatic rings in Ar1, Ar2, and Ar3 is preferably three or more, and more preferably four or more, in order to obtain a film with a lower dielectric loss tangent. There is no particular upper limit to the number of aromatic rings, but for example, it may be eight or less, or six or less.

[0023] Regarding the counting of aromatic rings in "three or more aromatic rings," polycyclic aromatic rings, which are formed by the fusion of two or more aromatic rings such as naphthalene rings and anthracene rings, are counted as one aromatic ring. Therefore, a naphthalene ring is counted as one aromatic ring. On the other hand, a biphenyl ring is not a fused ring, so it is counted as two aromatic rings. And a perylene ring is counted as two aromatic rings. Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles.

[0024] From the viewpoint of suitably obtaining the effects of the present invention, it is preferable that Ar1, Ar2, and Ar3 represent tetravalent organic groups represented by the following formula (4). [ka] [In formula (4), X1 and X2 independently represent a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-), a urea bond (-NHCONH-), a thioether bond (-S-), or a sulfonyl bond (-SO2-). R a1 and R a2 Each of these represents an alkyl group having 1 to 6 carbon atoms, which may be independently substituted. Z1 represents a divalent organic group represented by the following formula (5-a), formula (5-b), or formula (5-c). n1 and n2 each independently represent integers between 0 and 3. R a1 If there are multiple, then multiple R a1 They can be the same or different. a2 If there are multiple, then multiple R a2They can be the same or they can be different. * represents a bond.

[0025] R in equation (4) a1 and R a2 Examples of alkyl groups having 1 to 6 carbon atoms that may be substituted include alkyl groups having 1 to 6 carbon atoms. Examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. In this specification, alkyl groups and alkylene groups may be linear, branched, cyclic, or a combination of two or more of these, unless their structure is specifically mentioned. Examples of substituents on alkyl groups having 1 to 6 carbon atoms that may be substituted include halogen atoms, hydroxyl groups, mercapto groups, carboxyl groups, cyano groups, formyl groups, haloformyl groups, sulfo groups, amino groups, nitro groups, nitroso groups, oxo groups, thioxy groups, and alkoxy groups having 1 to 6 carbon atoms. Note that "alkyl groups with 1 to 6 carbon atoms that may be substituted" refers to the number of carbon atoms in the alkyl group excluding the substituents. Furthermore, the number of substituents is not particularly limited.

[0026] [ka] [In formula (5-a), R3 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and m1 represents an integer from 0 to 4. When m1 is 2 or greater, R3 may be the same or different. In formula (5-b), Z2 represents a direct bond or a divalent organic group represented by formula (6-a) or formula (6-b) below, R4 and R5 each independently represent an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and m2 and m3 each independently represent an integer from 0 to 4. When m2 is 2 or greater, R4 may be the same or different. When m3 is 2 or greater, R5 may be the same or different. In formula (5-c), R6 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and m4 represents an integer from 0 to 6. When m4 is 2 or greater, R6 may be the same or different. * represents a bond.

[0027] [ka] [In formula (6-a), R7 and R8 each independently represent an alkyl group having 1 to 6 carbon atoms, which may be substituted with a hydrogen atom or a halogen atom. In equation (6-b), R9 and R 10 Each of these independently represents an alkylene group having 1 to 6 carbon atoms or an arylene group having 6 to 12 carbon atoms that may be substituted. * represents a bond.

[0028] From the viewpoint of suitably obtaining the effects of the present invention, Z1 preferably represents a divalent organic group represented by formula (5-b).

[0029] Examples of C1-C6 alkyl groups that may be substituted with halogen atoms in R7 and R8 include C1-C6 alkyl groups and C1-C6 halogenated alkyl groups. Examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Examples of halogen atoms in alkyl halides having 1 to 6 carbon atoms include fluorine, chlorine, bromine, and iodine. The halogenation of the halogenated alkyl group having 1 to 6 carbon atoms may be partial or complete.

[0030] R9 and R 10 Examples of substituents on the alkylene group having 1 to 6 carbon atoms that may be substituted include halogen atoms, hydroxyl groups, mercapto groups, carboxyl groups, cyano groups, formyl groups, haloformyl groups, sulfo groups, amino groups, nitro groups, nitroso groups, oxo groups, thioxy groups, and alkoxy groups having 1 to 6 carbon atoms. Examples of alkylene groups having 1 to 6 carbon atoms that may be substituted include alkylene groups having 1 to 6 carbon atoms and halogenated alkylene groups having 1 to 6 carbon atoms. Examples of alkylene groups having 1 to 6 carbon atoms include methylene groups, ethylene groups, propylene groups, and butylene groups. Furthermore, the "1 to 6 carbon atoms" in "alkylene groups with 1 to 6 carbon atoms that may be substituted" refers to the number of carbon atoms in the alkylene group excluding the substituents. The number of substituents is not particularly limited.

[0031] R9 and R 10 Examples of substituents on the 6-10 carbon atom arylene group that may be substituted include halogen atoms, halogenated alkyl groups with 1-6 carbon atoms, and halogenated alkoxy groups with 1-6 carbon atoms. The halogenation may be partial or complete. Examples of arylene groups include phenylene groups and naphthylene groups. Furthermore, the "6 to 10 carbon atoms" in "arylene group having 6 to 10 carbon atoms that may be substituted" refers to the number of carbon atoms in the "arylene group" excluding substituents. The number of substituents is not particularly limited.

[0032] Examples of divalent organic groups represented by formula (6-a) include the divalent organic group represented by the following formula. [ka] In the formula, * represents a bond.

[0033] Examples of divalent organic groups represented by formula (6-b) include the divalent organic group represented by the following formula. [ka] In the formula, R 31 ~R 33 Each of the following independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms that may be substituted with a halogen atom, or an alkoxy group having 1 to 6 carbon atoms that may be substituted with a halogen atom. n31 represents an integer from 0 to 5. n32 and n33 each independently represent an integer from 0 to 4. R 31 If there are multiple, then multiple R 31 They can be the same or different. 32 If there are multiple, then multiple R 32 They can be the same or different. 33 If there are multiple, then multiple R 33 They can be the same or different. * represents a combination.

[0034] R 31 ~R 33 Specific examples of C1-C6 alkyl groups that may be substituted with halogen atoms include, for example, C1-C6 alkyl groups and C1-C6 halogenated alkyl groups. Examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Examples of halogen atoms in alkyl halides having 1 to 6 carbon atoms include fluorine, chlorine, bromine, and iodine. The halogenation of the alkyl halides having 1 to 6 carbon atoms may be partial or complete. R31 ~R 33 Specific examples of alkoxy groups having 1 to 6 carbon atoms that may be substituted with halogen atoms include alkyl groups having 1 to 6 carbon atoms that may be substituted with halogen atoms, which are then converted into alkoxy groups.

[0035] Examples of Ar1, Ar2, and Ar3 include tetravalent organic groups represented by the following formulas. [ka] [ka] In the formula, * represents a bond.

[0036] Furthermore, Ar1, Ar2, and Ar3 may be, for example, tetravalent organic groups represented by the following formula. [ka] [ka] In the formula, * represents a bond.

[0037] << <X、X 11 , and X 12 >>> X represents a divalent organic group. For example, X represents a divalent aromatic group that has a photopolymerizable group. X 11 X represents a divalent organic group having a photopolymerizable group. 11 This represents, for example, a divalent aromatic group having a photopolymerizable group. X 12 This represents a divalent organic group. X 12 For example, it has a photopolymerizable group. 12 For example, this represents a divalent organic group having a photopolymerizable group. 12 This represents, for example, a divalent aromatic group having a photopolymerizable group.

[0038] Examples of photopolymerizable groups include radical polymerizable groups, cationic polymerizable groups, and anionic polymerizable groups. Among these, radical polymerizable groups are preferred. Examples of radical polymerizable groups include acryloyl groups, methacryloyl groups, propenyl ether groups, vinyl ether groups, and vinyl groups.

[0039] Examples of aromatic rings in divalent aromatic groups having photopolymerizable groups include benzene rings, naphthalene rings, and anthracene rings.

[0040] A divalent aromatic group having a photopolymerizable group is, for example, a residue obtained by removing two amino groups from an aromatic diamine compound having a photopolymerizable group.

[0041] As a divalent aromatic group having a photopolymerizable group, a divalent organic group represented by the following formula (9-a) is preferred. [ka] [In formula (9-a), V1 represents a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-), or a urea bond (-NHCONH-), W1 represents an oxygen atom or an NH group, R 15 R represents an alkylene group having 2 to 6 carbon atoms, which may be directly bonded or substituted with a hydroxyl group. 16 * represents a hydrogen atom or a methyl group, and * represents a bonding bond.

[0042] The two bonds in equation (9-a) are, for example, bonds that bond to a nitrogen atom.

[0043] In this specification, examples of alkylene groups having 2 to 6 carbon atoms that may be substituted with hydroxyl groups include 1,1-ethylene group, 1,2-ethylene group, 1,2-propylene group, 1,3-propylene group, 1,4-butylene group, 1,2-butylene group, 2,3-butylene group, 1,2-pentylene group, 2,4-pentylene group, 1,2-hexylene group, 1,2-cyclopropylene group, 1,2-cyclobutylene group, 1,3-cyclobutylene group, 1,2-cyclopentylene group, 1,2-cyclohexylene group, and alkylene groups in which at least some of the hydrogen atoms are substituted with hydroxyl groups (e.g., 2-hydroxy-1,3-propylene group).

[0044] V1 preferably represents an ester bond (-COO-). W1 preferably represents an oxygen atom. R 15 Preferably, represents a 1,2-ethylene group.

[0045] Examples of divalent organic groups represented by formula (9-a) include the divalent organic groups represented by the following formulas. [ka] In the formula, * represents a bond. The two bonds are located, for example, in the meta position relative to the substituent having a photopolymerizable group.

[0046] X, and X 12 It is preferable that this represents a divalent organic group having three or more aromatic rings, as this allows for the acquisition of a film with a lower dielectric loss tangent. Here, a divalent organic group having three or more aromatic rings refers to an organic group different from the divalent aromatic group having a photopolymerizable group as described above.

[0047] A divalent organic group having three or more aromatic rings is, for example, a residue obtained by removing two amino groups from an aromatic diamine compound having three or more aromatic rings.

[0048] The number of aromatic rings in a divalent organic group having three or more aromatic rings is not particularly limited as long as there are three or more, but for example, it may be four or more. The upper limit of the number of aromatic rings is not particularly limited, but for example, it may be eight or less, or six or less.

[0049] The divalent organic group having three or more aromatic rings is not particularly limited, but is preferably a divalent organic group represented by the following formula (13). [ka] [In formula (13), X 21 and X 22 Each of these independently represents a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), an urethane bond (-NHCOO-), an urea bond (-NHCONH-), a thioether bond (-S-), or a sulfonyl bond (-SO2-). R 21 and R 22 Each of these represents an alkyl group having 1 to 6 carbon atoms, which may be independently substituted. Y 20 represents a divalent organic group represented by the above formula (5-a), formula (5-b), or formula (5-c). n21 and n22 each independently represent integers from 0 to 4. R 21 If there are multiple, then multiple R 21 They can be the same or different. 22 If there are multiple, then multiple R 22 They can be the same or they can be different. * represents a bond.

[0050] R in equation (13) 21 and R 22Examples of the optionally substituted alkyl group having 1 to 6 carbon atoms include alkyl groups having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. In the present specification, unless specifically stated otherwise with respect to the structure thereof, an alkyl group or an alkylene group may be linear, branched or cyclic, or may be a combination of two or more of these. Examples of the substituent in the optionally substituted alkyl group having 1 to 6 carbon atoms include a halogen atom, a hydroxy group, a mercapto group, a carboxy group, a cyano group, a formyl group, a haloformyl group, a sulfo group, an amino group, a nitro group, a nitroso group, an oxo group, a thiooxy group, and an alkoxy group having 1 to 6 carbon atoms. Note that "1 to 6 carbon atoms" in "optionally substituted alkyl group having 1 to 6 carbon atoms" refers to the number of carbon atoms of the "alkyl group" excluding substituents. There is no particular limitation on the number of substituents.

[0051] Examples of the divalent organic group having three or more aromatic rings include divalent organic groups represented by the following formulae.

Chemical Formula

Chemical Formula

[0052] Examples of other divalent organic groups include divalent organic groups represented by the following formulae. These divalent organic groups are, for example, residues obtained by removing two amino groups from a diamine.

Chemical Formula

[0053] <<<L1 and L2>>> L1 and L2 each independently represent a monovalent organic group. Examples of monovalent organic groups include alkyl groups having 1 to 30 carbon atoms. Examples of alkyl groups having 1 to 30 carbon atoms include linear alkyl groups, branched alkyl groups, and alicyclic alkyl groups. Examples of linear alkyl groups having 1 to 30 carbon atoms include methyl, ethyl, propyl, butyl, pentyl (amyl), hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl (myristyl), pentadecyl, hexadecyl (palmityl), heptadecyl (margaryl), octadecyl (stearyl), nonadecyl, icosyl (arachidyl), henicosyl, docosyl (behenyl), tricosyl, tetracosyl (lignoceryl), pentacosyl, hexacosyl, and heptacosyl groups. Examples of branched alkyl groups having 1 to 30 carbon atoms include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, sec-isoamyl group, isohexyl group, neohexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 2-ethylpentyl group, heptane-3-yl group, heptane-4-yl group, 4-methylhexane- 2-yl group, 3-methylhexane-3-yl group, 2,3-dimethylpentan-2-yl group, 2,4-dimethylpentan-2-yl group, 4,4-dimethylpentan-2-yl group, 6-methylheptyl group, 2-ethylhexyl group, octan-2-yl group, 6-methylheptan-2-yl group, 6-methyloctyl group, 3,5,5-trimethylhexyl group, nonane-4-yl group, 2,6-dimethylheptan-3-yl group, 3,6-dimethylheptan-3-yl group, 3-ethylheptan-3-yl group, 3,7-di Methyl octyl group, 8-methyl nonyl group, 3-methyl nonan-3-yl group, 4-ethyl octane-4-yl group, 9-methyl decyl group, undecane-5-yl group, 3-ethyl nonan-3-yl group, 5-ethyl nonan-5-yl group, 2,2,4,5,5-pentamethylhexane-4-yl group, 10-methyl undecyl group, 11-methyl dodecyl group, tridecane-6-yl group, tridecane-7-yl group, 7-ethyl undecane-2-yl group, 3-ethyl undecane-3-yl group, 5-ethyl undecane-5- Iyl group, 12-methyltridecyl group, 13-methyltetradecyl group, pentadecane-7-yl group, pentadecane-8-yl group, 14-methylpentadecyl group, 15-methylhexadecyl group, heptadecane-8-yl group, heptadecane-9-yl group, 3,13-dimethylpentadecane-7-yl group, 2,2,4,8,10,10-hexamethylundecane-5-yl group, 16-methylheptadecyl group, 17-methyloctadecyl group, nonadecane-9-yl group, nonadecane-10-yl group, 2,6,10,Examples include 14-tetramethylpentadecane-7-yl group, 18-methylnonadecyl group, 19-methylicosyl group, henicosane-10-yl group, 20-methylhenicosyl group, 21-methyldocosyl group, tricosan-11-yl group, 22-methyltricosyl group, 23-methyltetracosyl group, pentacosane-12-yl group, pentacosane-13-yl group, 2,22-dimethyltricosane-11-yl group, 3,21-dimethyltricosane-11-yl group, 9,15-dimethyltricosane-11-yl group, 24-methylpentacosyl group, 25-methylhexacosyl group, and heptacosane-13-yl group. Examples of alicyclic alkyl groups having 1 to 30 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 4-tert-butylcyclohexyl group, 1,6-dimethylcyclohexyl group, menthyl group, cycloheptyl group, cyclooctyl group, bicyclo[2.2.1]heptan-2-yl group, bornyl group, isobornyl group, 1-adamantyl group, 2-adamantyl group, tricyclo[5.2.1.0 2,6 ] Decane-4-yl group, tricyclo[5.2.1.0 2,6 Examples include the decane-8-yl group and the cyclododecyl group.

[0054] Furthermore, L1 and L2 may have photopolymerizable groups. That is, L1 and L2 may be monovalent organic groups having photopolymerizable groups. Examples of photopolymerizable groups include radical polymerizable groups, cationic polymerizable groups, and anionic polymerizable groups. Among these, radical polymerizable groups are preferred. Examples of radical polymerizable groups include acryloyl groups, methacryloyl groups, propenyl ether groups, vinyl ether groups, and vinyl groups.

[0055] As a monovalent organic group having a photopolymerizable group, a monovalent organic group represented by the following formula (9-b) is preferred. [ka] [In formula (9-b), W2 represents an oxygen atom or an NH group, R17 R represents an alkylene group having 2 to 6 carbon atoms, which may be directly bonded or substituted with a hydroxyl group. 18 * represents a hydrogen atom or a methyl group, and * represents a bonding bond.

[0056] W2 preferably represents an oxygen atom. R 17 Preferably, represents a 1,2-ethylene group.

[0057] Polyimide (1) is, for example, an imidide of a polyamic acid, which is a reaction product of a diamine component and a tetracarboxylic acid derivative. The imidization rate of polyimide(1) does not need to be 100%. The imidization rate of polyimide(1) may be, for example, 90% or more, 95% or more, or 98% or more.

[0058] Polyamic acid (2) is, for example, a reaction product of a diamine component and a tetracarboxylic acid derivative. Polyamic acid ester (3) is, for example, a reaction product of a diamine component and a tetracarboxylic acid diester.

[0059] Examples of tetracarboxylic acid derivatives include tetracarboxylic acids, tetracarboxylic acid diesters, tetracarboxylic acid dihalides, and tetracarboxylic acid dianhydrides.

[0060] <<Method for producing polyimides and their precursors>> The method for producing polyimides and their precursors is not particularly limited, and includes known methods such as reacting a diamine component with a tetracarboxylic acid derivative to obtain polyamic acid, polyamic acid ester, or polyimide. Polyamic acid, polyamic acid ester, and polyimide can be synthesized by known methods, such as those described in publication WO2013 / 157586.

[0061] The production of polyamic acids or polyamic acid esters is carried out, for example, by reacting a diamine component with a tetracarboxylic acid derivative in a solvent (condensation polymerization).

[0062] Specific examples of the above solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylisobutyric acid amide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidinone. Furthermore, if the solvent solubility of the polymer is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or solvents represented by the following formulas [D-1] to [D-3] can be used. [ka] (In formula [D-1], D 1 D represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-2], D 2 D represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], D 3 (This represents an alkyl group with 1 to 4 carbon atoms.)

[0063] These solvents may be used individually or in combination. Furthermore, even solvents that do not dissolve polyamic acid may be mixed with the above solvents, provided that no precipitation occurs of the polyamic acid or polyamic acid ester.

[0064] When reacting a diamine component with a tetracarboxylic acid derivative in a solvent, the reaction can be carried out at any concentration, but preferably at 1% to 50% by mass, and more preferably at 5% to 30% by mass. The reaction can be carried out at a high concentration initially, and then more solvent can be added. In the reaction, the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid derivative is preferably 0.8 to 1.2. As with typical condensation polymerization reactions, the closer this molar ratio is to 1.0, the larger the molecular weight of the resulting polyamic acid.

[0065] When reacting a diamine component with a tetracarboxylic acid derivative, a thermal polymerization inhibitor may be added to the reaction system to avoid polymerization of the photopolymerizable group. Examples of thermal polymerization inhibitors include hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-p-cresol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt. The amount of thermal polymerization inhibitor used is not particularly limited.

[0066] Polyimides are obtained by dehydrating and cyclizing the polyamic acid obtained in the above reaction. Methods for obtaining polyimide include thermal imidation, in which the solution of polyamic acid obtained in the above reaction is heated directly, and chemical imidation, in which a catalyst is added to the solution of polyamic acid. When thermal imidation is performed in solution, the temperature is 100°C to 400°C, preferably 120°C to 250°C, and it is preferable to remove the water produced by the imidation reaction from the system.

[0067] The above chemical imidation can be carried out by adding a basic catalyst and an acid anhydride to a solution of the polyamic acid obtained from the reaction, and stirring at -20°C to 250°C, preferably 0°C to 180°C. The amount of basic catalyst is 0.1 to 30 times the amount of amidic acid groups, preferably 0.2 to 20 times, and the amount of acid anhydride is 1 to 50 times the amount of amidic acid groups, preferably 1.5 to 30 times. Examples of basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine, among which triethylamine is preferred because it does not easily produce polyisoimide as a byproduct. Examples of acid anhydrides include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride, among which acetic anhydride is preferred because it facilitates purification after the reaction is complete. The imidization rate by chemical imidation (the ratio of ring-closed repeating units to the total repeating units of the polyimide precursor, also called the ring-closing rate) can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

[0068] To recover the imidide product from the above imidation reaction solution, the reaction solution can be precipitated by adding it to a solvent. Examples of solvents that can be used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer precipitated in the solvent can be recovered by filtration and then dried at room temperature or by heating under normal or reduced pressure.

[0069] Polyimides and their precursors may be end-capped. The method of end-capping is not particularly limited, and conventionally known methods using monoamines or acid anhydrides can be used, for example.

[0070] <<Polybenzoxazoles and their precursors>> The polybenzoxazole is not particularly limited as long as it is a polymer containing benzoxazole in its repeating units, and may also be a copolymer having other repeating units. Polybenzoxazoles can be obtained, for example, by dehydrating and cyclizing a dicarboxylic acid and a bisaminophenol compound as a diamine using polyphosphate. Alternatively, polybenzoxazoles can be obtained by dehydrating and cyclizing a polyhydroxyamide using heat or a reaction with phosphoric anhydride, a base, or a carbodiimide compound.

[0071] The precursor of the polybenzoxazole is not particularly limited as long as it is a polymer containing a constituent unit that gives benzoxazole units, and may also be a copolymer having other repeating units. Polybenzoxazole precursors can be obtained, for example, by reacting a dicarboxylic acid, a corresponding dicarboxylic acid dichloride, or a dicarboxylic acid active diester with a diamine such as a bisaminophenol compound. Examples of polybenzoxazole precursors include polyhydroxyamides.

[0072] When the resin composition is a photosensitive resin composition, it is preferable that the polybenzoxazole and its precursor have polymerizable unsaturated groups. Examples of polymerizable unsaturated groups include (meth)acryloyl groups.

[0073] The weight-average molecular weight of polyimide and the like is not particularly limited, but the weight-average molecular weight measured in terms of polyethylene oxide by gel permeation chromatography (hereinafter abbreviated as GPC in this specification) is preferably 5,000 to 100,000, more preferably 7,000 to 50,000, even more preferably 10,000 to 50,000, and particularly preferably 10,000 to 40,000.

[0074] <Compound represented by formula (A)> The resin composition contains a compound represented by the following formula (A). By including a compound represented by formula (A) in a resin composition containing polyimide, a film can be obtained on a substrate having metal wiring on its surface that exhibits excellent adhesion, excellent oxidation resistance, and low dielectric loss tangent.

[0075] The inventors of the present invention have diligently conducted research to obtain a resin composition that provides a film with excellent adhesion, excellent oxidation resistance, and low dielectric loss tangent on a substrate having metal wiring on its surface. In this study, various additives such as triazole compounds (e.g., 5-methyl-1H-benzotriazole), phenolic antioxidants (e.g., IRGANOX® 3114), silane coupling agents (e.g., KBM-5103), and triazine-based metal ion scavengers (e.g., 2,4-diamino-6-butylamino-1,3,5-triazine, 2,4-diamino-6-diallylamino-1,3,5-triazine, 6-(dibutylamino)-1,3,5-triazine-2,4-dithiol) were used to obtain a resin composition that provides a film with excellent adhesion, excellent antioxidant properties, and low dielectric loss tangent on substrates having metal wiring on their surface. [ka] [In formula (A), R a R represents a hydrogen atom, a hydroxyl group, a methylol group, or an alkyl group having 1 to 30 carbon atoms. b 'm' represents an alkyl group with 1 to 30 carbon atoms. 'm' represents an integer from 0 to 3, and 'n' represents an integer from 1 to 4. The maximum sum of m and n is 4.

[0076] Among alkyl groups having 1 to 30 carbon atoms, alkyl groups having 1 to 20 carbon atoms are preferred, alkyl groups having 1 to 10 carbon atoms are more preferred, and alkyl groups having 1 to 6 carbon atoms are particularly preferred.

[0077] Examples of alkyl groups having 1 to 30 carbon atoms include linear alkyl groups, branched alkyl groups, and cyclic alkyl groups. Examples of linear alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, and docosyl groups. Examples of branched alkyl groups include isopropyl group, isobutyl group, isovaleryl group, isohexyl group, 2-ethylhexyl group, 3-ethylheptyl group, 2-ethyloctyl group, 3-ethyldecyl group, 2-hexyldecyl group, 2-hexylundecyl group, 2-octyldecyl group, 2-octyldodecyl group, 2-decyldodecyl group, 2-decyltetradecyl group, 2-decylhexadecyl group, 3-hexyldecyl group, 3-octyldecyl group, 3-octyldodecyl group, 3-decyltetradecyl group, 3-decylhexadecyl group, 4-hexyldecyl group, 4-octyldecyl group, 4-octyldodecyl group, 4-decyltetradecyl group, 4-decylhexadecyl group, 4-cyclohexylbutyl group, and 8-cyclohexyloctyl group. Examples of cyclic alkyl groups include cyclopentyl, cyclohexyl, cycloheptyl, 3-decylcyclopentyl, and 4-decylcyclohexyl groups.

[0078] The compounds represented by formula (A) can be used individually or in combination of two or more.

[0079] R a A hydrogen atom is preferred. m is preferably 0. n is preferably 1.

[0080] The compounds represented by formula (A) are preferably 1H-benzotriazole-5-carboxylic acid (5-carboxybenzotriazole), 1H-benzotriazole-4-carboxylic acid (4-carboxybenzotriazole), and combinations thereof.

[0081] The compound represented by formula (A) may be a commercially available product. Examples of commercially available products include CBT-5 and CBT-SG from Johoku Chemical Industry Co., Ltd., and VERZONE® C-BTA from Yamato Chemical Co., Ltd.

[0082] The content of the compound represented by formula (A) in the resin composition is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass, per 100 parts by mass of polyimide, etc.

[0083] <Solvent> As the solvent contained in the resin composition, it is preferable to use an organic solvent from the viewpoint of solubility in polyimide and the like. Specifically, examples include N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylisobutyrate amide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, methyl 2-hydroxyisobutyrate, ethyl lactate, or solvents represented by the following formulas [D-1] to [D-3], which can be used individually or in combination of two or more. [ka] (In formula [D-1], D 1 D represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-2], D 2 D represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], D 3 (This represents an alkyl group with 1 to 4 carbon atoms.)

[0084] The solvent can be used in an amount ranging from 30 to 1500 parts by mass, preferably 100 to 1000 parts by mass, per 100 parts by mass of polyimide or the like, depending on the desired coating thickness and viscosity of the resin composition.

[0085] <Other ingredients> In the embodiment, the resin composition may further contain other components other than the compound represented by formula (A) and the solvent, such as polyimide. Examples of other components include photoradical polymerization initiators (also called "photoradical initiators"), crosslinkable compounds (also called "crosslinking agents"), thermosetting agents, other resin components, fillers, sensitizers, adhesion aids, thermal polymerization inhibitors, azole compounds, hindered phenol compounds, and the like.

[0086] <<Photoradical polymerization initiator>> When the resin composition is used as a photosensitive resin composition, the resin composition includes, for example, a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited as long as it is a compound that absorbs the light source used during photocuring, but examples include tert-butylperoxy-iso-butyrate, 2,5-dimethyl-2,5-bis(benzoyldioxy)hexane, 1,4-bis[α-(tert-butyldioxy)-iso-propoxy]benzene, di-tert-butylperoxide, 2,5-dimethyl-2,5-bis(tert-butyldioxy)hexenehydroperoxide, α-(iso-propylphenyl)-iso-propylhydroperoxide, tert-butylhydroperoxide, 1,1-bis(tert-butyldioxy)-3,3,5-trimethylcyclohexane, butyl-4,4-bis(tert-butyldioxy)valerate, cyclohexanone peroxide, and 2,2',5,5'-tetra(tert-butylperoxide). Organic peroxides such as oxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-amylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-hexylperoxycarbonyl)benzophenone, 3,3'-bis(tert-butylperoxycarbonyl)-4,4'-dicarboxybenzophenone, tert-butylperoxybenzoate, di-tert-butyldiperoxyisophthalate, etc.; quinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, etc.; benzoin derivatives such as benzoin methyl, benzoin ethyl ether, α-methylbenzoin, α-phenylbenzoin, etc.2,2-Dimethoxy-1,2-Diphenylethane-1-one, 1-Hydroxycyclohexylphenyl ketone, 2-Hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-Hydroxyethoxy)-phenyl]-2-Hydroxy-2-methyl-1-propan-1-one, 2-Hydroxy-1-[4-{4-(2-Hydroxy-2-methylpropionyl)benzyl}phenyl]-2-methyl-propan-1-one, Phenylglyoxylic acid methyl ester, 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl Examples include alkylphenone compounds such as (L)-1-butanone and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholine-4-ylphenyl)-butan-1-one; acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; and oxime ester compounds such as 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione and 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone.

[0087] Photoradical polymerization initiators are available commercially, for example, IRGACURE® 651, 184, 2959, 127, 907, 369, 379EG, 819, 819DW, 1800, 1870, 784, OXE01, OXE02, OXE03, OXE04, 250, 1173, MBF, TPO, 4265, TPO (all manufactured by BASF), KAYACURE® DETX-S, MBP, DMBI, EPA, OA (all manufactured by Nippon Kayaku Co., Ltd.), VICURE-10, 55 (all manufactured by STAUFFER Co., Ltd.), ESACURE Examples include KIP150, TZT, 1001, KTO46, KB1, KL200, KS300, EB3, Triazine-PMS, Triazine A, Triazine B (all manufactured by Nippon Siber Hegner Co., Ltd.), Adeka Optomer N-1717, N-1414, N-1606, Adeka Arclus N-1919T, NCI-831E, NCI-930, and NCI-730 (all manufactured by ADEKA Corporation). These photoradical polymerization initiators may be used individually or in combination of two or more.

[0088] The content of the photoradical polymerization initiator is not particularly limited, but is preferably 0.1 to 20 parts by mass per 100 parts by mass of polyimide, and more preferably 0.5 to 15 parts by mass from the viewpoint of photosensitivity characteristics. When the photoradical polymerization initiator is contained in amounts of 0.1 parts by mass or more per 100 parts by mass of polyimide, the photosensitivity of the resin composition tends to improve, while when it is contained in amounts of 20 parts by mass or less, the thick film curability of the resin composition tends to improve.

[0089] <<Crosslinkable compound>> In the embodiment, when the resin composition is used as a photosensitive resin composition, monomers (crosslinkable compounds) having photoradical polymerizable unsaturated bonds can be optionally included in the resin composition to improve the resolution of the relief pattern. Preferred crosslinkable compounds include compounds containing polymerizable groups that undergo radical polymerization reactions with photoradical polymerization initiators, such as (meth)acrylic compounds and maleimide compounds, but are not limited to the following. (Meth)acrylic compounds include diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, ethylene glycol or polyethylene glycol mono or di(meth)acrylate, propylene glycol or polypropylene glycol mono or di(meth)acrylate, glycerol mono, di or tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, cyclohexanedimethyl di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, dioxaneglycol di(meth)acrylate, bisphenol A mono or di(meth)acrylate, bisphenol F di(meth)acrylate, hydrogenated bisphenol A di( Meth)acrylate, benzene trimethacrylate, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, isobornyl(meth)acrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane tri(meth)acrylate, di or tri(meth)acrylate of glycerol, di, tri or tetra(meth)acrylate of pentaerythritol Examples include (meth)acrylates, compounds such as ethylene oxide or propylene oxide adducts of these compounds, 2-isocyanate ethyl (meth)acrylate or isocyanate-containing (meth)acrylate, and compounds obtained by adding blocking agents such as methyl ethyl ketone oxime, ε-caprolactam, γ-caprolactam, 3,5-dimethylpyrazole, diethyl malonate, ethanol, isopropanol, n-butanol, and 1-methoxy-2-propanol.Examples of maleimide compounds include 1,2-bis(maleimide)ethane, 1,4-bis(maleimide)butane, 1,6-bis(maleimide)hexane, N,N'-1,4-phenylenebismaleimide, N,N'-1,3-phenylenedimaleimide, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, bis(2-maleimideethyl)disulfide, 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane, and 1,6'-bismaleimide-(2,2,4-trimethyl)hexane. Commercially available maleimide compounds include BMI-689, BMI-1500, BMI-1700, and BMI-3000 (all manufactured by Designer Molecules Inc.). These compounds may be used individually or in combination of two or more. Furthermore, in this specification, (meth)acrylate means acrylate and methacrylate.

[0090] The content of the crosslinkable compound is not particularly limited, but is preferably 1 to 100 parts by mass, and more preferably 1 to 50 parts by mass, per 100 parts by mass of polyimide, etc.

[0091] <<Thermosetting agent>> Examples of thermosetting agents include hexamethoxymethylmelamine, tetramethoxymethyl glycoluryl, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl) glycoluryl, 1,3,4,6-tetrakis(butoxymethyl) glycoluryl, 1,3,4,6-tetrakis(hydroxymethyl) glycoluryl, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, and 1,1,3,3-tetrakis(methoxymethyl)urea. The content of the thermosetting agent in the resin composition is not particularly limited.

[0092] <<Filler>> Examples of fillers include inorganic fillers, specifically sols of silica, aluminum nitride, boron nitride, zirconia, and alumina. The content of fillers in the resin composition is not particularly limited.

[0093] <<Other resin components>> In the embodiment, the resin composition may further contain resin components other than polyimide, etc. Examples of resin components that can be included in the resin composition include polyoxazole, polyoxazole precursor, phenolic resin, polyamide, epoxy resin, siloxane resin, acrylic resin, and the like. The content of these resin components is not particularly limited, but is preferably in the range of 0.01 parts by mass to 20 parts by mass per 100 parts by mass of polyimide, etc.

[0094] <<Sensitizer>> In the embodiment, when the resin composition is used as a photosensitive resin composition, a sensitizer may be optionally added to the resin composition to improve photosensitivity. Examples of sensitizers include Michla's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylaminocinnamyridane indano n, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetone Examples include 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-mercaptotetrazol, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, and 2-(p-dimethylaminobenzoyl)styrene. These can be used individually or in combination.

[0095] The amount of sensitizer is not particularly limited, but it is preferably 0.1 to 25 parts by mass per 100 parts by mass of polyimide, etc.

[0096] <<Adhesive enhancer>> In this embodiment, an adhesive aid can be optionally added to the resin composition to further improve the adhesion between the film formed using the resin composition and the substrate. Examples of adhesives include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-(meth)acryloxypropyldimethoxymethylsilane, 3-(meth)acryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, and N-[3-(triethoxysilyl)propyl] Examples include talamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane and other silane coupling agents, as well as aluminum-based adhesive aids such as aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0097] Of these adhesive aids, silane coupling agents are more preferable in terms of adhesive strength.

[0098] The content of the adhesive aid is not particularly limited, but it is preferably in the range of 0.5 to 25 parts by mass per 100 parts by mass of polyimide, etc.

[0099] <<Thermal polymerization inhibitor>> In this embodiment, a thermal polymerization inhibitor can be optionally added to improve the viscosity and photosensitivity stability of the resin composition, particularly when stored in a solvent solution. Examples of thermal polymerization inhibitors include hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-p-cresol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

[0100] The content of the thermal polymerization inhibitor is not particularly limited, but it is preferably in the range of 0.005 parts by mass to 12 parts by mass per 100 parts by mass of polyimide, etc.

[0101] <<Azole Compounds>> For example, when using a substrate made of copper or a copper alloy, an azole compound can be optionally added to the resin composition to further suppress oxidation of the substrate. The azole compound referred to here is a compound different from the compound represented by formula (A). Examples of azole compounds include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis( Examples include α,α-dimethylbenzyl)phenyl]-benzotriazole, 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, 1H-tetrazol, 5-methyl-1H-tetrazol, 5-phenyl-1H-tetrazol, 5-amino-1H-tetrazol, 1-methyl-1H-tetrazol, etc. Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. Furthermore, these azole compounds may be used individually or as a mixture of two or more.

[0102] The content of the azole compound is not particularly limited, but is preferably 0.1 to 20 parts by mass per 100 parts by mass of polyimide, and more preferably 0.5 to 5 parts by mass from the viewpoint of photosensitivity characteristics when the resin composition is used as a photosensitive resin composition. When the content of the azole compound per 100 parts by mass of polyimide, etc. is 0.1 parts by mass or more, discoloration of the copper or copper alloy surface is further suppressed when the resin composition is formed on copper or a copper alloy, while when it is 20 parts by mass or less, it is preferable because it provides excellent photosensitivity when the resin composition is used as a photosensitive resin composition.

[0103] <<Hindered phenol compounds>> In this embodiment, a hindered phenol compound can be optionally incorporated into the resin composition to prevent oxidation of the film formed from the resin composition and to prevent oxidation of the azole compound. Examples of hindered phenol compounds include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), and 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-hydroxyhydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t -butylphenol), 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-hydroxybenzoyl) Roxy-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, 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, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H, Examples include, but are not limited to, 3H,5H)-triones, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-triones, and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-triones. 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.

[0104] The content of the hindered phenol compound is not particularly limited, but is preferably 0.1 to 20 parts by mass per 100 parts by mass of polyimide, and more preferably 0.5 to 10 parts by mass from the viewpoint of photosensitivity characteristics when the resin composition is used as a photosensitive resin composition. When the content of the hindered phenol compound per 100 parts by mass of polyimide, etc. is 20 parts by mass or less, it is preferable because the photosensitivity is excellent when the resin composition is used as a photosensitive resin composition.

[0105] The resin composition can be suitably used as a negative-type photosensitive resin composition for the manufacture of the cured relief pattern described later.

[0106] The resin composition of the present invention is preferably used as a resin composition for forming an insulating film. The resin composition of the present invention is preferably a photosensitive resin composition, and more preferably a negative-type photosensitive resin composition.

[0107] (Resin film) The resin film of the present invention is a fired product of a coated film of the resin composition of the present invention. As for the coating method, conventional methods used for coating resin compositions, such as coating with a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., or spray coating with a spray coater, can be used. Various methods can be used for firing to obtain fired products, such as using a hot plate, an oven, or a heating oven with a set temperature program. Firing can be carried out, for example, at temperatures between 130°C and 250°C for 30 minutes to 5 hours. Air may be used as the atmospheric gas during heat curing, or inert gases such as nitrogen or argon may be used. The thickness of the resin film is not particularly limited, but is preferably 1 μm to 100 μm, and more preferably 2 μm to 50 μm. The resin film is, for example, an insulating film.

[0108] (Photosensitive resist film) When the resin composition of the present invention is a photosensitive resin composition, the resin composition of the present invention can be used in a photosensitive resist film (so-called dry film resist). A photosensitive resist film comprises a base film, a photosensitive resin layer (photosensitive resin film) formed from a photosensitive resin composition, and a cover film. Typically, a photosensitive resin layer and a cover film are laminated on a base film in that order.

[0109] A photosensitive resist film can be manufactured, for example, by applying a photosensitive resin composition to a substrate film, drying it to form a photosensitive resin layer, and then laminating a cover film onto the photosensitive resin layer. As for the coating method, conventional methods used for coating photosensitive resin compositions, such as coating with a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., or spray coating with a spray coater, can be used. For example, drying methods include conditions of 20°C to 200°C for 1 minute to 1 hour. The thickness of the resulting photosensitive resin layer is not particularly limited, but is preferably 1 μm to 100 μm, and more preferably 2 μm to 50 μm.

[0110] A known base film can be used, such as a thermoplastic resin film. Examples of thermoplastic resins include polyesters such as polyethylene terephthalate. The thickness of the base film is preferably 2 μm to 150 μm. A known cover film can be used, such as polyethylene film or polypropylene film. A cover film with lower adhesion to the photosensitive resin layer than the base film is preferred. The thickness of the cover film is preferably 2 μm to 150 μm, more preferably 2 μm to 100 μm, and particularly preferably 5 μm to 50 μm. The base film and the cover film may be made of the same film material, or different films may be used.

[0111] (Manufacturing method for substrates with cured relief patterns) The present invention provides a method for manufacturing a substrate with a cured relief pattern, (1) A step of applying a photosensitive resin composition, which is one embodiment of the resin composition according to the present invention, onto a substrate to form a photosensitive resin layer (photosensitive resin film) on the substrate, (2) A step of exposing the photosensitive resin layer, (3) A step of developing the photosensitive resin layer after exposure to form a relief pattern, (4) A step of heat-treating the relief pattern to form a hardened relief pattern. Includes.

[0112] The following describes each step.

[0113] (1) A step of applying the photosensitive resin composition according to the present invention onto a substrate to form a photosensitive resin layer on the substrate. In this process, the photosensitive resin composition according to the present invention is applied to a substrate, and if necessary, it is then dried to form a photosensitive resin layer. Conventional application methods for photosensitive resin compositions can be used, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, or spray application using a spray coater.

[0114] A substrate to which a photosensitive resin composition is coated has, for example, metal wiring on its surface. Examples of metal wiring include copper wiring and copper alloy wiring. There are no particular restrictions on the method of forming the metal wiring; for example, conventionally known methods can be used.

[0115] If necessary, the coating film made of the photosensitive resin composition can be dried. Drying methods include, for example, air drying, heating with an oven or hot plate, or vacuum drying. Specifically, when air drying or heating is performed, drying can be carried out at 20°C to 200°C for 1 minute to 1 hour. A photosensitive resin layer can then be formed on the substrate.

[0116] (2) Exposure of the photosensitive resin layer In this process, the photosensitive resin layer formed in step (1) above is exposed to ultraviolet light or the like using an exposure device such as a contact aligner, mirror projection, or stepper, either through a patterned photomask or reticle or directly. Examples of light sources used during exposure include g-line, h-line, i-line, ghi-line broadband, and KrF excimer lasers. The exposure dose is 25 mJ / cm². 2 ~2000 mJ / cm 2 That is preferable.

[0117] Subsequently, if necessary, post-exposure baking (PEB) and / or pre-development baking may be performed using any combination of temperature and time to improve photosensitivity, etc. The baking conditions are preferably in the range of 50°C to 200°C and 10 seconds to 600 seconds, but are not limited to this range as long as they do not impair the properties of the photosensitive resin composition.

[0118] (3) A process of developing the photosensitive resin layer after exposure to form a relief pattern. In this process, the unexposed portion of the photosensitive resin layer after exposure is developed and removed. The development method for developing the photosensitive resin layer after exposure (irradiation) can be selected from any of the conventionally known photoresist development methods, such as the rotary spray method, the paddle method, or the immersion method with ultrasonic treatment. Furthermore, rinsing may be performed after development to remove the developer solution. Additionally, post-development baking may be performed using any combination of temperature and time as needed, for purposes such as adjusting the shape of the relief pattern. Organic solvents are preferred as the developing solution used for development. Examples of preferred organic solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Furthermore, two or more of these solvents, for example, can be used in combination. For rinsing, an organic solvent that is miscible with the developer and has low solubility in the photosensitive resin composition is preferred. Examples of preferred rinsing solutions include methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, toluene, and xylene. Furthermore, two or more of these solvents, for example, can be used in combination.

[0119] (4) A process of heat-treating the relief pattern to form a hardened relief pattern. In this process, the relief pattern obtained by the above development is heated to convert it into a cured relief pattern. Various methods can be selected for heat curing, such as using a hot plate, using an oven, or using a heating oven with a set temperature program. Heating can be carried out, for example, at 130°C to 250°C for 30 minutes to 5 hours. Air may be used as the atmospheric gas during heat curing, or an inert gas such as nitrogen or argon may be used.

[0120] The thickness of the cured relief pattern is not particularly limited, but is preferably 1 μm to 100 μm, and more preferably 2 μm to 50 μm.

[0121] (Semiconductor device) In one embodiment, a semiconductor device is also provided, comprising a semiconductor element and a cured film provided on the upper or lower part of the semiconductor element. The cured film is a cured film formed from the resin composition of the present invention. In one embodiment, the resin composition is a photosensitive resin composition, and the cured film is a cured relief pattern formed from the photosensitive resin composition. The cured relief pattern can be obtained, for example, by steps (1) to (4) in the method for manufacturing a substrate with a cured relief pattern described above. Furthermore, the present invention can also be applied to a method for manufacturing a semiconductor device that uses a semiconductor element as a substrate and includes the above-described method for manufacturing a substrate with a cured relief pattern as part of the process. The semiconductor device of the present invention can be manufactured by forming the cured relief pattern as a surface protective film, an interlayer insulating film, a redistribution insulating film, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure, and combining it with a known method for manufacturing a semiconductor device.

[0122] (Display device) In one embodiment, the display device comprises a display element and a cured film provided on the upper part of the display element, wherein the cured film is a film formed from the resin composition of the present invention. In another embodiment, the resin composition is a photosensitive resin composition, and the cured film is a cured relief pattern formed from the photosensitive resin composition. Here, the cured film (for example, the cured relief pattern) may be laminated in direct contact with the display element, or it may be laminated with another layer in between. For example, the cured film can be a surface protective film, insulating film, and planarization film for TFT (Thin Film Transistor) liquid crystal display elements and color filter elements, a projection for MVA (Multi-domain Vertical Alignment) type liquid crystal display devices, and a partition wall for the cathode of an organic EL (Electro-Luminescence) element.

[0123] In addition to applications in semiconductor devices as described above, the resin composition of the present invention is also useful for applications such as interlayer insulating films for multilayer circuits, cover coats for flexible copper-clad sheets, solder resist films, and liquid crystal alignment films. [Examples]

[0124] The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples.

[0125] The weight-average molecular weight (Mw) shown in the synthesis example below is the result of measurement by gel permeation chromatography (hereinafter abbreviated as GPC in this specification). A GPC instrument (HLC-8320GPC (manufactured by Tosoh Corporation)) was used for the measurement, and the measurement conditions were as follows. • Column: Shodex® KD-805 / Shodex® KD-803 (Showa Denko K.K.) Column temperature: 50℃ ·Flow rate: 1mL / min Eluent: N,N-dimethylformamide (DMF), lithium bromide monohydrate (30mM) / phosphoric acid (30mM) / tetrahydrofuran (1%) • Standard sample: Polyethylene oxide

[0126] The chemical imidation rates shown in the synthesis example below were calculated using the following method. 100 mg of polyimide powder was placed in an NMR sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Chemical Co., Ltd.)), 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) mixture) was added, and the powder was completely dissolved by sonication. The proton NMR of this solution was measured at 500 MHz using an NMR spectrometer (JNM-ECA500) (manufactured by JEOL Ltd.). The chemical imidation rate was determined by using the following formula, with the peak integration value of this proton and the proton peak integration value of the NH group of the amic acid appearing around 9.59 ppm to 11.0 ppm, with the proton derived from the structure that does not change before and after imidation being determined as the reference proton. Chemical imidization rate (%) = (1 - α·x / y) × 100 In the above formula, x is the integrated value of proton peaks derived from the NH group of the amic acid, y is the integrated value of the reference proton peaks, and α is the ratio of the number of reference protons to one NH group proton of the amic acid in the case of polyamic acid (imidization rate of 0%).

[0127] <Synthesis Example 1> Synthesis of polyamic acid (P-1) 9.71 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Mitsuboshi Chemical Industries, Ltd.), 35.38 g of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 0.10 g of 4-methoxyphenol, and 218.35 g of N-ethyl-2-pyrrolidone were dissolved by stirring under air at room temperature. Then, 25.13 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 33.74 g of 9,9-bis[4-(3,4-dicarboxyphenoxy)phenylfluorenidioanhydride (BPF-PA, manufactured by JFE Chemical Corporation)], and 93.58 g of N-ethyl-2-pyrrolidone were added to the system, and after stirring at room temperature for 1 hour, a polyamic acid solution was obtained by stirring at 50°C for 19 hours. The weight-average molecular weight (Mw) of the obtained polyamic acid (P-1), determined by GPC, was 29,554.

[0128] <Synthesis Example 2> Synthesis of Solvent-Soluble Polyimide (P-2) To 415.9 g of polyamic acid (P-1) obtained in Synthesis Example 1, 623.84 g of N-ethyl-2-pyrrolidone, 32.16 g of acetic anhydride, and 5.31 g of triethylamine were added and stirred at room temperature under air for 30 minutes, then stirred at 60°C for 3 hours. This solution was slowly added to 3,770 g of stirred methanol and stirred for 10 minutes, and the resulting precipitate was filtered off. This precipitate was washed with 3,770 g of methanol, and the resulting precipitate was filtered off again. After further washing of this precipitate with 3,770 g of methanol, the resulting precipitate was filtered off and dried under reduced pressure at 50°C to obtain solvent-soluble polyimide (P-2) powder. The chemical imidization rate was 95.3%.

[0129] <Synthesis Example 3> Synthesis of polyamic acid (P-3) 4.62 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Mitsuboshi Chemical Industries, Ltd.), 16.84 g of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 0.05 g of 4-methoxyphenol, and 80.9 g of N-ethyl-2-pyrrolidone were dissolved by stirring under air at room temperature. Then, 11.97 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 16.07 g of 9,9-bis[4-(3,4-dicarboxyphenoxy)phenylfluorenidioanhydride (BPF-PA, manufactured by JFE Chemical Corporation) and 34.65 g of N-ethyl-2-pyrrolidone were added to the system, stirred at room temperature for 1 hour, and then stirred at 40°C for 20 hours to obtain a polyamic acid solution. The weight-average molecular weight (Mw) of the obtained polyamic acid (P-3), determined by GPC, was 32,482.

[0130] <Synthesis Example 4> Synthesis of polyamic acid (P-4) 3,5-Diaminobenzoate 2-(methacryloyloxy)ethyl (BEM-S, manufactured by Mitsuboshi Chemical Co., Ltd.) 31.78g, 4-Octadecyloxy-1,3-phenylenediamine (DAB-C18, manufactured by Wakayama Seika Kogyo Co., Ltd.) 38.81g, 2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane 62.34g, and N-ethyl-2-pyrrolidone 1012.4g were dissolved by stirring under air at room temperature, and then dodecahydro-5,5'-bi-2-benzofuran-1,1'3,3'-tetron (H-BPDA, WeiHai Newera Kesense New 31.57 g of (Materials Inc.) was added and stirred for 40 minutes. Then, 85.00 g of 2,2',3,3',5,5'-hexamethyl-[1,1'-biphenyl]-4,4'-diirbis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate) (TMPBP-TME, Honshu Chemical Industry Co., Ltd.) was added and stirred for 1.5 hours. Then, 48.28 g of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride (SD1100-P, Sabic Inc.) was added and stirred at 50°C for 20 hours to obtain a polyamic acid solution. The weight-average molecular weight (Mw) of the obtained polyamic acid (P-4) determined by GPC was 29,350.

[0131] <Synthesis Example 5> Synthesis of Solvent-Soluble Polyimide (P-5) To 1985.1 g of polyamic acid (P-4) obtained in Synthesis Example 4, 992.6 g of N-ethyl-2-pyrrolidone, 105.22 g of acetic anhydride, and 17.38 g of triethylamine were added and stirred at room temperature under air for 30 minutes, then stirred at 60°C for 3 hours. After dilution with the addition of 992.6 g of N-ethyl-2-pyrrolidone, 1922 g of the solution was taken and slowly added to 4265 g of stirred methanol. After stirring for 10 minutes, the resulting precipitate was filtered off. This precipitate was washed with 1922 g of methanol, and the resulting precipitate was filtered off again. This precipitate was washed again with 1922 g of methanol, and the resulting precipitate was filtered off. Solvent-soluble polyimide (P-5) powder was obtained by drying under reduced pressure at 60°C. The chemical imidization rate was 98.6%.

[0132] <Synthesis Example 6> Synthesis of polyamic acid ester (P-6) 200.00 g (0.68 mol) of 4,4'-biphthalic acid dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a 2-liter four-necked flask, 176.92 g (1.366 mol) of 2-hydroxyethyl methacrylate (manufactured by Sigma-Aldrich Japan GK), 0.74 g (0.007 mol) of hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.), and 600 g of γ-butyrolactone were added, and the mixture was stirred at 23°C. After adding 108.63 g (1.36 mol) of pyridine, the temperature was raised to 50°C, and the mixture was stirred at 50°C for 2 hours to obtain a solution containing the compound represented by the following formula. [ka]

[0133] 82.46 g of the obtained solution and 19.45 g of γ-butyrolactone were placed in a 500 ml four-necked flask. 13.13 g of N,N'-diisopropylcarbodiimide (DIC, manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 30 g of γ-butyrolactone was added dropwise to the reaction mixture over 0.5 hours at approximately 5°C while stirring, and the mixture was stirred for another 0.5 hours. Subsequently, 19.68 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 30 g of N-methyl-2-pyrrolidinone was added dropwise over 2 hours while stirring. The mixture was then heated to approximately 25°C and stirred for 6 hours, after which 4.5 g of ethanol was added and the mixture was stirred for 1 hour. The resulting reaction mixture was added to 1500 g of methanol to produce a precipitate consisting of the crude polymer. The supernatant was decanted to separate the crude polymer, which was then dissolved in 150.0 g of N-methyl-2-pyrrolidinone to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 2250 g of water to precipitate the polymer. The resulting precipitate was filtered off, washed twice with 600 g of methanol, and vacuum-dried to obtain powdered polyamic acid ester (P-6). The weight-average molecular weight (Mw) of the obtained polyamic acid ester (P-6) determined by GPC was 8,016. The yield was 73.6%.

[0134] The main compounds shown in the examples and comparative examples are as follows: • NK ester A-DOD-N:1,10-decanediol diacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) IRGACURE[registered trademark]OXE01: 1,2-Octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime)] (manufactured by BASF Japan Ltd.) IRGANOX[registered trademark]3114: (1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF Japan Ltd.)) • KBM-5103: 3-Acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) ·BMI-689:1H-pyrrole-2,5-zione,1,1'-C 36 -Alkylenbis- (Designer: Molecules Inc.)

[0135] <Example 1> A negative-type photosensitive resin composition was prepared by mixing 1.63 g of solvent-soluble polyimide (P-2) powder obtained in Synthesis Example 2, 3.80 g of N-ethyl-2-pyrrolidone, 0.49 g of NK ester A-DOD-N as a crosslinking agent, 0.081 g of IRGACURE® OXE01 as a photoradical initiator, and 0.024 g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan GK) and dissolving the mixture, then filtering it through a polypropylene filter with a pore size of 5 μm.

[0136] <Example 2> A negative-type photosensitive resin composition was prepared by mixing and dissolving 1.63 g of solvent-soluble polyimide (P-2) powder obtained in Synthesis Example 2, 3.80 g of N-ethyl-2-pyrrolidone, 0.49 g of NK ester A-DOD-N as a crosslinking agent, 0.081 g of IRGACURE® OXE01 as a photoradical initiator, and 0.049 g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan GK), and then filtering the mixture through a polypropylene filter with a pore size of 5 μm.

[0137] <Example 3> A negative-type photosensitive resin composition was prepared by mixing and dissolving 1.63 g of solvent-soluble polyimide (P-2) powder obtained in Synthesis Example 2, 3.80 g of N-ethyl-2-pyrrolidone, 0.49 g of NK ester A-DOD-N as a crosslinking agent, 0.081 g of IRGACURE® OXE01 as a photoradical initiator, and 0.081 g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan GK), and then filtering the mixture through a polypropylene filter with a pore size of 5 μm.

[0138] <Example 4> A negative-type photosensitive resin composition was prepared by mixing and dissolving 1.63 g of solvent-soluble polyimide (P-2) powder obtained in Synthesis Example 2, 3.80 g of N-ethyl-2-pyrrolidone, 0.49 g of NK ester A-DOD-N as a crosslinking agent, 0.081 g of IRGACURE® OXE01 as a photoradical initiator, 0.024 g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan GK), and 0.024 g of 1,2,3-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.), and then filtering the mixture through a polypropylene filter with a pore size of 5 μm.

[0139] <Example 5> A negative-type photosensitive resin composition was prepared by mixing and dissolving 1.63 g of solvent-soluble polyimide (P-2) powder obtained in Synthesis Example 2, 3.80 g of N-ethyl-2-pyrrolidone, 0.49 g of NK ester A-DOD-N as a crosslinking agent, 0.081 g of IRGACURE® OXE01 as a photoradical initiator, 0.024 g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan GK), and 0.024 g of IRGANOX® 3114 as photoradical initiators, and then filtering the mixture through a polypropylene filter with a pore size of 5 μm.

[0140] <Example 6> A negative-type photosensitive resin composition was prepared by mixing and dissolving 1.63 g of solvent-soluble polyimide (P-2) powder obtained in Synthesis Example 2, 3.80 g of N-ethyl-2-pyrrolidone, 0.49 g of NK ester A-DOD-N as a crosslinking agent, 0.081 g of IRGACURE® OXE01 as a photoradical initiator, 0.024 g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan GK), and 0.024 g of 5-methyl-1H-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.), and then filtering the mixture through a polypropylene filter with a pore size of 5 μm.

[0141] <Example 7> A negative-type photosensitive resin composition was prepared by mixing and dissolving 1.63 g of solvent-soluble polyimide (P-2) powder obtained in Synthesis Example 2, 3.80 g of N-ethyl-2-pyrrolidone, 0.49 g of NK ester A-DOD-N as a crosslinking agent, 0.081 g of IRGACURE® OXE01 as a photoradical initiator, 0.049 g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan GK), and 0.033 g of KBM-5103, and then filtering the mixture through a polypropylene filter with a pore size of 5 μm.

[0142] <Example 8> A negative-type photosensitive resin composition was prepared by mixing and dissolving 1.63 g of solvent-soluble polyimide (P-2) powder obtained in Synthesis Example 2, 3.80 g of N-ethyl-2-pyrrolidone, 0.49 g of NK ester A-DOD-N as a crosslinking agent, 0.081 g of IRGACURE® OXE01 as a photoradical initiator, 0.049 g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan GK), and 0.024 g of 5-methyl-1H-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.), and then filtering the mixture through a polypropylene filter with a pore size of 5 μm.

[0143] <Example 9> A negative-type photosensitive resin composition was prepared by mixing and dissolving 1.63 g of solvent-soluble polyimide (P-2) powder obtained in Synthesis Example 2, 3.80 g of N-ethyl-2-pyrrolidone, 0.49 g of NK ester A-DOD-N as a crosslinking agent, 0.081 g of IRGACURE® OXE01 as a photoradical initiator, 0.049 g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan GK), and 0.024 g of IRGANOX® 3114. The mixture was then filtered using a polypropylene filter with a pore size of 5 μm.

[0144] <Example 10> A negative-type photosensitive resin composition was prepared by mixing and dissolving 1.63 g of solvent-soluble polyimide (P-2) powder obtained in Synthesis Example 2, 3.80 g of N-ethyl-2-pyrrolidone, 0.49 g of NK ester A-DOD-N as a crosslinking agent, 0.081 g of IRGACURE® OXE01 as a photoradical initiator, and 0.024 g of CBT-SG (a mixture of 4-carboxybenzotriazole and 5-carboxybenzotriazole, manufactured by Johoku Chemical Industry Co., Ltd.), and then filtering the mixture through a polypropylene filter with a pore size of 5 μm.

[0145] <Example 11> A negative-type photosensitive resin composition was prepared by mixing and dissolving 1.63 g of solvent-soluble polyimide (P-2) powder obtained in Synthesis Example 2, 3.80 g of N-ethyl-2-pyrrolidone, 0.49 g of NK ester A-DOD-N as a crosslinking agent, 0.081 g of IRGACURE® OXE01 as a photoradical initiator, and 0.049 g of CBT-SG (a mixture of 4-carboxybenzotriazole and 5-carboxybenzotriazole, manufactured by Johoku Chemical Industry Co., Ltd.), and then filtering the mixture through a polypropylene filter with a pore size of 5 μm.

[0146] <Example 12> A negative-type photosensitive resin composition was prepared by mixing and dissolving 1.63 g of solvent-soluble polyimide (P-2) powder obtained in Synthesis Example 2, 3.80 g of N-ethyl-2-pyrrolidone, 0.49 g of NK ester A-DOD-N as a crosslinking agent, 0.081 g of IRGACURE® OXE01 as a photoradical initiator, and 0.024 g of CBT-5 (5-carboxybenzotriazole, manufactured by Johoku Chemical Industry Co., Ltd.), and then filtering the mixture through a polypropylene filter with a pore size of 5 μm.

[0147] <Example 13> A negative-type photosensitive resin composition was prepared by mixing and dissolving 1.63 g of solvent-soluble polyimide (P-2) powder obtained in Synthesis Example 2, 3.80 g of N-ethyl-2-pyrrolidone, 0.49 g of NK ester A-DOD-N as a crosslinking agent, 0.081 g of IRGACURE® OXE01 as a photoradical initiator, and 0.049 g of CBT-5 (5-carboxybenzotriazole, manufactured by Johoku Chemical Industry Co., Ltd.), and then filtering the mixture through a polypropylene filter with a pore size of 5 μm.

[0148] <Example 14> A negative-type photosensitive resin composition was prepared by mixing 22.44 g of a solution (solid content concentration: 30% by mass) containing the polyamic acid (P-3) obtained in Synthesis Example 3 with 2.02 g of NK ester A-DOD-N as a crosslinking agent, 0.34 g of IRGACURE® OXE01 as a photoradical initiator, and 0.20 g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan GK) and dissolving the mixture, then filtering it through a polypropylene filter with a pore size of 5 μm.

[0149] <Example 15> To 3.70 g of the solvent-soluble polyimide (P-5) obtained in Synthesis Example 5, 0.56 g of NK ester A-DOD-N was added as a crosslinking agent, 0.15 g of IRGACURE® OXE01 was added as a photoradical initiator, and 0.056 g of CBT-SG (a mixture of 4-carboxybenzotriazole and 5-carboxybenzotriazole, manufactured by Johoku Chemical Industry Co., Ltd.), 0.074 g of KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.), 0.22 g of BMI-689 (manufactured by Designer Molecules Inc.) as a bismaleimide compound, 3.67 g of N-ethyl-2-pyrrolidone, 4.90 g of γ-butyrolactone, and 3.67 g of cyclohexanone were mixed and dissolved. The mixture was then filtered using a polypropylene filter with a pore size of 5 μm to prepare a negative-type photosensitive resin composition.

[0150] <Example 16> A negative-type photosensitive resin composition was prepared by mixing and dissolving 6.34 g of the polyamic acid ester (P-6) powder obtained in Synthesis Example 6, 16.25 g of N-ethyl-2-pyrrolidone, 1.90 g of NK ester A-DOD-N as a crosslinking agent, 0.317 g of IRGACURE® OXE01 as a photoradical initiator, and 0.19 g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan GK), and then filtering the mixture through a polypropylene filter with a pore size of 5 μm.

[0151] <Comparative Example 1> 1.63 g of a powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80 g of N-ethyl-2-pyrrolidone, 0.49 g of NK Ester A-DOD-N as a crosslinking agent, and 0.081 g of IRGACURE [Registered Trademark] OXE01 as a photoradical initiator were mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 µm to prepare a negative photosensitive resin composition.

[0152] <Comparative Example 2> 1.63 g of a powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80 g of N-ethyl-2-pyrrolidone, 0.49 g of NK Ester A-DOD-N as a crosslinking agent, 0.081 g of IRGACURE [Registered Trademark] OXE01 as a photoradical initiator, and 0.033 g of KBM-5103 were mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 µm to prepare a negative photosensitive resin composition.

[0153] <Comparative Example 3> 1.63 g of a powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80 g of N-ethyl-2-pyrrolidone, 0.49 g of NK Ester A-DOD-N as a crosslinking agent, 0.081 g of IRGACURE [Registered Trademark] OXE01 as a photoradical initiator, and 0.024 g of IRGANOX [Registered Trademark] 3114 were mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 µm to prepare a negative photosensitive resin composition.

[0154] <Comparative Example 4> 1.63 g of a powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80 g of N-ethyl-2-pyrrolidone, 0.49 g of NK Ester A-DOD-N as a crosslinking agent, 0.081 g of IRGACURE [Registered Trademark] OXE01 as a photoradical initiator, and 0.024 g of 5-methyl-1H-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 µm to prepare a negative photosensitive resin composition.

[0155] <Comparative Example 5> 1.63 g of a powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80 g of N-ethyl-2-pyrrolidone, 0.49 g of NK Ester A-DOD-N as a crosslinking agent, 0.081 g of IRGACURE[Registered Trademark] OXE01 as a photoradical initiator, and 0.049 g of 5-methyl-1H-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 μm, thereby preparing a negative-type photosensitive resin composition.

[0156] <Comparative Example 6> 1.63 g of a powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80 g of N-ethyl-2-pyrrolidone, 0.49 g of NK Ester A-DOD-N as a crosslinking agent, 0.081 g of IRGACURE[Registered Trademark] OXE01 as a photoradical initiator, 0.024 g of 5-methyl-1H-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.24 g of IRGANOX[Registered Trademark] 3114 were mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 μm, thereby preparing a negative-type photosensitive resin composition.

[0157] <Comparative Example 7> 1.63 g of a powder of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, 3.80 g of N-ethyl-2-pyrrolidone, 0.49 g of NK Ester A-DOD-N as a crosslinking agent, 0.081 g of IRGACURE[Registered Trademark] OXE01 as a photoradical initiator, 0.049 g of 5-methyl-1H-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.24 g of IRGANOX[Registered Trademark] 3114 were mixed and dissolved, and then filtered using a polypropylene filter with a pore diameter of 5 μm, thereby preparing a negative-type photosensitive resin composition.

[0158] <Comparative Example 8> A negative-type photosensitive resin composition was prepared by mixing and dissolving 1.63 g of solvent-soluble polyimide (P-2) powder obtained in Synthesis Example 2, 3.80 g of N-ethyl-2-pyrrolidone, 0.49 g of NK ester A-DOD-N as a crosslinking agent, 0.081 g of IRGACURE® OXE01 as a photoradical initiator, and 0.024 g of 2,4-diamino-6-butylamino-1,3,5-triazine (manufactured by Tokyo Chemical Industry Co., Ltd.), and then filtering the mixture through a polypropylene filter with a pore size of 5 μm.

[0159] <Comparative Example 9> A negative-type photosensitive resin composition was prepared by mixing and dissolving 1.63 g of solvent-soluble polyimide (P-2) powder obtained in Synthesis Example 2, 3.80 g of N-ethyl-2-pyrrolidone, 0.49 g of NK ester A-DOD-N as a crosslinking agent, 0.081 g of IRGACURE® OXE01 as a photoradical initiator, and 0.024 g of 2,4-diamino-6-diallylamino-1,3,5-triazine (manufactured by Tokyo Chemical Industry Co., Ltd.), and then filtering the mixture through a polypropylene filter with a pore size of 5 μm.

[0160] <Comparative Example 10> A negative-type photosensitive resin composition was prepared by mixing and dissolving 1.63 g of solvent-soluble polyimide (P-2) powder obtained in Synthesis Example 2, 3.80 g of N-ethyl-2-pyrrolidone, 0.49 g of NK ester A-DOD-N as a crosslinking agent, 0.081 g of IRGACURE® OXE01 as a photoradical initiator, and 0.024 g of 6-(dibutylamino)-1,3,5-triazine-2,4-dithiol (manufactured by Tokyo Chemical Industry Co., Ltd.), and then filtering the mixture through a polypropylene filter with a pore size of 5 μm.

[0161] [Evaluation of adhesion strength] An 8-inch silicon wafer with a 1.5 μm thickness of copper deposited on it was cut into 1 cm x 1 cm pieces. This silicon wafer was washed with 10% sulfuric acid for 1 minute, then washed with pure water for 30 seconds, dried, and coated with the negative-type photosensitive resin compositions prepared in Examples 1 to 16 and Comparative Examples 1 to 10. A 22 μm photosensitive resin film was formed on the substrate (the silicon wafer with the deposited copper) by pre-firing at 115°C for 270 seconds. Next, an i-line aligner (PLA-501, manufactured by Canon Inc.) was used to measure 500 mJ / cm². 2 After full-surface exposure, the substrates were baked in a high-temperature clean oven (CLH-21CD(V)-S, Koyo Thermo Systems Co., Ltd.) in a nitrogen atmosphere at 230°C for 2 hours. Next, as a reliability test, the substrates were subjected to 125°C for 24 hours and 30°C for 168 hours in air, followed by a reflow process of 260°C for 1 second, including heating, three times in a nitrogen atmosphere. Finally, they underwent a high-accelerated life test (EHS-212MD, ESPEC Corporation) at 130°C, 85% humidity, and 230kPa vapor pressure for 192 hours. Subsequently, epoxy adhesive-backed stud pins were bonded to the resin film surface, and stud pull peel strength measurements were performed using ROMURUS V (Quad Group, USA) to evaluate the adhesion between the Cu surface and the resin film. Separately, substrates that had not undergone reliability testing (substrates with the resin film formed on them) were also prepared, and stud pull peel strength measurements were performed on each in the same manner. The delamination interface after the test was observed. If delamination occurred due to cohesive failure of the epoxy adhesive both before and after the reliability test, or if delamination occurred at the interface between the epoxy adhesive and the resin film surface, it was marked as "○" indicating good adhesion. If delamination occurred at the interface between the photosensitive resin film and Cu in either case before or after the reliability test, it was marked as "×" indicating poor adhesion. The results are shown in Tables 1-1 and 1-2.

[0162] [Evaluation of antioxidant capacity] A test substrate (1 cm × 1 cm) with a PI (polyimide) base and Cu wiring with a height of 5 μm and a width of 10 μm mL / S was washed with 10% sulfuric acid for 1 minute, then washed with pure water for 30 seconds and dried. The negative-type photosensitive resin compositions prepared in Examples 1 to 16 and Comparative Examples 1 to 10 were applied to this substrate under the same conditions as in the [adhesion strength evaluation], and a photosensitive resin film was formed by pre-baking at 115°C for 270 seconds. Next, using an i-line aligner (PLA-501, manufactured by Canon Inc.), 500 mJ / cm² was administered. 2 The entire surface was exposed to light. Next, it was baked in a high-temperature clean oven (CLH-21CD(V)-S, Koyo Thermo Systems Co., Ltd.) in a nitrogen atmosphere at 230°C for 2 hours. Then, as a reliability test, it was subjected to 125°C for 24 hours and 30°C for 168 hours in air, and as a reflow treatment, it was performed three times in a nitrogen atmosphere with heating up to 260°C for 1 second. Finally, it was treated in a high-accelerated life test (EHS-212MD, ESPEC Corporation) at 130°C, 85% humidity, vapor pressure 230kPa for 192 hours, after which the Cu wiring of the evaluation test substrate was cut using FIB-SEM (Nippon FEI Co., Ltd.) and the cross-section was observed with SEM. If the thickness of the oxide film formed on the Cu wiring in the reliability test was thinner than that of Comparative Example 1 (73.7nm), it was indicated as a good result with "○", and if it was thicker, it was indicated as a bad result with "×". The results are shown in Table 1.

[0163] [Electrical Characteristics Evaluation] The negative-type photosensitive resin compositions prepared in Examples 1 to 15 and Comparative Examples 1 to 10 were spin-coated onto a 4-inch silicon wafer coated with 20 μm thick aluminum foil, and then baked on a hot plate at 115°C for 270 seconds to form a photosensitive resin film of approximately 22 μm on the aluminum foil. An i-line aligner (PLA-501, manufactured by Canon Inc.) was used to apply 500 mJ / cm² to the resulting photosensitive resin film on the wafer. 2After full-surface exposure, the aluminum foil was fired in a high-temperature clean oven (CLH-21CD(V)-S, Koyo Thermo Systems Co., Ltd.) in a nitrogen atmosphere at 230°C for 2 hours. Furthermore, the fired aluminum foil was immersed in 6N hydrochloric acid to dissolve the aluminum foil and obtain a film. The obtained film was dried, and the dielectric loss tangent at 60 GHz was measured using a split-cylinder resonator. The measurement conditions for the dielectric loss tangent were as follows. • Measurement method: Split cylinder resonator • Vector network analyzer: FieldFox N9926A (manufactured by Keysight Technologies, Inc.) ·Resonator: CR-760 (manufactured by EM Lab Co., Ltd.) ·Measurement frequency: approx. 60GHz The dielectric loss tangent values ​​obtained in this measurement were marked as good ("○") if they were less than or equal to those of Comparative Example 1 (0.0087), and as poor ("×") if they were greater than those of Comparative Example 1. The results are shown in Tables 1-1 and 1-2.

[0164] [Table 1-1]

[0165] [Table 1-2]

[0166] From the results in Tables 1-1 and 1-2, the resin films obtained from the negative-type photosensitive resin compositions of Examples 1 to 16 all exhibited good adhesion. Furthermore, the Cu wiring on which the resin films obtained from the negative-type photosensitive resin compositions of Examples 1 to 16 were formed showed a thinner oxide film thickness after reliability testing than the Cu wiring on which the resin film obtained from the negative-type photosensitive resin composition of Comparative Example 1, confirming better reliability. In addition, the films obtained from the negative-type photosensitive resin compositions of Examples 1 to 15 showed a dielectric loss tangent lower than or equal to that of the film obtained from the negative-type photosensitive resin composition of Comparative Example 1.

Claims

1. A resin composition comprising a polyimide having structural units represented by the following formulas (1-a) and (1-b-1), a compound represented by the following formula (A), and a solvent, wherein the polyimide has a divalent organic group represented by the following formula (9-a). 【Chemistry 1】 [In formula (A), R ａ R represents a hydrogen atom, a hydroxyl group, a methylol group, or an alkyl group having 1 to 30 carbon atoms. ｂ [where m represents an alkyl group with 1 to 30 carbon atoms, and n represents an integer from 0 to 3, with the maximum sum of m and n being 4.] 【Chemistry 2】 [In formulas (1-a) and (1-b-1), Ar １ represents a tetravalent organic group represented by the following formula (4), X １１ This represents a divalent organic group having a photopolymerizable group. 【Transformation 3】 [In formula (9-a), V 1 represents a direct bond, ether bond, ester bond, amide bond, urethane bond, or urea bond; W 1 represents an oxygen atom or an NH group; R 15 represents a direct bond or an alkylene group having 2 to 6 carbon atoms, which may be substituted with a hydroxyl group; R 16 represents a hydrogen atom or a methyl group; and * represents a bond.] 【Chemistry 4】 [In formula (4), X1 and X2 each independently represent a direct bond, an ether bond (-O-), an ester bond (-COO-), a thioether bond (-S-), or a sulfonyl bond (-SO2-). Ra1 and Ra2 each represent an alkyl group having 1 to 6 carbon atoms, which may be independently substituted. Z1 represents a divalent organic group represented by the following formula (5-a), formula (5-b), or formula (5-c). n1 and n2 each independently represent integers between 0 and 3. If there are multiple R a1s, they may be the same or different. If there are multiple R a2s, they may be the same or different. * represents a bonding operation. 【Transformation 5】 [In formula (5-a), R3 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and m1 represents an integer from 0 to 4. When m1 is 2 or greater, R3 may be the same or different. In formula (5-b), Z2 represents a direct bond or a divalent organic group represented by the following formula (6-a) or formula (6-b), R4 and R5 each independently represent an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and m2 and m3 each independently represent an integer from 0 to 4. When m² is 2 or greater, R₄ may be the same or different. When m3 is 2 or greater, R5 may be the same or different. In formula (5-c), R 6 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and m 4 represents an integer from 0 to 6. When m 4 is 2 or greater, R 6 may be the same or different. * represents a bonding operation. 【Transformation 6】 [In formula (6-a), R7 and R8 each independently represent an alkyl group having 1 to 6 carbon atoms, which may be substituted with a hydrogen atom or a halogen atom. In formula (6-b), R9 and R10 each independently represent an alkylene group having 1 to 6 carbon atoms or an arylene group having 6 to 12 carbon atoms that may be substituted. * represents a bonding operation.

2. The resin composition according to claim 1, wherein in formula (4), Z1 represents a divalent organic group represented by formula (5-b).

3. V in the above formula (9-a) １ This represents an ester bond, and furthermore, W １ The resin composition according to claim 1, wherein represents an oxygen atom.

4. R in formula (9-a) １５ The resin composition according to claim 1, wherein is a 1,2-ethylene group.

5. R in formula (A) ａ The resin composition according to claim 1, wherein represents a hydrogen atom.

6. The resin composition according to claim 1, wherein m in formula (A) is 0.

7. The resin composition according to claim 1, wherein the compound represented by formula (A) comprises at least one of 1H-benzotriazole-5-carboxylic acid and 1H-benzotriazole-4-carboxylic acid.

8. The resin composition according to claim 1, further comprising a photoradical polymerization initiator.

9. The resin composition according to claim 1, further comprising a crosslinking compound.

10. The resin composition according to claim 1, for use in forming an insulating film.

11. The resin composition according to claim 1, which is a photosensitive resin composition.

12. The resin composition according to claim 1, which is a negative-type photosensitive resin composition.

13. A resin film which is a fired product of a coating film of the resin composition according to any one of claims 1 to 12.

14. The resin film according to claim 13, which is an insulating film.

15. A photosensitive resist film comprising a base film, a photosensitive resin layer formed from the resin composition described in claim 11 or 12, and a cover film.

16. (1) A step of applying the resin composition according to claim 11 or 12 onto a substrate to form a photosensitive resin layer on the substrate, (2) A step of exposing the photosensitive resin layer, (3) A step of developing the photosensitive resin layer after exposure to form a relief pattern, (4) A step of heat-treating the relief pattern to form a hardened relief pattern, A method for manufacturing a substrate with a cured relief pattern, including the method described above.

17. The method for manufacturing a substrate with a cured relief pattern according to claim 16, wherein in step (1) above, the resin composition is applied to the substrate having metal wiring on its surface.

18. The method for manufacturing a substrate with a cured relief pattern according to claim 16, wherein the developing solution used for the development is an organic solvent.

19. A substrate with a cured relief pattern manufactured by the method described in claim 16.

20. A semiconductor device comprising a semiconductor element and a cured film provided on the upper or lower part of the semiconductor element, wherein the cured film is a cured film formed from the resin composition described in any one of claims 1 to 12.

21. The resin composition is a photosensitive resin composition, The semiconductor device according to claim 20, wherein the cured film is a cured relief pattern formed from the photosensitive resin composition.

Images