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

resin composition

[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 having a cured relief pattern, and a semiconductor device.

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

[0003] When an insulating film or the like is formed from a resin composition containing a polyimide resin, the adhesion may be reduced if the insulating film or the like is formed on a metal wiring (e.g., copper wiring, copper alloy wiring, etc.). Therefore, in order to suppress the reduction in adhesion, it has been proposed to include triazole or a derivative thereof in a photosensitive polyimide resin composition (Patent Document 2).

[0004] Furthermore, when an insulating film or the like is formed from a resin composition containing a polyimide resin, if the insulating film or the like is formed on a metal wiring (e.g., 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 add an antioxidant such as a phenolic antioxidant to the polyimide resin composition (Patent Document 3).

[0005] JP 2012-194520 A JP 2005-010360 A International Publication No. 2015 / 020020 Pamphlet

[0006] In recent years, semiconductor devices have become increasingly sensitive to the need to transmit and process large amounts of information at high speeds, leading to an increase in the frequency of electrical signals. Because high-frequency electrical signals are prone to attenuation, it is necessary to reduce transmission loss. Therefore, resins used in semiconductor devices are required to have a low dielectric dissipation factor.

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

[0008] In view of the above circumstances, an object of the present invention is to provide a resin composition that can provide a film having excellent adhesion, excellent antioxidant properties, and a low dielectric loss tangent on a substrate having metal wiring on its surface; a resin film obtained from the resin composition; a photosensitive resist film using the resin composition; a method for producing a substrate having a cured relief pattern; and a semiconductor device.

[0009] As a result of extensive research to achieve the above object, the present inventors have found 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 can form a film having excellent adhesion, excellent antioxidant properties, and a low dielectric loss tangent on a substrate having metal wiring on the surface thereof, and have completed the present invention.

[0010] [1] A resin composition comprising at least one resin selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof, a compound represented by the following formula (A), and a solvent: [In formula (A), R ａ represents a hydrogen atom, a hydroxyl group, a methylol group, or an alkyl group having 1 to 30 carbon atoms. ｂ represents an alkyl group having 1 to 30 carbon atoms. m represents an integer of 0 to 3, n represents an integer of 1 to 4, and 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 precursors thereof. [3] The resin composition according to [1] or [2], wherein the resin is a polyimide having structural units represented by the following formulas (1-a) and (1-b-1) or a polyimide precursor having structural units represented by the following formulas (3) and (1-b-2). [In formula (1-a) and formula (1-b-1), Ar １ represents a tetravalent organic group, and X １１ represents a divalent organic group having a photopolymerizable group. ３ represents a tetravalent organic group, L １ and L ２ each independently represents a monovalent organic group; X １２ represents a divalent organic group, L１ , L ２ and X １２ At least one of the resins 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): [In formula (9-a), V １ represents a direct bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a 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.] [5] V in the formula (9-a) １ represents an ester bond, and W １ [6] The resin composition according to [4], wherein R in the formula (9-a) represents an oxygen atom. １５ [7] The resin composition according to [4] or [5], wherein R in formula (A) represents a 1,2-ethylene group. ａrepresents a hydrogen atom. [8] The resin composition according to any one of [1] to [7], wherein m in formula (A) represents 0. [9] The resin composition according to any one of [1] to [8], wherein the compound represented by 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 photoradical 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 used 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 having a base film, a photosensitive resin layer formed from the resin composition according to

[13] or

[14] , and a cover film.

[18] A method for producing a substrate having a cured relief pattern, comprising: (1) applying the resin composition according to

[13] or

[14] onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer; (3) developing the exposed photosensitive resin layer to form a relief pattern; and (4) heat-treating the relief pattern to form a cured relief pattern.

[19] A method for producing a substrate having a cured relief pattern according to

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

[20] A method for producing a substrate having a cured relief pattern according to

[18] or

[19] , wherein the developer used for the development is an organic solvent.

[21] A substrate having a cured relief pattern produced by the method according to any one of

[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, the cured film being a cured film formed from the resin composition according to any one of [1] to

[14] .

[23] The semiconductor device according to

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

[0011] According to the present invention, there are provided a resin composition that can be used to form a film having excellent adhesion, excellent antioxidant properties, and a low dielectric tangent on a substrate having metal wiring on its surface; a resin film obtained from the resin composition; a photosensitive resist film using the resin composition; a method for producing a substrate having a cured relief pattern; and a semiconductor device.

[0012] (Resin Composition) The resin composition of the present invention contains at least one resin selected from the group consisting of polyimide, polybenzoxazole and precursors thereof, a compound represented by formula (A), and a solvent.

[0013] <Polyimide, etc.> The resin composition contains at least one resin selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof (hereinafter, may be referred to as "polyimide, etc.").

[0014] From the viewpoint of imparting photosensitivity when the resin composition is used as a photosensitive resin composition, the polyimide or the like preferably has a photopolymerizable group, more preferably has a polymerizable unsaturated group, even more preferably has a (meth)acryloyl group, and particularly preferably has a divalent organic group represented by the following formula (9-a): [In formula (9-a), V １ 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—), and 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.

[0015] <<Polyimide and Precursor Thereof>> Examples of polyimide and precursors thereof include polyimide, polyamic acid, and polyamic acid ester.

[0016] An example of a polyimide is polyimide (1) below. An example of a polyamic acid is polyamic acid (2) below. An example of a polyamic acid ester is polyamic acid ester (3) below. 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 formulas (2) and (1-b). Polyamic acid ester (3) is a polyamic acid ester having structural units represented by the following formulas (3) and (1-b).

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

[0018] [In formula (2), Ar ２ represents a tetravalent organic group.

[0019] [In formula (3), Ar ３ represents a tetravalent organic group, L １ , and L ２ each independently represents a monovalent organic group.

[0020] An example of the polyimide is a polyimide having structural units represented by formula (1-a) and the following formula (1-b-1). An example of the polyimide precursor is a polyimide precursor having structural units represented by formula (3) and the following formula (1-b-2). However, in the polyimide precursor, L １ , L ２ and X １２ At least one of them has a photopolymerizable group. [In formula (1-b-1), X １１ represents a divalent organic group having a photopolymerizable group. １２represents a divalent organic group.

[0021] <<<Ar １ , Ar ２ , and Ar ３ >>> Ar １ , Ar ２ , and Ar ３ represents a tetravalent organic group. There is no particular limitation on the tetravalent organic group, and examples thereof include the tetravalent organic group derived from aliphatic tetracarboxylic dianhydride, the tetravalent organic group derived from alicyclic tetracarboxylic dianhydride, and the tetravalent organic group derived from aromatic tetracarboxylic dianhydride. As the tetravalent organic group, a tetravalent organic group having three or more aromatic rings is preferred, since it can obtain a film with a lower dielectric loss tangent.

[0022] Ar １ , Ar ２ , and Ar ３ The number of aromatic rings contained in the film is preferably 3 or more, more preferably 4 or more, in order to obtain a film having a lower dielectric loss tangent. The upper limit of the number of aromatic rings is not particularly limited, but may be, for example, 8 or less, or 6 or less.

[0023] Regarding the counting of aromatic rings in "three or more aromatic rings," polycyclic aromatic rings formed by condensing 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 counted as two aromatic rings because it is not a condensed ring. And a perylene ring is counted as two aromatic rings. Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles.

[0024] Ar １ , Ar ２ , and Ar ３ From the viewpoint of suitably obtaining the effects of the present invention, it is preferable that R represents a tetravalent organic group represented by the following formula (4). [In formula (4), X １ and X ２are each independently 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 (-SO ２ -) represents. ａ１ and R ａ２ each independently represents an alkyl group having 1 to 6 carbon atoms which may be substituted. １ represents a divalent organic group represented by the following formula (5-a), (5-b), or (5-c). n1 and n2 each independently represent an integer of 0 to 3. R ａ１ If there are multiple R ａ１ may be the same or different. ａ２ If there are multiple R ａ２ may be the same or different. * represents a bond.]

[0025] R in formula (4) ａ１ and R ａ２ Examples of the optionally substituted alkyl group having 1 to 6 carbon atoms in the formula (I) 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. In this specification, unless otherwise specified, alkyl and alkylene groups may be linear, branched, or cyclic, or may be a combination of two or more of these. Examples of substituents in the optionally substituted alkyl group having 1 to 6 carbon atoms include halogen atoms, hydroxy groups, mercapto groups, carboxy 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 the "1 to 6 carbon atoms" in the "optionally substituted alkyl group having 1 to 6 carbon atoms" refers to the number of carbon atoms in the "alkyl group" excluding the substituent. Furthermore, the number of substituents is not particularly limited.

[0026] [In formula (5-a), R ３represents 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; m １ represents an integer of 0 to 4. １ When is 2 or more, R ３ may be the same or different. ２ represents a direct bond or a divalent organic group represented by the following formula (6-a) or (6-b), and R ４ and R ５ each independently 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; m ２ and m ３ Each independently represents an integer of 0 to 4. ２ When is 2 or more, R ４ may be the same or different. ３ When is 2 or more, R ５ may be the same or different. 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; m ４ represents an integer of 0 to 6. ４ When is 2 or more, R ６ may be the same or different. * represents a bond.]

[0027] [In formula (6-a), R ７ , and R ８ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom. ９ , and R １０ each independently represents an optionally substituted alkylene group having 1 to 6 carbon atoms or an optionally substituted arylene group having 6 to 12 carbon atoms. * represents a bond.]

[0028] Z １ From the viewpoint of suitably obtaining the effects of the present invention, it is preferable that represents a divalent organic group represented by formula (5-b).

[0029] R ７and R ８ Examples of the alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom in the above formula include an alkyl group having 1 to 6 carbon atoms and a halogenated alkyl group 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. Examples of the halogen atom in the halogenated alkyl group having 1 to 6 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogenation in the halogenated alkyl group having 1 to 6 carbon atoms may be partial or complete.

[0030] R ９ and R １０ Examples of the substituent in the optionally substituted alkylene group having 1 to 6 carbon atoms in the formula (I) 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 thioxy group, and an alkoxy group having 1 to 6 carbon atoms. Examples of the optionally substituted alkylene group having 1 to 6 carbon atoms include an alkylene group having 1 to 6 carbon atoms and a halogenated alkylene group having 1 to 6 carbon atoms. Examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a propylene group, and a butylene group. Note that the "1 to 6 carbon atoms" in the "optionally substituted alkylene group having 1 to 6 carbon atoms" refers to the number of carbon atoms in the "alkylene group" excluding the substituent. Furthermore, the number of substituents is not particularly limited.

[0031] R ９ and R １０Examples of the substituent in the optionally substituted arylene group having 6 to 10 carbon atoms in the formula (I) include a halogen atom, an optionally halogenated alkyl group having 1 to 6 carbon atoms, and an optionally halogenated alkoxy group having 1 to 6 carbon atoms. The halogenation may be partial or complete. Examples of the arylene group include a phenylene group and a naphthylene group. The "6 to 10 carbon atoms" in the "optionally substituted arylene group having 6 to 10 carbon atoms" refers to the number of carbon atoms in the "arylene group" excluding the substituent. The number of substituents is not particularly limited.

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

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

[0034] R ３１ ~R ３３Specific examples of the alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom in the formula (I) include an alkyl group having 1 to 6 carbon atoms and a halogenated alkyl group 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. Examples of the halogen atom in the halogenated alkyl group having 1 to 6 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogenation in the halogenated alkyl group having 1 to 6 carbon atoms may be partial or complete. R ３１ ~R ３３ Specific examples of the alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom in the formula (I) include an alkoxy group formed from an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom.

[0035] Ar １ , Ar ２ , and Ar ３ Examples of the tetravalent organic group include the tetravalent organic group represented by the following formula: In the formula, * represents a bond.

[0036] Also, Ar １ , Ar ２ , and Ar ３ The group may be, for example, a tetravalent organic group represented by the following formula: In the formula, * represents a bond.

[0037] <<<X, X １１ , and X １２ >>> X represents a divalent organic group. X represents, for example, a divalent aromatic group having a photopolymerizable group. X １１ represents a divalent organic group having a photopolymerizable group. １１ represents, for example, a divalent aromatic group having a photopolymerizable group. １２ represents a divalent organic group. １２ has, for example, a photopolymerizable group. １２ represents, for example, a divalent organic group having a photopolymerizable group. １２represents, for example, a divalent aromatic group having a photopolymerizable group.

[0038] Examples of the photopolymerizable group include a radically polymerizable group, a cationically polymerizable group, and an anionically polymerizable group. Among these, the radically polymerizable group is preferred. Examples of the radically polymerizable group include an acryloyl group, a methacryloyl group, a propenyl ether group, a vinyl ether group, and a vinyl group.

[0039] Examples of the aromatic ring in the divalent aromatic group having a photopolymerizable group include a benzene ring, a naphthalene ring, and an anthracene ring.

[0040] The 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] The divalent aromatic group having a photopolymerizable group is preferably a divalent organic group represented by the following formula (9-a). [In formula (9-a), V １ 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—), and 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.

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

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

[0044] V １ preferably represents an ester bond (—COO—). １ preferably represents an oxygen atom. １５ preferably represents a 1,2-ethylene group.

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

[0046] X and X １２ is preferably a divalent organic group having three or more aromatic rings, since this allows a film with a lower dielectric loss tangent to be obtained. The divalent organic group having three or more aromatic rings herein refers to an organic group different from the divalent aromatic group having the photopolymerizable group described above.

[0047] The 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 it is three or more, and may be, for example, four or more. The upper limit of the number of aromatic rings is not particularly limited, and may be, for example, 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). [In formula (13), X ２１ and X ２２ are each independently 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 (-SO ２ -) represents. ２１ and R ２２ Y each independently represents an alkyl group having 1 to 6 carbon atoms which may be substituted. ２０ represents a divalent organic group represented by the above formula (5-a), (5-b), or (5-c). n21 and n22 each independently represent an integer of 0 to 4. R ２１ If there are multiple R ２１ may be the same or different. ２２ If there are multiple R ２２ may be the same or different. * represents a bond.]

[0050] R in formula (13) ２１ and R ２２Examples of the optionally substituted alkyl group having 1 to 6 carbon atoms in the formula (I) 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. In this specification, unless otherwise specified, alkyl and alkylene groups may be linear, branched, or cyclic, or may be a combination of two or more of these. Examples of substituents in the optionally substituted alkyl group having 1 to 6 carbon atoms include halogen atoms, hydroxy groups, mercapto groups, carboxy 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 the "1 to 6 carbon atoms" in the "optionally substituted alkyl group having 1 to 6 carbon atoms" refers to the number of carbon atoms in the "alkyl group" excluding the substituent. Furthermore, the number of substituents is not particularly limited.

[0051] Examples of the divalent organic group having three or more aromatic rings include divalent organic groups represented by the following formula: In the formula, * represents a bond.

[0052] Other divalent organic groups include, for example, divalent organic groups represented by the following formulas: These divalent organic groups are, for example, residues obtained by removing two amino groups from a diamine. In the formula, * represents a bond.

[0053] <<<L １ and L ２ >>> L １ , and L ２each independently represents a monovalent organic group. Examples of the monovalent organic group include an alkyl group having 1 to 30 carbon atoms. Examples of the alkyl group having 1 to 30 carbon atoms include a linear alkyl group, a branched alkyl group, and an alicyclic alkyl group. Examples of the linear alkyl group 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 (arachyl), heneicosyl, docosyl (behenyl), tricosyl, tetracosyl (lignoceryl), pentacosyl, hexacosyl, and heptacosyl groups. Examples of branched alkyl groups having 1 to 30 carbon atoms include an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a sec-isoamyl group, an isohexyl group, a neohexyl group, a 4-methylhexyl group, a 5-methylhexyl group, a 1-ethylhexyl group, a 2-ethylhexyl group, a 3-ethylhexyl group, a 4-ethylhexyl group, a 2-ethylpentyl group, a heptan-3-yl group, a heptan-4-yl group, a 4-methylhexane-2-yl group, a 3-methylhexane-3-yl group, a 2,3-dimethylpentan-2-yl group, a 2,4-dimethylpentan-2-yl group, a 2,5-dimethylpentan-2-yl group, a 2,6-dimethylpentan-2-yl group, a 2,7-dimethylpentan-2-yl group, a 2,8-dimethylpentan-2-yl group, a 2,9-dimethylpentan-2-yl group, a 2,10-dimethylpentan-2-yl group, a 2,11-dimethylpentan-2-yl group, a 2,12-dimethylpentan-2-yl group, a 2,13-dimethylpentan-2-yl group, a 2,14-dimethylpentan-2-yl group, a 2,15-dimethylpentan-2-yl group, a 2,16-dimethylpentan-2-yl group, a 2,17-dimethylpentan-2-yl group, a 2,18-dimethylpentan-2-yl group, a 2,19-dimethylpentan-2-yl group, a 2,20-dimethylpentan-2-yl group, a 2,21-dimethylpentan-2-yl group, a 2,22-dimethylpentan-2-yl group, a 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, nonan-4-yl group, 2,6-dimethylheptan-3-yl group, 3,6-dimethylheptan-3-yl group, 3-ethylheptan-3-yl group, 3,7-dimethyloctyl group, 8-methylnonyl group, 3-methylnonan-3-yl group, 4-ethyloctan-4-yl group, 9-methyldecyl group, undecane-5-yl group, 3-ethylnonan-3-yl group, 5-ethylnonan-5-yl group, 2,2,4,5,5-pentamethylhexan-4-yl group, 10-methylundecyl group, 11-methyldodecyl group, tridecane-6-yl group, tridecane-7-yl group, 7-ethylundecane-2-yl group, 3-ethylundecane-3-yl group, 5-ethylundecane-5-yl group, 12-methyltridecyl group, 13-methyltetradecyl group, pentadecane-7-yl group, pentadecane-8-yl group, 14-methylpentadecyl group, 15-methylhexadecyl group, heptadecan-8-yl group, heptadecan-9-yl group, 3,13-dimethylpentadecan-7-yl group, 2,2,4,8,10,10-hexamethylundecane-5-yl group, 16-methylheptadecyl group, 17-methyloctadecyl group Examples thereof include a nonadecane-9-yl group, a nonadecane-10-yl group, a 2,6,10,14-tetramethylpentadecan-7-yl group, an 18-methylnonadecyl group, a 19-methylicosyl group, a henicosyl group, a 20-methylhenicosyl group, a 21-methyldocosyl group, a tricosan-11-yl group, a 22-methyltricosyl group, a 23-methyltetracosyl group, a pentacosan-12-yl group, a pentacosan-13-yl group, a 2,22-dimethyltricosyl group, a 3,21-dimethyltricosyl group, a 9,15-dimethyltricosyl group, a 24-methylpentacosyl group, a 25-methylhexacosyl group, and a heptacosan-13-yl group. Examples of the alicyclic alkyl group having 1 to 30 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-tert-butylcyclohexyl group, a 1,6-dimethylcyclohexyl group, a menthyl group, a cycloheptyl group, a cyclooctyl group, a bicyclo[2.2.1]heptan-2-yl group, a bornyl group, an isobornyl group, a 1-adamantyl group, a 2-adamantyl group, a tricyclo[5.2.1.0, ２，６ ] decan-4-yl group, tricyclo[5.2.1.0 ２，６ ] decan-8-yl group, cyclododecyl group, and the like.

[0054] Also, L １ , and L ２ may have a photopolymerizable group. １ , and L ２may be a monovalent organic group having a photopolymerizable group. Examples of the photopolymerizable group include a radically polymerizable group, a cationic polymerizable group, and an anionic polymerizable group. Among these, the radically polymerizable group is preferred. Examples of the radically polymerizable group include an acryloyl group, a methacryloyl group, a propenyl ether group, a vinyl ether group, and a vinyl group.

[0055] The monovalent organic group having a photopolymerizable group is preferably a monovalent organic group represented by the following formula (9-b). [In formula (9-b), W ２ represents an oxygen atom or an NH group, R １７ represents a direct bond or an alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxyl group, R １８ represents a hydrogen atom or a methyl group, and * represents a bond.

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

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

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

[0059] Here, examples of the tetracarboxylic acid derivative include tetracarboxylic acid, tetracarboxylic acid diester, tetracarboxylic acid dihalide, and tetracarboxylic acid dianhydride.

[0060] <<Method for Producing Polyimide and Precursor Thereof>> The method for producing a polyimide and a precursor thereof is not particularly limited, and examples thereof include known methods for producing a polyamic acid, a polyamic acid ester, or a polyimide by reacting a diamine component with a tetracarboxylic acid derivative. Polyamic acid, polyamic acid ester, and polyimide can be synthesized by known methods such as those described in WO2013 / 157586.

[0061] The polyamic acid or polyamic acid ester is produced, for example, by reacting a diamine component with a tetracarboxylic acid derivative in a solvent (condensation polymerization).

[0062] Specific examples of the solvent 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. When the polymer has high solubility in the solvent, 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. (In formula [D-1], D １ represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-2], D ２ represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], D ３ represents an alkyl group having 1 to 4 carbon atoms.

[0063] These solvents may be used alone or in combination. Furthermore, even if a solvent does not dissolve polyamic acid, it may be mixed with the above-mentioned solvent to the extent that the polyamic acid or polyamic acid ester does not precipitate.

[0064] When reacting the diamine component and the tetracarboxylic acid derivative in a solvent, the reaction can be carried out at any concentration, preferably 1% by mass to 50% by mass, and more preferably 5% by mass to 30% by mass. The reaction can be carried out at a high concentration initially, with additional solvent added later. 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 a typical condensation polymerization reaction, the closer this molar ratio is to 1.0, the higher the molecular weight of the polyamic acid produced.

[0065] When reacting a diamine component with a tetracarboxylic acid derivative, a thermal polymerization inhibitor may be added to the reaction system to prevent 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 ether diaminetetraacetic 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 the thermal polymerization inhibitor used is not particularly limited.

[0066] Polyimide can be obtained by dehydrating and cyclizing the polyamic acid obtained by the above reaction. Methods for obtaining polyimide include thermal imidization, in which the solution of polyamic acid obtained by the above reaction is heated as is, and chemical imidization, in which a catalyst is added to the polyamic acid solution. When thermal imidization is performed in solution, the temperature is 100°C to 400°C, preferably 120°C to 250°C, and it is preferable to perform the imidization while removing water generated by the imidization reaction from the system.

[0067] The chemical imidization can be carried out by adding a basic catalyst and an acid anhydride to a solution of the polyamic acid obtained by the reaction and stirring the mixture at temperatures ranging from -20°C to 250°C, preferably from 0°C to 180°C. The amount of the basic catalyst is 0.1 to 30 times, preferably 0.2 to 20 times, the molar ratio of the amic acid groups, and the amount of the acid anhydride is 1 to 50 times, preferably 1.5 to 30 times, the molar ratio of the amic acid groups. Examples of basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Of these, triethylamine is preferred because it is less likely to produce polyisoimide as a by-product. Examples of acid anhydrides include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Of these, acetic anhydride is preferred because it facilitates purification after the reaction. The imidization rate (the ratio of ring-closed repeating units to all repeating units in the polyimide precursor, also referred to as the ring-closure rate) in chemical imidization can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

[0068] When recovering the imidized product produced from the imidization reaction solution, the reaction solution may be poured into a solvent to cause precipitation. Examples of solvents 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 by pouring into the solvent can be recovered by filtration and then dried at room temperature or by heating under normal or reduced pressure.

[0069] The polyimide and its precursor may be end-capped. The method for end-capping is not particularly limited, and a conventional method using a monoamine or an acid anhydride may be used, for example.

[0070] <<Polybenzoxazole and its precursor>> Polybenzoxazole is not particularly limited as long as it is a polymer containing benzoxazole in the repeating unit, and may also be a copolymer having other repeating units. Polybenzoxazole can be obtained, for example, by dehydrating and cyclizing a dicarboxylic acid and a bisaminophenol compound as a diamine using polyphosphoric acid. Polybenzoxazole can also be obtained, for example, by dehydrating and cyclizing a polyhydroxyamide using heating or a reaction using phosphoric anhydride, a base, or a carbodiimide compound.

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

[0072] When the resin composition is a photosensitive resin composition, the polybenzoxazole and its precursor preferably have a polymerizable unsaturated group, such as a (meth)acryloyl group.

[0073] The weight-average molecular weight of the polyimide or 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, still 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): When the resin composition containing polyimide or the like contains the compound represented by formula (A), a film having excellent adhesion, excellent antioxidant properties, and a low dielectric loss tangent can be obtained on a substrate having metal wiring on its surface.

[0075] The present inventors have conducted extensive research to obtain a resin composition that can provide a film having excellent adhesion, excellent antioxidant properties, and a low dielectric loss tangent on a substrate having metal wiring on its surface. In the research, various additives such as triazole compounds (e.g., 5-methyl-1H-benzotriazole, etc.), phenolic antioxidants (e.g., IRGANOX [registered trademark] 3114, etc.), silane coupling agents (e.g., KBM-5103, etc.), and triazine 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, etc.) were used. As a result, it was found that by using a compound represented by formula (A), a resin composition can be obtained that can provide a film having excellent adhesion, excellent antioxidant properties, and a low dielectric loss tangent on a substrate having metal wiring on its surface. [In formula (A), R ａ represents a hydrogen atom, a hydroxyl group, a methylol group, or an alkyl group having 1 to 30 carbon atoms. ｂ represents an alkyl group having 1 to 30 carbon atoms, m represents an integer of 0 to 3, n represents an integer of 1 to 4, and the maximum sum of m and n is 4.

[0076] As the alkyl group having 1 to 30 carbon atoms, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 10 carbon atoms is more preferred, and an alkyl group having 1 to 6 carbon atoms is 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 an isopropyl group, an isobutyl group, an isovaleryl group, an isohexyl group, a 2-ethylhexyl group, a 3-ethylheptyl group, a 2-ethyloctyl group, a 3-ethyldecyl group, a 2-hexyldecyl group, a 2-hexylundecyl group, a 2-octyldecyl group, a 2-octyldodecyl group, a 2-decyldodecyl group, a 2-decyltetradecyl group, a 2-decylhexadecyl group, a 3-hexyldecyl group, a 3-octyldecyl group, a 3-octyldodecyl group, a 3-decyltetradecyl group, a 3-decylhexadecyl group, a 4-hexyldecyl group, a 4-octyldecyl group, a 4-octyldodecyl group, a 4-decyltetradecyl group, a 4-decylhexadecyl group, a 4-cyclohexylbutyl group, and an 8-cyclohexyloctyl group. Examples of the cyclic alkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a 3-decylcyclopentyl group, and a 4-decylcyclohexyl group.

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

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

[0080] The compound represented by formula (A) is preferably 1H-benzotriazole-5-carboxylic acid (5-carboxybenzotriazole), 1H-benzotriazole-4-carboxylic acid (4-carboxybenzotriazole), or a combination thereof.

[0081] The compound represented by formula (A) may be a commercially available product, such as CBT-5 and CBT-SG manufactured by Johoku Chemical Industry Co., Ltd., and VERZONE (registered trademark) C-BTA manufactured by Daiwa Kasei 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 parts by mass to 20 parts by mass, more preferably 0.3 parts by mass to 10 parts by mass, and particularly preferably 0.5 parts by mass to 5 parts by mass, relative to 100 parts by mass of polyimide or the like.

[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. Specific examples of the solvent include N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylisobutyric acid 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, and solvents represented by the following formulas [D-1] to [D-3]. These may be used alone or in combination of two or more. (In formula [D-1], D １ represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-2], D ２ represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], D ３ represents an alkyl group having 1 to 4 carbon atoms.

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

[0085] <Other Components> In an embodiment, the resin composition may further contain other components in addition to the compound represented by Formula (A) such as polyimide and the solvent. Examples of the other components include a photoradical polymerization initiator (also referred to as a "photoradical initiator"), a crosslinking compound (also referred to as a "crosslinking agent"), a thermosetting agent, other resin components, a filler, a sensitizer, an adhesion aid, a thermal polymerization inhibitor, an azole compound, and a hindered phenol compound.

[0086] <<Photoradical Polymerization Initiator>> When the resin composition is used as a photosensitive resin composition, the resin composition contains, for example, a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited as long as it is a compound that has absorption in the light source used for photocuring, and examples thereof include tert-butylperoxy-iso-butylate, 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)hexene hydroperoxide, α-(iso-propylphenyl)-iso-propyl hydroperoxide, tert-butyl hydroperoxide, 1,1-bis(tert-butyldioxy)-3,3,5-trimethylcyclohexane, butyl-4,4-bis(tert-butyldioxy)valerate, cyclohexanone peroxide, 2,2',5,5'-tetra(tert-butylperoxy)- ... Organic peroxides such as 3,3'-bis(tert-butylperoxycarbonyl)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, and di-tert-butyldiperoxyisophthalate; quinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, and 1,2-benzanthraquinone; benzoin derivatives such as benzoin methyl, benzoin ethyl ether, α-methylbenzoin, and α-phenylbenzoin;2,2-Dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexyl phenyl 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-methyl-propionyl)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)phenyl alkylphenone compounds such as bis(2,4,6-trimethylbenzoyl)-1-butanone and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one; acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine 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-carbazol-3-yl]ethanone.

[0087] The photoradical polymerization initiator is commercially available, for example, IRGACURE [registered trademark] 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 [registered trademark] DETX-S, MBP, DMBI, EPA, OA (all manufactured by Nippon Kayaku Co., Ltd.), VICURE-10, VICURE-55 (all manufactured by Stauffer Co. Ltd.), ESACURE Examples of the photo-radical polymerization initiator include KIP150, TZT, 1001, KTO46, KB1, KL200, KS300, EB3, Triazine-PMS, Triazine A, and Triazine B (all manufactured by Nippon SiberHegner Co., Ltd.), ADEKA OPTOMER N-1717, N-1414, and N-1606, ADEKA ARCLES N-1919T, NCI-831E, NCI-930, and NCI-730 (all manufactured by ADEKA Corporation). These photo-radical polymerization initiators may be used alone 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, and more preferably 0.5 to 15 parts by mass, from the viewpoint of photosensitivity characteristics, relative to 100 parts by mass of polyimide, etc. When the photoradical polymerization initiator is contained in an amount of 0.1 part by mass or more relative to 100 parts by mass of polyimide, etc., the photosensitivity of the resin composition is likely to be improved, while when the photoradical polymerization initiator is contained in an amount of 20 parts by mass or less, the thick-film curability of the resin composition is likely to be improved.

[0089] <<Crosslinkable Compound>> In the embodiment, when the resin composition is used as a photosensitive resin composition, a monomer having a photoradical polymerizable unsaturated bond (crosslinkable compound) can be optionally contained in the resin composition in order to improve the resolution of the relief pattern. Such a crosslinkable compound is preferably a compound having a polymerizable group that undergoes a radical polymerization reaction in the presence of a photoradical polymerization initiator, and examples of such a crosslinkable compound include, but are not limited to, a (meth)acrylic compound and a maleimide compound.Examples of the (meth)acrylic compound 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, cyclohexane di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dioxane glycol di(meth)acrylate, bisphenol A mono- or di(meth)acrylate, bisphenol F di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, (meth)acrylate, benzene trimethacrylate, di(meth)acrylate of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, di(meth)acrylate of tris(2-hydroxyethyl)isocyanurate, 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 of such compounds include (meth)acrylates, and ethylene oxide or propylene oxide adducts of these compounds, 2-isocyanate ethyl (meth)acrylate or isocyanate-containing (meth)acrylates, and compounds obtained by adding a blocking agent such as methyl ethyl ketone oxime, ε-caprolactam, γ-caprolactam, 3,5-dimethylpyrazole, diethyl malonate, ethanol, isopropanol, n-butanol, or 1-methoxy-2-propanol to these compounds.Examples of maleimide compounds include 1,2-bis(maleimido)ethane, 1,4-bis(maleimido)butane, 1,6-bis(maleimido)hexane, N,N'-1,4-phenylenebismaleimide, N,N'-1,3-phenylenedimaleimide, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(2-maleimidoethyl)disulfide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, and 1,6'-bismaleimido-(2,2,4-trimethyl)hexane. Examples of 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 alone or in combination of two or more. 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 or the like.

[0091] <<Thermosetting Agent>> Examples of the thermosetting agent include hexamethoxymethylmelamine, tetramethoxymethylglycoluril, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 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 the filler include inorganic fillers, and specific examples include sols of silica, aluminum nitride, boron nitride, zirconia, alumina, etc. The content of the filler in the resin composition is not particularly limited.

[0093] <<Other Resin Components>> In an embodiment, the resin composition may further contain a resin component other than polyimide, etc. Examples of resin components that can be contained in the resin composition include polyoxazole, polyoxazole precursor, phenolic resin, polyamide, epoxy resin, siloxane resin, acrylic resin, etc. 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 can be optionally blended into the resin composition to improve photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylaminocinnamylideneindano. p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl

[0039] Examples of the methylaminobenzoate include methylaminobenzoate, ... These may be used alone or in combination.

[0095] The content of the sensitizer is not particularly limited, but is preferably 0.1 to 25 parts by mass per 100 parts by mass of polyimide or the like.

[0096] <<Adhesion Aid>> In an embodiment, in order to further improve the adhesion between a film formed using the resin composition and a substrate, an adhesion aid can be optionally blended into the resin composition. Examples of the adhesion aid 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, N-[3-(triethoxysilyl)propyl]furan, and the like. Examples of the adhesive agent include silane coupling agents such as thalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride and N-phenylaminopropyltrimethoxysilane, and aluminum-based adhesion promoters such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate) and ethylacetoacetate aluminum diisopropylate.

[0097] Among these adhesion aids, it is more preferable to use a silane coupling agent in terms of adhesive strength.

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

[0099] <<Thermal Polymerization Inhibitor>> In an embodiment, a thermal polymerization inhibitor can be optionally blended to improve the viscosity and photosensitivity stability of the resin composition, particularly during storage in a solvent-containing solution. Examples of thermal polymerization inhibitors that can be used include hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic 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 is preferably in the range of 0.005 to 12 parts by mass per 100 parts by mass of polyimide or the like.

[0101] <<Azole Compound>> For example, when a substrate made of copper or a copper alloy is used, an azole compound can be optionally blended into the resin composition to further suppress oxidation of the substrate. The azole compound here refers to a compound different from the compound represented by formula (A). Examples of the azole compound 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 of the azole compounds include 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-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, and 1-methyl-1H-tetrazole. Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or in 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 relative to 100 parts by mass of polyimide, etc., 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 relative to 100 parts by mass of polyimide, etc. is 0.1 part 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 the content is 20 parts by mass or less, the resin composition has excellent photosensitivity when used as a photosensitive resin composition, which is preferable.

[0103] <<Hindered Phenol Compound>> In an embodiment, a hindered phenol compound can be optionally blended 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 the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), and 4,4'-butylidene. -bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamate) amide), 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 ... Tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 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- Examples of suitable hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione include 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, but are not limited to these. 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 relative to 100 parts by mass of polyimide, etc., 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 relative to 100 parts by mass of polyimide, etc. is 20 parts by mass or less, this is preferred because the resin composition has excellent photosensitivity when used as a photosensitive resin composition.

[0105] The resin composition can be suitably used as a negative photosensitive resin composition for producing a cured relief pattern as described below.

[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, more preferably a negative photosensitive resin composition.

[0107] (Resin Film) The resin film of the present invention is a baked product of a coating film of the resin composition of the present invention. Examples of coating methods include conventional methods used to apply resin compositions, such as coating with a spin coater, bar coater, blade coater, curtain coater, or screen printer, and spray coating with a spray coater. Various methods can be selected for the baking method used to obtain the baked product, including, for example, using a hot plate, an oven, or a temperature-programmable oven. Baking can be performed, 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 can also 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 for a photosensitive resist film (so-called dry film resist). The photosensitive resist film has a substrate film, a photosensitive resin layer (photosensitive resin film) formed from the photosensitive resin composition, and a cover film. Usually, the photosensitive resin layer and the cover film are laminated in this order on the substrate film.

[0109] The photosensitive resist film can be produced, for example, by applying a photosensitive resin composition to a substrate film, drying the composition to form a photosensitive resin layer, and then laminating a cover film on the photosensitive resin layer. The application method can be a conventional method used to apply a photosensitive resin composition, such as using a spin coater, bar coater, blade coater, curtain coater, or screen printer, or spray coating with a spray coater. Drying can be performed, for example, at 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] Known materials can be used for the base film, such as a thermoplastic resin film. Examples of such thermoplastic resins include polyesters such as polyethylene terephthalate. The thickness of the base film is preferably 2 μm to 150 μm. Known materials can be used for the cover film, such as a polyethylene film or a polypropylene film. The cover film is preferably a film that has a lower adhesive strength with the photosensitive resin layer than the base film. 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] (Method for manufacturing a substrate having a cured relief pattern) The method for manufacturing a substrate having a cured relief pattern of the present invention includes the steps of: (1) applying a photosensitive resin composition, which is one embodiment of the resin composition of the present invention, onto a substrate to form a photosensitive resin layer (photosensitive resin film) on the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; and (4) heat-treating the relief pattern to form a cured relief pattern.

[0112] Each step will be described below.

[0113] (1) Step of applying the photosensitive resin composition of the present invention onto a substrate to form a photosensitive resin layer on the substrate In this step, the photosensitive resin composition of the present invention is applied onto a substrate, and then dried as necessary to form a photosensitive resin layer. As the application method, a method conventionally used for applying a photosensitive resin composition can be used, such as a method of applying using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., or a method of spray application using a spray coater, etc.

[0114] The substrate to which the photosensitive resin composition is applied has, for example, metal wiring on its surface. Examples of the metal wiring include copper wiring, copper alloy wiring, etc. The method for forming the metal wiring is not particularly limited, and for example, a conventionally known method can be used.

[0115] If necessary, the coating film made of the photosensitive resin composition can be dried, and examples of the drying method include air drying, heat drying using an oven or a hot plate, vacuum drying, etc. Specifically, when air drying or heat drying is performed, drying can be carried out under conditions of 20°C to 200°C for 1 minute to 1 hour. In this manner, a photosensitive resin layer can be formed on the substrate.

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

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

[0118] (3) Step of Developing the Exposed Photosensitive Resin Layer to Form a Relief Pattern In this step, the unexposed portions of the exposed photosensitive resin layer are developed and removed. The development method for developing the exposed (irradiated) photosensitive resin layer can be any of the conventional photoresist development methods, such as the rotary spray method, the paddle method, and the immersion method accompanied by ultrasonic treatment. After development, rinsing may be performed to remove the developer. Furthermore, post-development baking may be performed at any temperature and time combination, as needed, for purposes such as adjusting the shape of the relief pattern. The developer used for development is preferably an organic solvent. 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. Two or more of each solvent, for example, a combination of several solvents, may also be used. The rinse solution used for rinsing is preferably an organic solvent that is miscible with the developer and has low solubility in the photosensitive resin composition. Examples of preferred rinse solutions include methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, toluene, and xylene. Two or more of each solvent, for example, a combination of several types, can also be used.

[0119] (4) Step of Heating the Relief Pattern to Form a Hardened Relief Pattern In this step, the relief pattern obtained by the development described above is heated to convert it into a hardened relief pattern. Various methods can be selected for heat curing, such as using a hot plate, an oven, or a temperature-programmable heating oven. Heating can be performed, for example, at 130°C to 250°C for 30 minutes to 5 hours. The atmospheric gas used during heat curing may be air, or an inert gas such as nitrogen or argon.

[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 an embodiment, a semiconductor device is provided that includes a semiconductor element and a cured film disposed above or below the semiconductor element. The cured film is a cured film formed from the resin composition of the present invention. In an 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 above-described method for manufacturing a substrate having a cured relief pattern. The present invention is also applicable 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 having a cured relief pattern as part of its processes. The semiconductor device of the present invention can be manufactured by forming a cured relief pattern as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure, and combining this with a known method for manufacturing a semiconductor device.

[0122] (Display Device) In an embodiment, a display device includes a display element and a cured film provided on the display element, the cured film being a film formed from the resin composition of the present invention. In an 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 (e.g., the cured relief pattern) may be laminated in direct contact with the display element, or may be laminated with another layer sandwiched therebetween. Examples of the cured film include surface protection films, insulating films, and planarizing films for TFT (Thin Film Transistor) liquid crystal display elements and color filter elements, protrusions for MVA (Multi-Domain Vertical Alignment) liquid crystal display devices, and partition walls for cathodes of organic EL (Electro-Luminescence) elements.

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

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

[0125] The weight average molecular weights (Mw) shown in the following synthesis examples are the results of measurement by gel permeation chromatography (hereinafter abbreviated as GPC in this specification). For the measurement, a GPC device (HLC-8320GPC (manufactured by Tosoh Corporation)) was used, and the measurement conditions were as follows: Column: Shodex (registered trademark) KD-805 / Shodex (registered trademark) KD-803 (Showa Denko K.K.) Column temperature: 50°C Flow rate: 1 mL / min Eluent: N,N-dimethylformamide (DMF), lithium bromide monohydrate (30 mM) / phosphoric acid (30 mM) / tetrahydrofuran (1%) Standard sample: polyethylene oxide

[0126] The chemical imidization ratio shown in the synthesis examples below was calculated by the following method. 100 mg of polyimide powder was placed in an NMR sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Scientific Co., Ltd.)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) mixture) (0.53 ml) was added. Complete dissolution was achieved by applying ultrasound. This solution was subjected to 500 MHz proton NMR measurement using an NMR apparatus (JNM-ECA500) (manufactured by JEOL Ltd.). A proton derived from a structure that remained unchanged before and after imidization was determined as the reference proton, and the chemical imidization ratio was calculated using the integrated peak value of this proton and the integrated peak value of a proton derived from the NH group of the amic acid that appeared in the vicinity of 9.59 ppm to 11.0 ppm, according to the following formula: chemical imidization ratio (%)=(1−α·x / y)×100 In the above formula, x is the integrated value of the proton peak derived from the NH group of the amic acid, y is the integrated value of the peak of the reference proton, and α is the ratio of the number of the reference protons to one NH group proton of the amic acid in the case of polyamic acid (imidization rate 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 Samsung Chemical Co., 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 at room temperature in air. Thereafter, 25.13 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 33.74 g of 9,9-bis[4-(3,4-dicarboxyphenoxy)phenylfluorenedioic anhydride (BPF-PA, manufactured by JFE Chemical Corporation), and 93.58 g of N-ethyl-2-pyrrolidone were added to the system, and the mixture was stirred at room temperature for 1 hour and then at 50°C for 19 hours to obtain a polyamic acid solution. The weight average molecular weight (Mw) of the obtained polyamic acid (P-1) measured by GPC was 29,554.

[0128] Synthesis Example 2: Synthesis of Solvent-Soluble Polyimide (P-2) To 415.9 g of the 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 in air at room temperature for 30 minutes, followed by stirring at 60°C for 3 hours. This solution was slowly added to 3,770 g of stirring methanol, and the mixture was stirred for 10 minutes. The resulting precipitate was filtered off. This precipitate was washed with 3,770 g of methanol and then filtered off. This precipitate was washed again with 3,770 g of methanol, and the resulting precipitate was filtered off and dried under reduced pressure at 50°C to obtain a powder of solvent-soluble polyimide (P-2). 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 Samsung Chemical Co., 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, and then 11.97 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 16.07 g of 9,9-bis[4-(3,4-dicarboxyphenoxy)phenylfluorenedioic anhydride (BPF-PA, manufactured by JFE Chemical Corporation), and 34.65 g of N-ethyl-2-pyrrolidone were added to the system, and the mixture was stirred at room temperature for 1 hour and then at 40°C for 20 hours to obtain a polyamic acid solution. The weight average molecular weight (Mw) of the resulting polyamic acid (P-3) determined by GPC was 32,482.

[0130] Synthesis Example 4 Synthesis of Polyamic Acid (P-4) 31.78 g of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Samsung Chemical Co., Ltd.), 38.81 g of 4-octadecyloxy-1,3-phenylenediamine (DAB-C18, manufactured by Wakayama Seika Kogyo Co., Ltd.), 62.34 g of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, and 1012.4 g of N-ethyl-2-pyrrolidone were dissolved by stirring under air at room temperature, and then dodecahydro-5,5′-bi-2-benzofuran-1,1′,3,3′-tetrone (H-BPDA, manufactured by Weihai Newera Ksense New After stirring for 40 minutes, 31.57 g of 2,2',3,3',5,5'-hexamethyl-[1,1'-biphenyl]-4,4'-diylbis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate) (TMPBP-TME, Honshu Chemical Industry Co., Ltd.) was added and stirred for 1.5 hours, followed by addition of 48.28 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (SD1100-P, Sabic) and stirring at 50°C for 20 hours to obtain a polyamic acid solution. The weight average molecular weight (Mw) of the resulting polyamic acid (P-4) measured by GPC was 29,350.

[0131] Synthesis Example 5: Synthesis of Solvent-Soluble Polyimide (P-5) 992.6 g of N-ethyl-2-pyrrolidone, 105.22 g of acetic anhydride, and 17.38 g of triethylamine were added to 1985.1 g of the polyamic acid (P-4) obtained in Synthesis Example 4, and the mixture was stirred at room temperature for 30 minutes in air, followed by stirring at 60°C for 3 hours. After diluting the solution with 992.6 g of N-ethyl-2-pyrrolidone, 1922 g of the resulting solution was taken and slowly added to 4265 g of stirring methanol. After stirring for 10 minutes, the resulting precipitate was filtered off. This precipitate was washed with 1922 g of methanol, and then filtered off. This precipitate was washed again with 1922 g of methanol, and the resulting precipitate was filtered off and dried under reduced pressure at 60°C to obtain a powder of solvent-soluble polyimide (P-5). 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 dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a 2-liter four-neck flask, and 176.92 g (1.366 mol) of 2-hydroxyethyl methacrylate (manufactured by Sigma-Aldrich Japan G.K.), 0.74 g (0.007 mol) of hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.), and 600 g of γ-butyrolactone were added and stirred at 23° C., and 108.63 g (1.36 mol) of pyridine was added, followed by heating to 50° C. and stirring at 50° C. for 2 hours to obtain a solution containing a compound represented by the following formula:

[0133] 82.46 g of the resulting solution and 19.45 g of γ-butyrolactone were placed in a 500 mL four-neck flask, and a solution of 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 solution over 0.5 hours at approximately 5°C with stirring. After the dropwise addition, stirring was continued for 0.5 hours. Subsequently, a solution of 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 with stirring. The temperature was then raised to approximately 25°C and stirred for 6 hours. After that, 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, producing a precipitate consisting of a 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 2,250 g of water to precipitate the polymer, and the resulting precipitate was filtered, washed twice with 600 g of methanol, and vacuum dried to obtain a powdery polyamic acid ester (P-6). The weight average molecular weight (Mw) of the obtained polyamic acid ester (P-6) measured 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 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-dione, 1,1'-C ３６ -Alkylenebis- (manufactured by Designer Molecules Inc.)

[0135] Example 1 A negative photosensitive resin composition was prepared by mixing and dissolving 1.63 g of the powder of 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-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan G.K.). The mixture was then filtered using a polypropylene filter having a pore size of 5 μm.

[0136] Example 2 1.63 g of the 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-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan G.K.) were mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5 μm, to prepare a negative photosensitive resin composition.

[0137] Example 3 1.63 g of the 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 0.081 g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan G.K.) were mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5 μm, to prepare a negative photosensitive resin composition.

[0138] Example 4 1.63 g of the powder of 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-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan G.K.), and 0.024 g of 1,2,3-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5 μm, to prepare a negative photosensitive resin composition.

[0139] Example 5 1.63 g of the 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-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan G.K.), and 0.024 g of IRGANOX (registered trademark) 3114 were mixed and dissolved, and the mixture was then filtered using a polypropylene filter having a pore size of 5 μm, to prepare a negative photosensitive resin composition.

[0140] Example 6 1.63 g of the 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-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan G.K.), 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 having a pore size of 5 μm, to prepare a negative photosensitive resin composition.

[0141] Example 7 1.63 g of the 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-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan G.K.), and 0.033 g of KBM-5103 were mixed and dissolved, and the mixture was then filtered using a polypropylene filter having a pore size of 5 μm, to prepare a negative photosensitive resin composition.

[0142] Example 8 1.63 g of the 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-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan G.K.), and 0.024 g of 5-methyl-1H-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and dissolved, and the mixture was then filtered using a polypropylene filter having a pore size of 5 μm, to prepare a negative photosensitive resin composition.

[0143] Example 9 1.63 g of the 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-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan G.K.), and 0.024 g of IRGANOX (registered trademark) 3114 were mixed and dissolved, and the mixture was then filtered using a polypropylene filter having a pore size of 5 μm, to prepare a negative photosensitive resin composition.

[0144] Example 10 1.63 g of the 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 CBT-SG (a mixture of 4-carboxybenzotriazole and 5-carboxybenzotriazole, manufactured by Johoku Chemical Industry Co., Ltd.) were mixed and dissolved, and then filtered using a polypropylene filter having a pore size of 5 μm, to prepare a negative photosensitive resin composition.

[0145] Example 11 A negative photosensitive resin composition was prepared by mixing and dissolving 1.63 g of the 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 CBT-SG (a mixture of 4-carboxybenzotriazole and 5-carboxybenzotriazole, manufactured by Johoku Chemical Industry Co., Ltd.), and filtering the mixture using a polypropylene filter having a pore size of 5 μm.

[0146] Example 12 1.63 g of the 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 CBT-5 (5-carboxybenzotriazole, manufactured by Johoku Chemical Industry Co., Ltd.) were mixed and dissolved, and then filtered using a polypropylene filter having a pore size of 5 μm, to prepare a negative photosensitive resin composition.

[0147] Example 13 1.63 g of the 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 CBT-5 (5-carboxybenzotriazole, manufactured by Johoku Chemical Industry Co., Ltd.) were mixed and dissolved, and then filtered using a polypropylene filter having a pore size of 5 μm, to prepare a negative photosensitive resin composition.

[0148] Example 14 2.02 g of NK ester A-DOD-N as a crosslinking agent, 0.34 g of IRGACURE [registered trademark] OXE01 as a photoradical initiator, and 0.20 g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan G.K.) were mixed and dissolved in 22.44 g of a solution (solid content concentration: 30 mass %) containing the polyamic acid (P-3) obtained in Synthesis Example 3, and the mixture was filtered using a polypropylene filter having a pore size of 5 μm, thereby preparing a negative photosensitive resin composition.

[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 as a crosslinking agent, 0.15 g of IRGACURE [registered trademark] OXE01 as a photoradical initiator, 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.), and BMI-689 (Designer Molecules) as a bismaleimide compound were added. A negative photosensitive resin composition was prepared by mixing and dissolving 0.22 g of methylparaben (manufactured by Ajinomoto Co., Inc.), 3.67 g of N-ethyl-2-pyrrolidone, 4.90 g of γ-butyrolactone, and 3.67 g of cyclohexanone, and then filtering the mixture using a polypropylene filter having a pore size of 5 μm.

[0150] Example 16 6.34 g of the powder of polyamic acid ester (P-6) 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 [registered trademark] OXE01 as a photoradical initiator, and 0.19 g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan G.K.) were mixed and dissolved, and then filtered using a polypropylene filter having a pore size of 5 μm, to prepare a negative photosensitive resin composition.

[0151] Comparative Example 1 A negative photosensitive resin composition was prepared by mixing and dissolving 1.63 g of the 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, and then filtering the mixture using a polypropylene filter having a pore size of 5 μm.

[0152] Comparative Example 2 1.63 g of the 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 size of 5 μm, to prepare a negative photosensitive resin composition.

[0153] Comparative Example 3 1.63 g of the 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 having a pore size of 5 μm, to prepare a negative photosensitive resin composition.

[0154] Comparative Example 4 1.63 g of the 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 having a pore size of 5 μm, to prepare a negative photosensitive resin composition.

[0155] Comparative Example 5 1.63 g of the 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 having a pore size of 5 μm, to prepare a negative photosensitive resin composition.

[0156] Comparative Example 6 1.63 g of the 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 the mixture was then filtered using a polypropylene filter having a pore size of 5 μm, to prepare a negative photosensitive resin composition.

[0157] Comparative Example 7 1.63 g of the 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 the mixture was filtered using a polypropylene filter having a pore size of 5 μm, to prepare a negative photosensitive resin composition.

[0158] Comparative Example 8 1.63 g of the 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 2,4-diamino-6-butylamino-1,3,5-triazine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and dissolved, and then filtered using a polypropylene filter having a pore size of 5 μm, to prepare a negative photosensitive resin composition.

[0159] Comparative Example 9 1.63 g of the 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 2,4-diamino-6-diallylamino-1,3,5-triazine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and dissolved, and then filtered using a polypropylene filter having a pore size of 5 μm, to prepare a negative photosensitive resin composition.

[0160] Comparative Example 10 A negative photosensitive resin composition was prepared by mixing and dissolving 1.63 g of the 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 6-(dibutylamino)-1,3,5-triazine-2,4-dithiol (manufactured by Tokyo Chemical Industry Co., Ltd.), and filtering the mixture using a polypropylene filter having a pore size of 5 μm.

[0161] [Adhesion Evaluation] An 8-inch silicon wafer on which Cu had been vapor-deposited to a thickness of 1.5 μm was cut into a 1 cm × 1 cm piece. This silicon wafer was washed with 10% sulfuric acid for 1 minute, then washed with pure water for 30 seconds, and then dried. The negative photosensitive resin compositions prepared in Examples 1 to 16 and Comparative Examples 1 to 10 were then coated onto the wafer. This was pre-baked at 115°C for 270 seconds to form a 22 μm thick photosensitive resin film on the substrate (silicon wafer on which Cu had been vapor-deposited). Next, an i-line aligner (PLA-501, manufactured by Canon Inc.) was used to apply 500 mJ / cm ２After the entire surface was exposed to light, the sample was baked in a high-temperature clean oven (CLH-21CD(V)-S, Koyo Thermo Systems Co., Ltd.) at 230°C for 2 hours in a nitrogen atmosphere. Next, a reliability test was performed in air at 125°C for 24 hours and at 30°C and 60% humidity for 168 hours. Then, a reflow treatment was performed in a nitrogen atmosphere at 260°C for 1 second, including a temperature increase, three times. Finally, a highly accelerated life test (EHS-212MD, Espec Corporation) was performed at 130°C, 85% humidity, and a vapor pressure of 230 kPa for 192 hours. A stud pin with an epoxy adhesive was then bonded to the resin film surface, and a stud-pull peel strength measurement was performed using a ROMURUS V (Quad Group, USA) to evaluate the adhesion between the Cu surface and the resin film. Separately, a substrate (substrate with a resin film formed thereon) that had not been subjected to a reliability test was also prepared, and a stud-pull peel strength measurement was similarly performed on each substrate. The peeling interface after the test was observed, and if peeling occurred due to cohesive failure of the epoxy adhesive both before and after the reliability test, or if peeling occurred at the interface between the epoxy adhesive and the resin film surface, the adhesion was deemed good and marked with a "Good." If peeling occurred at the interface between the photosensitive resin film and Cu either before or after the reliability test, the adhesion was deemed poor and marked with a "Poor." The results are shown in Tables 1-1 and 1-2.

[0162] [Evaluation of Antioxidant Ability] A test substrate (1 cm x 1 cm) for evaluation, having a PI (polyimide) base and Cu wiring with a height of 5 μm and a width of 10 μmL / S thereon, was washed with 10% sulfuric acid for 1 minute, washed with pure water for 30 seconds, and then dried. The negative 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 [Evaluation of Adhesion], and pre-baked at 115°C for 270 seconds to form a photosensitive resin film. Next, an i-line aligner (PLA-501, manufactured by Canon Inc.) was used to apply 500 mJ / cm ２The entire surface was exposed to light. The substrate was then baked in a high-temperature clean oven (CLH-21CD(V)-S, Koyo Thermo Systems Co., Ltd.) at 230°C for 2 hours in a nitrogen atmosphere. Reliability tests were then conducted in air at 125°C for 24 hours and at 30°C and 60% humidity for 168 hours. Reflow treatments were then conducted three times at 260°C for 1 second, including temperature rise, in a nitrogen atmosphere. Finally, the substrate was subjected to a highly accelerated life test (EHS-212MD, Espec Corp.) at 130°C, 85% humidity, and a vapor pressure of 230 kPa for 192 hours. The Cu wiring of the evaluation test substrate was then cut using a FIB-SEM (manufactured by Japan FEI Inc.), and the cross section was observed using a SEM. The oxide film formed on the Cu wiring in the reliability test that was thinner than that of Comparative Example 1 (73.7 nm) was evaluated as good and marked with a "◯," while the oxide film that was thicker was evaluated as bad and marked with a "X." The results are shown in Table 1.

[0163] [Evaluation of Electrical Properties] The negative photosensitive resin compositions prepared in Examples 1 to 15 and Comparative Examples 1 to 10 were spin-coated onto a 4-inch silicon wafer covered with 20 μm-thick aluminum foil, and 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 / cm to the obtained photosensitive resin film on the wafer. ２After the entire surface was exposed to light with a UV ray, the foil was baked in a nitrogen atmosphere at 230°C for 2 hours using a high-temperature clean oven (CLH-21CD(V)-S, Koyo Thermo Systems Co., Ltd.). The baked aluminum foil was then immersed in 6N hydrochloric acid to dissolve the aluminum foil, yielding a film. The resulting film was dried, and its 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: approximately 60 GHz A dielectric loss tangent value obtained by this measurement that was equal to or less than that of Comparative Example 1 (0.0087) was evaluated as good and marked with "◯," and a value greater than that of Comparative Example 1 was evaluated as bad and marked with "X." The results are shown in Tables 1-1 and 1-2.

[0164]

[0165]

[0166] The results in Tables 1-1 and 1-2 show that the resin films obtained from the negative photosensitive resin compositions of Examples 1 to 16 all had good adhesion. Furthermore, the Cu wirings on which the resin films obtained from the negative photosensitive resin compositions of Examples 1 to 16 were formed had thinner oxide film thicknesses after reliability tests than the Cu wirings on which the resin films obtained from the negative photosensitive resin composition of Comparative Example 1 were formed, confirming their good reliability. Furthermore, the films obtained from the negative photosensitive resin compositions of Examples 1 to 15 exhibited dielectric loss tangents equal to or lower than those of the film obtained from the negative photosensitive resin composition of Comparative Example 1.

Claims

1. A resin composition comprising a polyimide having structural units represented by the following formula (1-a) and the following formula (1-b-1), a compound represented by the following formula (A), and a solvent: 【Chemical 1】 [In formula (A), R ａ represents a hydrogen atom, a hydroxyl group, a methylol group, or an alkyl group having 1 to 30 carbon atoms. ｂ represents an alkyl group having 1 to 30 carbon atoms, m represents an integer of 0 to 3, n represents an integer of 1 to 4, and the maximum sum of m and n is 4. 【Chemistry 2】 [In formula (1-a) and formula (1-b-1), Ar 1 represents a tetravalent organic group, and X 11 represents a divalent organic group having a photopolymerizable group.]

2. The resin composition according to claim 1, wherein the polyimide has a divalent organic group represented by the following formula (9-a): 【Chemistry 3】 [In formula (9-a), V １ represents a direct bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a 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.

3. V in the formula (9-a) １ represents an ester bond, and W １ The resin composition according to claim 2, wherein represents an oxygen atom.

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

5. R in the 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) represents 0.

7. 2. The resin composition according to claim 1, wherein the compound represented by formula (A) includes 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, which is used for forming an insulating film.

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

12. 2. The resin composition according to claim 1, which is a negative 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 substrate film, a photosensitive resin layer formed from the resin composition according to claim 11 or 12, and a cover film.

16. (1) applying the resin composition according to claim 11 or 12 onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) heat-treating the relief pattern to form a hardened relief pattern; A method for producing a substrate with a cured relief pattern, comprising:

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

18. The method for producing a substrate having a cured relief pattern according to claim 16, wherein the developer used for the development is an organic solvent.

19. 17. A substrate with a cured relief pattern produced by the method of 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 formed from the resin composition according to any one of claims 1 to 12.

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

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