WO2023106101A1

WO2023106101A1 - Resin composition

Info

Publication number: WO2023106101A1
Application number: PCT/JP2022/043286
Authority: WO
Inventors: 浩司荻野; 崇洋坂口; 秀則石井; 貴文遠藤; 有輝星野
Original assignee: 日産化学株式会社
Priority date: 2021-12-09
Filing date: 2022-11-24
Publication date: 2023-06-15
Also published as: TW202338002A

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

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 manufacturing a substrate with a cured relief pattern, and a semiconductor device.

Conventionally, polyimide resins, polybenzoxazole resins, etc., which have excellent heat resistance, electrical properties, and mechanical properties, have been used as insulating materials for electronic parts, and for passivation films, surface protective films, interlayer insulating films, etc. for semiconductor devices. (See Patent Document 1).

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

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

JP 2012-194520 A Japanese Patent Application Laid-Open No. 2005-010360 International Publication No. 2015/020020 Pamphlet

In recent years, in semiconductor devices, due to the need to transmit and process large amounts of information at high speed, the frequency of electrical signals is increasing. Since high-frequency electrical signals are easily attenuated, it is necessary to reduce transmission loss. Therefore, resins used in semiconductor devices are required to have a low dielectric loss tangent.

Therefore, there is a demand for a resin composition that can form a film having excellent adhesion, excellent antioxidant 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 characteristics.

In view of the above circumstances, an object of the present invention is to provide a resin composition capable of obtaining a film having both excellent adhesion, excellent antioxidant properties, and low dielectric loss tangent on a substrate having metal wiring on its surface, and the resin composition. The object of the present invention is to provide a resin film obtained from (1), a photosensitive resist film using the resin composition, a method for producing a substrate with a cured relief pattern, and a semiconductor device.

The present inventors have made intensive studies to solve the above problems, and found that a resin composition containing polyimide or the like contains a compound represented by the following formula (A), whereby metal wiring is formed on the surface. The present inventors have completed the present invention based on the finding that a resin composition can be obtained on a substrate having the above-described properties, which can provide a film having excellent adhesion, excellent antioxidant properties, and a low dielectric loss tangent.

[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 the formula (A), R _a represents a hydrogen atom, a hydroxyl group, a methylol group, or an alkyl group having 1 to 30 carbon atoms. R _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 is a polyimide having structural units represented by the following formulas (1-a) and (1-b-1) or the following formulas (3) and (1-b-2) The resin composition according to [1] or [2], which is a polyimide precursor having the structural unit represented.

[In formulas (1-a) and (1-b-1), Ar ₁ represents a tetravalent organic group, and X ₁₁ represents a divalent organic group having a photopolymerizable group.
In formulas (3) and (1-b-2), Ar ₃ represents a tetravalent organic group, L ₁ and L ₂ each independently represent a monovalent organic group, and X ₁₂ represents a divalent represents an organic group, and at least one of L ₁ , L ₂ and X ₁₂ 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 represents 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] The resin composition according to [4], wherein V ₁ in formula (9-a) represents an ester bond, and W ₁ represents an oxygen atom.
[6] The resin composition according to [4] or [5], wherein R ₁₅ in formula (9-a) represents a 1,2-ethylene group.
[7] The resin composition according to any one of [1] to [6], wherein R _a in formula (A) represents a hydrogen atom.
[8] The resin composition according to any one of [1] to [7], wherein m in formula (A) represents 0.
[9] Any one of [1] to [8], wherein the compound represented by formula (A) contains at least one of 1H-benzotriazole-5-carboxylic acid and 1H-benzotriazole-4-carboxylic acid The resin composition according to .
[10] The resin composition according to any one of [1] to [9], further comprising a radical photopolymerization 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 baked product of the coating film of the resin composition according to any one of [1] to [14].
[16] The resin film according to [15], which is an insulating film.
[17] A photosensitive resist film comprising a base film, a photosensitive resin layer formed from the resin composition according to [13] or [14], and a cover film.
[18] (1) A step of applying the resin composition according to [13] or [14] onto a substrate to form a photosensitive resin layer on the substrate;
(2) exposing the photosensitive resin layer;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) heat-treating the relief pattern to form a cured relief pattern;
A method of manufacturing a cured relief patterned substrate, comprising:
[19] The method for producing a cured relief patterned substrate according to [18], wherein in the step (1), the resin composition is applied to the substrate having metal wiring on its surface.
[20] The method for producing a cured relief patterned substrate according to [18] or [19], wherein the developer used for the development is an organic solvent.
[21] A substrate with 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 above or below the semiconductor element, wherein the cured film is formed from the resin composition according to any one of [1] to [14]. A semiconductor device that is a cured film to be coated.
[23] The resin composition is a photosensitive resin composition,
The semiconductor device according to [22], wherein the cured film is a cured relief pattern formed from the photosensitive resin composition.

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a resin composition capable of obtaining a film having both excellent adhesion, excellent antioxidation properties, and low dielectric loss tangent on a substrate having metal wiring on its surface, and a resin film obtained from the resin composition. , a photosensitive resist film using the resin composition, a method for producing a substrate with a cured relief pattern, and a semiconductor device are obtained.

(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.

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

Polyimide or the like preferably has a photopolymerizable group in terms of imparting photosensitivity when the resin composition is used as a photosensitive resin composition, more preferably has a polymerizable unsaturated group, (meth) Having an acryloyl group is even more preferable, and having a divalent organic group represented by the following formula (9-a) is particularly preferable.

[In the formula (9-a), V ₁ is a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-), or a urea bond (-NHCONH-), 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, and R ₁₆ represents hydrogen represents an atom or a methyl group, and * represents a bond. ]

<<polyimide and its precursor>>
Examples of polyimides and their precursors include polyimides, polyamic acids, polyamic acid esters, and the like.

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

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

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

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

An example of polyimide is polyimide having structural units represented by formula (1-a) and formula (1-b-1) below.
An example of the polyimide precursor is a polyimide precursor having structural units represented by formula (3) and formula (1-b-2) below. However, in the polyimide precursor, at least one of L ₁ , L ₂ and X ₁₂ has a photopolymerizable group.

[In formula (1-b-1), X ₁₁ represents a divalent organic group having a photopolymerizable group.
In formula (1-b-2), X ₁₂ represents a divalent organic group. ]

<<<Ar ₁ , Ar ₂ and Ar ₃ >>>
Ar ₁ , Ar ₂ and Ar ₃ each represent a tetravalent organic group.
The tetravalent organic group is not particularly limited. tetravalent organic groups derived from group tetracarboxylic dianhydrides, and the like.
As the tetravalent organic group, a tetravalent organic group having three or more aromatic rings is preferable in that a film having a lower dielectric loss tangent can be obtained.

The number of aromatic rings possessed by Ar ₁ , Ar ₂ and Ar ₃ is preferably 3 or more, more preferably 4 or more, in that a film having a lower dielectric loss tangent can be obtained. 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.

Regarding how to count aromatic rings in "3 or more aromatic rings", polycyclic aromatic rings formed by condensing two or more aromatic rings such as naphthalene ring and anthracene ring are counted as one aromatic ring. . Therefore, a naphthalene ring is counted as one aromatic ring. On the other hand, a biphenyl ring is not a fused ring and counts as two aromatic rings. A perylene ring is then counted as two aromatic rings.
Aromatic rings include aromatic hydrocarbon rings, aromatic heterocycles, and the like.

Ar ₁ , Ar ₂ and Ar ₃ preferably represent a tetravalent organic group represented by the following formula (4) from the viewpoint of suitably obtaining the effects of the present invention.

[In the formula (4), X ₁ and X ₂ are each independently a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-) , represents a urea bond (-NHCONH-), a thioether bond (-S-) or a sulfonyl bond (-SO ₂ -).
R _a1 and R _a2 each independently represent an optionally substituted alkyl group having 1 to 6 carbon atoms.
Z ₁ represents a divalent organic group represented by the following formula (5-a), (5-b) or (5-c) below.
n1 and n2 each independently represent an integer of 0 to 3;
When there are multiple R _{a1 s} , the multiple R _a1s may be the same or different. When R _a2 is plural, the plural R _a2 may be the same or different.
* represents a bond. ]

Examples of optionally substituted alkyl groups having 1 to 6 carbon atoms in R _a1 and R _a2 in formula (4) include alkyl groups having 1 to 6 carbon atoms. Examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group. In the present specification, alkyl groups and alkylene groups may be linear, branched, or cyclic, unless otherwise specified for their structure. may be a combination of two or more of
Examples of substituents on the optionally substituted alkyl group having 1 to 6 carbon atoms include a halogen atom, a hydroxy group, a mercapto group, a carboxy group, a cyano group, a formyl group, a haloformyl group, a sulfo group, an amino group, nitro group, nitroso group, oxo group, thioxy group, alkoxy group having 1 to 6 carbon atoms, and the like.
The "1 to 6 carbon atoms" of the "optionally substituted alkyl group having 1 to 6 carbon atoms" refers to the number of carbon atoms in the "alkyl group" excluding substituents. Also, the number of substituents is not particularly limited.

[In the formula (5-a), R ₃ represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and m ₁ represents 0 to 4 represents an integer of When _m1 is 2 or more, _R3 may be the same or different.
In formula (5-b), Z ₂ represents a direct bond or a divalent organic group represented by formula (6-a) or (6-b) below, and R ₄ and R ₅ are each independent represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and m ₂ and m ₃ are each independently an integer of 0 to 4. show. When _m2 is 2 or more, _R4 may be the same or different. When _m3 is 2 or more, _R5 may be the same or different.
In formula (5-c), R ₆ represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and m ₄ represents 0 to 6 represents an integer. When _m4 is 2 or more, _R6 may be the same or different.
* represents a bond. ]

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

Z ₁ preferably represents a divalent organic group represented by formula (5-b) from the viewpoint of favorably obtaining the effects of the present invention.

Examples of alkyl groups having 1 to 6 carbon atoms which may be substituted with halogen atoms for R ₇ and R ₈ include alkyl groups having 1 to 6 carbon atoms and halogenated alkyl groups having 1 to 6 carbon atoms. etc.
Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group.
Examples of the halogen atom in the halogenated alkyl group having 1 to 6 carbon atoms include fluorine atom, chlorine atom, bromine atom and iodine atom.
A halogenated alkyl group having 1 to 6 carbon atoms may be partially or completely halogenated.

Examples of substituents on the optionally substituted alkylene group having 1 to 6 carbon atoms in R ₉ and R ₁₀ include a halogen atom, a hydroxy group, a mercapto group, a carboxy group, a cyano group, a formyl group, a haloformyl group, sulfo group, amino group, nitro group, nitroso group, oxo group, thioxy group, alkoxy group having 1 to 6 carbon atoms, and the like.
Examples of optionally substituted alkylene groups having 1 to 6 carbon atoms include alkylene groups having 1 to 6 carbon atoms and halogenated alkylene groups having 1 to 6 carbon atoms. Examples of the alkylene group having 1 to 6 carbon atoms include methylene group, ethylene group, propylene group and butylene group.
The "1 to 6 carbon atoms" of the "optionally substituted alkylene group having 1 to 6 carbon atoms" refers to the number of carbon atoms in the "alkylene group" excluding substituents. Also, the number of substituents is not particularly limited.

Examples of substituents on the optionally substituted arylene group having 6 to 10 carbon atoms in R ₉ and R ₁₀ include a halogen atom, an optionally halogenated alkyl group having 1 to 6 carbon atoms, halogen and an alkoxy group having 1 to 6 carbon atoms which may be substituted. Halogenation may be partially or wholly.
The arylene group includes, for example, a phenylene group and a naphthylene group.
The "6 to 10 carbon atoms" of the "optionally substituted arylene group having 6 to 10 carbon atoms" refers to the number of carbon atoms in the "arylene group" excluding substituents. Also, the number of substituents is not particularly limited.

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.

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 to R ₃₃ are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or a 1 to 6 carbon atoms which may be substituted with a halogen atom represents an alkoxy group. n31 represents an integer of 0-5. n32 and n33 each independently represent an integer of 0 to 4; When R ₃₁ is plural, the plural R ₃₁ may be the same or different. When R ₃₂ is plural, the plural R ₃₂ may be the same or different. When R ₃₃ is plural, the plural R ₃₃ may be the same or different. * represents a bond.

Specific examples of alkyl groups having 1 to 6 carbon atoms which may be substituted with halogen atoms for R ₃₁ to R ₃₃ include alkyl groups having 1 to 6 carbon atoms and halogen having 1 to 6 carbon atoms. alkyl group.
Examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group.
Examples of the halogen atom in the halogenated alkyl group having 1 to 6 carbon atoms include fluorine atom, chlorine atom, bromine atom and iodine atom. A halogenated alkyl group having 1 to 6 carbon atoms may be partially or completely halogenated.
Specific examples of the alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom for R ₃₁ to R ₃₃ are an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom. based on.

Ar ₁ , Ar ₂ and Ar ₃ include, for example, tetravalent organic groups represented by the following formulae.

In the formula, * represents a bond.

Ar ₁ , Ar ₂ and Ar ₃ may be, for example, tetravalent organic groups represented by the following formulas.

In the formula, * represents a bond.

<<<X, X ₁₁ , and X ₁₂ >>>
X represents a divalent organic group. X represents, for example, a divalent aromatic group having a photopolymerizable group.
_X11 represents a divalent organic group having a photopolymerizable group. X ₁₁ represents, for example, a divalent aromatic group having a photopolymerizable group.
X ₁₂ represents a divalent organic group.
X ₁₂ has, for example, a photopolymerizable group. X ₁₂ represents, for example, a divalent organic group having a photopolymerizable group. X ₁₂ represents, for example, a divalent aromatic group having a photopolymerizable group.

Examples of photopolymerizable groups include radically polymerizable groups, cationic polymerizable groups, and anionically polymerizable groups. Among these, a radically polymerizable group is preferred.
Examples of radically polymerizable groups include acryloyl groups, methacryloyl groups, propenyl ether groups, vinyl ether groups, and vinyl groups.

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

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

As the divalent aromatic group having a photopolymerizable group, a divalent organic group represented by the following formula (9-a) is preferable.

[In the formula (9-a), V ₁ is a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-), or a urea bond (—NHCONH—), 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, and R ₁₆ represents hydrogen represents an atom or a methyl group, and * represents a bond. ]

The two bonds in formula (9-a) are, for example, bonds that bond to a nitrogen atom.

In the present specification, the alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxyl group includes, for example, 1,1-ethylene group, 1,2-ethylene group, 1,2-propylene group, 1, 3-propylene group, 1,4-butylene group, 1,2-butylene group, 2,3-butylene group, 1,2-pentylene group, 2,4-pentylene group, 1,2-hexylene group, 1, 2-cyclopropylene group, 1,2-cyclobutylene group, 1,3-cyclobutylene group, 1,2-cyclopentylene group, 1,2-cyclohexylene group, at least part of these hydrogen atoms are hydroxyl groups and an alkylene group substituted with (eg, 2-hydroxy-1,3-propylene group).

V ₁ preferably represents an ester bond (--COO--).
_W1 preferably represents an oxygen atom.
R ₁₅ preferably represents a 1,2-ethylene group.

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. The two bonds are, for example, positioned meta to the substituent having a photopolymerizable group.

X and _X12 preferably represent a divalent organic group having three or more aromatic rings from the viewpoint of obtaining a film with a lower dielectric loss tangent. The divalent organic group having three or more aromatic rings as used herein refers to an organic group different from the divalent aromatic group having a photopolymerizable group.

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

The number of aromatic rings in the divalent organic group having 3 or more aromatic rings is not particularly limited as long as it is 3 or more, but may be 4 or more, for example. 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.

Although the divalent organic group having three or more aromatic rings is not particularly limited, it is preferably a divalent organic group represented by the following formula (13).

[In the 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-) , represents a urea bond (-NHCONH-), a thioether bond (-S-) or a sulfonyl bond (-SO ₂ -).
R ₂₁ and R ₂₂ each independently represent an optionally substituted alkyl group having 1 to 6 carbon atoms.
Y ₂₀ represents a divalent organic group represented by the formula (5-a), the formula (5-b) or the formula (5-c).
n21 and n22 each independently represents an integer of 0 to 4;
When R ₂₁ is plural, the plural R ₂₁ may be the same or different. When R ₂₂ is plural, the plural R ₂₂ may be the same or different.
* represents a bond. ]

The optionally substituted alkyl group having 1 to 6 carbon atoms in R ₂₁ and R ₂₂ in formula (13) includes, for example, an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group. In the present specification, alkyl groups and alkylene groups may be linear, branched, or cyclic, unless otherwise specified for their structure. may be a combination of two or more of
Examples of substituents on the optionally substituted alkyl group having 1 to 6 carbon atoms include a halogen atom, a hydroxy group, a mercapto group, a carboxy group, a cyano group, a formyl group, a haloformyl group, a sulfo group, an amino group, nitro group, nitroso group, oxo group, thioxy group, alkoxy group having 1 to 6 carbon atoms, and the like.
The "1 to 6 carbon atoms" of the "optionally substituted alkyl group having 1 to 6 carbon atoms" refers to the number of carbon atoms in the "alkyl group" excluding substituents. Also, the number of substituents is not particularly limited.

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

In the formula, * represents a bond.

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 diamine.

In the formula, * represents a bond.

<<<L ₁ and L ₂ >>>
L ₁ and L ₂ each independently represent a monovalent organic group.
Monovalent organic groups include, for example, alkyl groups having 1 to 30 carbon atoms.
Examples of alkyl groups having 1 to 30 carbon atoms include straight-chain alkyl groups, branched-chain alkyl groups and alicyclic alkyl groups.
Linear alkyl groups having 1 to 30 carbon atoms include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group (amyl group), hexyl group, heptyl group, octyl group, nonyl group and decyl group. , undecyl group, dodecyl group (lauryl group), tridecyl group, tetradecyl group (myristyl group), pentadecyl group, hexadecyl group (palmityl group), heptadecyl group (margaryl group), octadecyl group (stearyl group), nonadecyl group, icosyl group (arachyl group), henicosyl group, docosyl group (behenyl group), tricosyl group, tetracosyl group (lignoceryl group), pentacosyl group, hexacosyl group, heptacosyl group and the like.
Branched alkyl groups having 1 to 30 carbon atoms include, for example, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, sec-isoamyl group and isohexyl. group, neohexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 2-ethylpentyl group, heptane-3-yl group, heptane-4-yl group, 4-methylhexan-2-yl group, 3-methylhexan-3-yl group, 2,3-dimethylpentan-2-yl group, 2,4-dimethylpentane-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-ethylnonane-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-dimethylpentadecane -7-yl group, 2,2,4,8,10,10-hexamethylundecane-5-yl group, 16-methylheptadecyl group, 17-methyloctadecyl group, nonadecan-9-yl group, nonadecan-10 -yl group, 2,6,10,14-tetramethylpentadecan-7-yl group, 18-methylnonadecyl group, 19-methylicosyl group, henicosan-10-yl group, 20-methylhenicosyl group, 21-methyldocosyl group , tricosan-11-yl group, 22-methyltricosyl group, 23-methyltetracosyl group, pentacosan-12-yl group, pentacosan-13-yl group, 2,22-dimethyltricosan-11-yl group, 3,21-dimethyltricosan-11-yl group, 9,15-dimethyltricosan-11-yl group, 24-methylpentacosyl group, 25-methylhexacosyl group, heptacosan-13-yl group, etc. mentioned.
Examples of alicyclic alkyl groups having 1 to 30 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-tert-butylcyclohexyl, 1,6-dimethylcyclohexyl and menthyl groups. , cycloheptyl group, cyclooctyl group, bicyclo[2.2.1]heptan-2-yl group, bornyl group, isobornyl group, 1-adamantyl group, 2-adamantyl group, tricyclo[5.2.1.0 ^{2 ,6} ]decan-4-yl group, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl group, cyclododecyl group and the like.

Also, L ₁ and L ₂ may have a photopolymerizable group. That is, L ₁ and L ₂ may be monovalent organic groups having photopolymerizable groups.
Photopolymerizable groups include, for example, radically polymerizable groups, cationic polymerizable groups, and anionically polymerizable groups. Among these, a radically polymerizable group is preferred.
Examples of radically polymerizable groups include acryloyl groups, methacryloyl groups, propenyl ether groups, vinyl ether groups, and vinyl groups.

As the monovalent organic group having a photopolymerizable group, a monovalent organic group represented by the following formula (9-b) is preferable.

[In the 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, and R ₁₈ represents represents a hydrogen atom or a methyl group, and * represents a bond. ]

_W2 preferably represents an oxygen atom.
R ₁₇ preferably represents a 1,2-ethylene group.

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

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

Here, examples of tetracarboxylic acid derivatives include tetracarboxylic acids, tetracarboxylic acid diesters, tetracarboxylic acid dihalides, tetracarboxylic acid dianhydrides, and the like.

<<Method for producing polyimide and its precursor>>
The method for producing the polyimide and its precursor is not particularly limited, and includes, for example, a known method in which a diamine component and a tetracarboxylic acid derivative are reacted to obtain a polyamic acid, a polyamic acid ester, or a polyimide. Polyamic acids, polyamic acid esters and polyimides can be synthesized by known methods such as those described in WO2013/157586.

A polyamic acid or a polyamic acid ester is produced, for example, by reacting (condensation polymerization) a diamine component and a tetracarboxylic acid derivative in a solvent.

Specific examples of the above solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylisobutyric acid amide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone. Further, when the polymer has high solvent solubility, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formulas [D-1] to [D-3] Any of the indicated solvents can be used.

(In formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms; in formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms; -3], D ³ represents an alkyl group having 1 to 4 carbon atoms.)

These solvents may be used alone or in combination. Further, even a solvent that does not dissolve the polyamic acid may be mixed with the above solvent and used within the range that the polyamic acid or the polyamic acid ester does not precipitate.

When the diamine component and the tetracarboxylic acid derivative are reacted in a solvent, the reaction can be carried out at any concentration, preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass. is. The initial stage of the reaction can be carried out at a high concentration, and then the solvent can be added.
In the reaction, the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid derivative is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the closer this molar ratio is to 1.0, the greater the molecular weight of the polyamic acid produced.

When reacting the diamine component and the tetracarboxylic acid derivative, a thermal polymerization inhibitor may be added to the reaction system in order to avoid polymerization of the photopolymerizable group.
Examples of thermal polymerization inhibitors include hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, and 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, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt and the like.
The amount of thermal polymerization inhibitor to be used is not particularly limited.

Polyimide is obtained by dehydrating and ring-closing the polyamic acid obtained by the above reaction.
Methods for obtaining polyimide include thermal imidization in which the polyamic acid solution obtained by the above reaction is heated as it is, and chemical imidization in which a catalyst is added to the polyamic acid solution. The temperature for thermal imidization in a solution is 100° C. to 400° C., preferably 120° C. to 250° C. It is preferable to remove water generated by the imidization reaction from the system.

The chemical imidization is carried out by adding a basic catalyst and an acid anhydride to the polyamic acid solution obtained by the reaction and stirring at -20°C to 250°C, preferably 0°C to 180°C. can be done. The amount of the basic catalyst is 0.1 to 30 times the moles of the amic acid groups, preferably 0.2 to 20 times the moles, and the amount of the acid anhydride is 1 to 50 times the moles of the amic acid groups. times, preferably 1.5- to 30-fold. Examples of basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, triethylamine is preferred because polyisoimide as a by-product is less likely to form. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, acetic anhydride is preferable because purification after completion of the reaction is facilitated. The rate of imidization by chemical imidization (ratio of repeating units to be ring-closed to all repeating units of the polyimide precursor, also referred to as rate of ring closure) can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time. can.

In the case of recovering the produced imidized product from the imidization reaction solution, the reaction solution may be put into a solvent to precipitate. 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 putting it into a solvent can be filtered and recovered, and then dried at room temperature or under heat under normal pressure or reduced pressure.

The polyimide and its precursor may be end-sealed. A method for terminal blocking is not particularly limited, and for example, a conventionally known method using a monoamine or an acid anhydride can be used.

<<Polybenzoxazole and its precursor>>
Polybenzoxazole is not particularly limited as long as it is a polymer containing benzoxazole in the repeating unit, and may be a copolymer having other repeating units.
Polybenzoxazole can be obtained, for example, by dehydrating and ring-closing a dicarboxylic acid and a bisaminophenol compound as a diamine through a reaction using polyphosphoric acid. Polybenzoxazole can be obtained, for example, by subjecting polyhydroxyamide to dehydration and ring closure by heating or by reaction with phosphoric anhydride, a base, or a carbodiimide compound.

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

When the resin composition is a photosensitive resin composition, the polybenzoxazole and its precursor preferably have a polymerizable unsaturated group. Examples of polymerizable unsaturated groups include (meth)acryloyl groups.

The weight average molecular weight of 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 5,000 to 100, 000 is preferred, 7,000 to 50,000 is more preferred, 10,000 to 50,000 is even more preferred, and 10,000 to 40,000 is particularly preferred.

<Compound Represented by Formula (A)>
The resin composition contains a compound represented by the following formula (A).
A film having excellent adhesion, excellent antioxidant properties, and low dielectric loss tangent on a substrate having metal wiring on its surface by including the compound represented by formula (A) in a resin composition containing polyimide or the like. is obtained.

The present inventors have made intensive studies to obtain a resin composition that can provide a film having both excellent adhesion, excellent antioxidant properties, and low dielectric loss tangent on a substrate having metal wiring on its surface.
Among them, 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.), Triazine-based metal ion scavengers (for example, 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.) As a result of investigations using various additives, it was found that by using the compound represented by formula (A), metal wiring on the surface of the substrate, it has been found that a resin composition can be obtained that provides a film having excellent adhesion, excellent antioxidant properties, and a low dielectric loss tangent.

[In the formula (A), R _a represents a hydrogen atom, a hydroxyl group, a methylol group, or an alkyl group having 1 to 30 carbon atoms. R _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. ]

The alkyl group having 1 to 30 carbon atoms is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 1 to 6 carbon atoms.

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

The compounds represented by formula (A) can be used singly or in combination of two or more.

_Ra is preferably a hydrogen atom.
m is preferably 0.
n is preferably 1.

Compounds represented by formula (A) include 1H-benzotriazole-5-carboxylic acid (5-carboxybenzotriazole), 1H-benzotriazole-4-carboxylic acid (4-carboxybenzotriazole), and combinations thereof. is preferred.

The compound represented by formula (A) may be a commercial product. Commercially available products include, for example, CBT-5 and CBT-SG manufactured by Johoku Kagaku Kogyo Co., Ltd., and VERZONE [registered trademark] C-BTA manufactured by Daiwa Kasei Co., Ltd.

The content of the compound represented by the 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 0.1 parts by mass or more per 100 parts by mass of polyimide or the like. 20 parts by mass is preferable, 0.3 to 10 parts by mass is more preferable, and 0.5 to 5 parts by mass is particularly preferable.

<Solvent>
As the solvent contained in the resin composition, it is preferable to use an organic solvent from the viewpoint of solubility in polyimide and the like. Specifically, 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 or the following formulas [D-1] to [D-3] ], and these can be used alone or in combination of two or more.

The solvent is, for example, 30 parts by mass to 1500 parts by mass, preferably 100 parts by mass to 1000 parts by mass with respect to 100 parts by mass of polyimide or the like, depending on the desired coating film thickness and viscosity of the resin composition. can be used.

<Other ingredients>
In embodiments, the resin composition may further contain components other than the compound represented by Formula (A) and the solvent, such as polyimide. Other components include, for example, photoradical polymerization initiators (also referred to as “photoradical initiators”), crosslinkable compounds (also referred to as “crosslinkers”), thermosetting agents, other resin components, fillers, and sensitizers. , adhesion promoters, thermal polymerization inhibitors, azole compounds, hindered phenol compounds, and the like.

<<Photo radical polymerization initiator>>
When using the resin composition as a photosensitive resin composition, the resin composition contains, for example, a radical photopolymerization initiator.
The photoradical polymerization initiator is not particularly limited as long as it is a compound that absorbs the light source used for photocuring. benzoyldioxy)hexane, 1,4-bis[α-(tert-butyldioxy)-iso-propoxy]benzene, di-tert-butyl peroxide, 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-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, di-tert-butyldiperoxyisophthalate and other organic peroxides; 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloro quinones such as anthraquinone, octamethylanthraquinone, and 1,2-benzanthraquinone; benzoin derivatives such as benzoin methyl, benzoin ethyl ether, α-methylbenzoin, and α-phenylbenzoin; 2,2-dimethoxy-1,2-diphenylethane -1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2 -methyl-1-propan-1-one, 2-hydroxy-1-[4-{4-(2-hydroxy-2-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)- Alkylphenone compounds such as 1-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one; bis(2,4, Acylphosphine oxide compounds such as 6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl] -1,2-octanedione, 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone and other oxime ester compounds. be done.

Radical photopolymerization initiators are 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 (manufactured by BASF), KAYACURE [registered trademark] DETX-S, MBP, DMBI, EPA, OA (manufactured by Nippon Kayaku Co., Ltd.), VICURE-10, 55 (manufactured by STAUFFER Co. LTD), ESACURE KIP150, TZT, 1001 , KTO46, KB1, KL200, KS300, EB3, Triazine-PMS, Triazine A, Triazine B (manufactured by Nihon SiberHegner Co., Ltd.), Adeka Optomer N-1717, N-1414, N- 1606, ADEKA Arkles N-1919T, ADEKA NCI-831E, ADEKA NCI-930, and ADEKA NCI-730 (manufactured by ADEKA Corporation).
These radical photopolymerization initiators may be used alone or in combination of two or more.

The content of the photoradical polymerization initiator is not particularly limited, but is preferably 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of polyimide, etc., and from the viewpoint of photosensitivity characteristics, 0.5 parts by mass to 15 parts by mass. is more preferred. When the photoradical polymerization initiator contains 0.1 parts by mass or more with respect to 100 parts by mass of polyimide or the like, the photosensitivity of the resin composition tends to be improved, while when it contains 20 parts by mass or less, the resin It is easy to improve the thick film curability of the composition.

<<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) is optionally added in order to improve the resolution of the relief pattern. can be contained in the resin composition.
As such a crosslinkable compound, a compound containing a polymerizable group that undergoes a radical polymerization reaction with a photoradical polymerization initiator is preferable, and examples thereof include (meth)acrylic compounds and maleimide compounds, but are not particularly limited to the following. do not have. (Meth)acrylic compounds include diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, ethylene glycol or polyethylene glycol mono- or di(meth)acrylate, propylene glycol or polypropylene glycol mono- or di(meth)acrylate. , mono-, di- or tri(meth)acrylate of glycerol, di(meth)acrylate of 1,4-butanediol, di(meth)acrylate of 1,6-hexanediol, di(meth)acrylate of 1,9-nonanediol Acrylates, di(meth)acrylate of 1,10-decanediol, di(meth)acrylate of neopentyl glycol, cyclohexane di(meth)acrylate, di(meth)acrylate of cyclohexanedimethanol, di(meth)acrylate of tricyclodecanedimethanol 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, benzene trimethacrylate, 9, 9-bis[4-(2-hydroxyethoxy)phenyl]fluorene di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, isobornyl (meth)acrylate, acrylamide and its derivatives, methacryl Amide and derivatives thereof, trimethylolpropane tri(meth)acrylate, glycerol di- or tri-(meth)acrylate, pentaerythritol di-, tri-, or tetra-(meth)acrylate, and ethylene oxide or propylene oxide adducts of these compounds, etc. 2-isocyanatoethyl (meth)acrylate or isocyanate-containing (meth)acrylate, and methyl ethyl ketone oxime, ε-caprolactam, γ-caprolactam, 3,5-dimethylpyrazole, diethyl malonate, ethanol, isopropanol, n- Compounds added with blocking agents such as butanol and 1-methoxy-2-propanol can be mentioned. 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, 1,6'-bismaleimido-(2,2,4-trimethyl)hexane and the like can be mentioned. Commercially available maleimide compounds include BMI-689, BMI-1500, BMI-1700, and BMI-3000 (manufactured by Designer Molecules Inc.). In addition, these compounds may be used individually or may be used in combination of 2 or more types. Moreover, in this specification, (meth)acrylate means acrylate and methacrylate.

Although the content of the crosslinkable compound is not particularly limited, it is preferably 1 to 100 parts by mass, more preferably 1 to 50 parts by mass with respect to 100 parts by mass of polyimide or the like.

<<Heat curing agent>>
Examples of heat curing agents 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 and the like.
The content of the thermosetting agent in the resin composition is not particularly limited.

<<Filler>>
Examples of fillers include inorganic fillers, and specific examples include sols of silica, aluminum nitride, boron nitride, zirconia, alumina, and the like.
The content of the filler in the resin composition is not particularly limited.

<<Other resin components>>
In embodiments, the resin composition may further contain a resin component other than polyimide or the like. Examples of resin components that can be contained in the resin composition include polyoxazoles, polyoxazole precursors, phenol resins, polyamides, epoxy resins, siloxane resins, acrylic resins, and the like.
The content of these resin components is not particularly limited, but is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of polyimide or the like.

<<Sensitizer>>
In the embodiment, when the resin composition is used as a photosensitive resin composition, a sensitizer can be arbitrarily added to the resin composition in order to improve photosensitivity.
Sensitizers include, for example, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal) Cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyl denindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)iso naphthothiazole, 1,3-bis(4′-dimethylaminobenzal)acetone, 1,3-bis(4′-diethylaminobenzal)acetone, 3,3′-carbonyl-bis(7-diethylaminocoumarin), 3 -acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylamino Coumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercapto benzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl) ) naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene and the like.
These can be used alone or in multiple combinations.

Although the content of the sensitizer is not particularly limited, it is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of polyimide or the like.

<<Adhesion Aid>>
In the embodiment, an adhesion promoter can optionally be added to the resin composition in order to further improve the adhesion between the film formed using the resin composition and the substrate.
Examples of adhesion promoters 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]phthalamic acid, benzophenone-3,3′-bis(N-[3-triethoxysilyl]propylamide)-4,4′ -dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyl Silane coupling agents such as trimethoxysilane, and aluminum-based adhesion aids such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like.

Among these adhesion aids, it is more preferable to use a silane coupling agent in terms of adhesion.

The content of the adhesion aid is not particularly limited, but is preferably in the range of 0.5 parts by mass to 25 parts by mass with respect to 100 parts by mass of polyimide or the like.

<<Thermal polymerization inhibitor>>
In the embodiment, a thermal polymerization inhibitor can be arbitrarily blended in order to improve the stability of the viscosity and photosensitivity of the resin composition particularly during storage in the state of a solution containing a solvent.
Examples of thermal polymerization inhibitors include hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, and 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, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt and the like are used.

Although the content of the thermal polymerization inhibitor is not particularly limited, it is preferably in the range of 0.005 parts by mass to 12 parts by mass with respect to 100 parts by mass of polyimide or the like.

<<Azole compound>>
For example, when using a substrate made of copper or a copper alloy, an azole compound can optionally be added to 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).
Azole compounds include, for example, 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl -5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, Hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3, 5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 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, 1-methyl-1H-tetrazole and the like. Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole and 4-methyl-1H-benzotriazole.
In addition, these azole compounds may be used singly or as a mixture of two or more.

The content of the azole compound is not particularly limited, but it is preferably 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of polyimide, etc., and the photosensitivity when the resin composition is used as a photosensitive resin composition. From the viewpoint of properties, it is more preferably 0.5 parts by mass to 5 parts by mass. When the content of the azole compound per 100 parts by mass of polyimide or the like is 0.1 parts by mass or more, discoloration of the copper or copper alloy surface is further suppressed when the resin composition is formed on copper or a copper alloy. On the other hand, when it is 20 parts by mass or less, it is preferable because the photosensitivity when the resin composition is used as a photosensitive resin composition is excellent.

<<Hindered phenol compound>>
In embodiments, a hindered phenol compound may optionally be incorporated into the resin composition to prevent oxidation of the film formed from the resin composition and to prevent oxidation of the azole compound.
Hindered phenol compounds include, for example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl -4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4′-methylenebis(2,6-di-t-butylphenol), 4,4′-thio-bis(3-methyl-6-t-butylphenol), 4,4′-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3 -t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2 -thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydro cinnamamide), 2,2′-methylene-bis(4-methyl-6-t-butylphenol), 2,2′-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5- Trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl) -1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-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-dimethyl benzyl]-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-trimethyl benzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2 ,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3 -hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl -3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl -5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4 -t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t -butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t -Butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione and the like, but are not limited thereto. not something.
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.

The content of the hindered phenol compound is not particularly limited, but it is preferably 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of polyimide or the like. From the viewpoint of photosensitivity, it is more preferably 0.5 parts by mass to 10 parts by mass. When the content of the hindered phenol compound is 20 parts by mass or less per 100 parts by mass of the polyimide or the like, it is preferable because the photosensitivity when the resin composition is used as a photosensitive resin composition is excellent.

The resin composition can be suitably used as a negative photosensitive resin composition for producing a cured relief pattern, which will be described later.

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.

(resin film)
The resin film of the present invention is a baked product of the coating film of the resin composition of the present invention.
As the coating method, a method conventionally used for coating a resin composition, for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, etc., a method of spray coating with a spray coater, etc. can be used.
As a baking method for obtaining a baked product, various methods can be selected such as, for example, using a hot plate, using an oven, and using a heating oven in which a temperature program can be set. Firing 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 may be used.
The thickness of the resin film is not particularly limited, but is preferably 1 μm to 100 μm, more preferably 2 μm to 50 μm.
The resin film is, for example, an insulating film.

(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 photosensitive resist films (so-called dry film resists).
The photosensitive resist film has a base film, a photosensitive resin layer (photosensitive resin film) formed from a photosensitive resin composition, and a cover film.
Usually, a photosensitive resin layer and a cover film are laminated in this order on a base film.

A photosensitive resist film is produced, for example, by coating a base film with a photosensitive resin composition, drying it to form a photosensitive resin layer, and then laminating a cover film on the photosensitive resin layer. can.
As the coating method, a method conventionally used for coating a photosensitive resin composition, for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, etc., or a method of spray coating with a spray coater. method etc. can be used.
The drying method includes, for example, conditions of 20° C. to 200° C. for 1 minute to 1 hour.
The thickness of the resulting photosensitive resin layer is not particularly limited, but is preferably 1 μm to 100 μm, more preferably 2 μm to 50 μm.

A known base film can be used, and for example, a thermoplastic resin film or the like is used. Examples of the thermoplastic resin include polyester such as polyethylene terephthalate. The thickness of the base film is preferably 2 μm to 150 μm.
A known cover film can be used, for example, a polyethylene film, a polypropylene film, or the like. As the cover film, it is preferable to use a film having a weaker adhesion to 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, particularly preferably 5 μm to 50 μm.
The base film and the cover film may be made of the same film material, or may be made of different films.

(Manufacturing method of substrate with cured relief pattern)
The method for producing a cured relief patterned substrate of the present invention comprises:
(1) A step of applying a photosensitive resin composition, which is one embodiment of the resin composition according to the present invention, onto a substrate to form a photosensitive resin layer (photosensitive resin film) on the substrate;
(2) exposing the photosensitive resin layer;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) heat-treating the relief pattern to form a cured relief pattern.

Each step will be explained below.

(1) A step of applying the photosensitive resin composition according to the present invention onto a substrate to form a photosensitive resin layer on the substrate. In this step, the photosensitive resin composition according to the present invention is applied onto the substrate. Then, if necessary, it is dried to form a photosensitive resin layer. As the coating method, a method conventionally used for coating a photosensitive resin composition, for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, etc., or a method of spray coating with a spray coater. method etc. can be used.

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

If necessary, the coating film made of the photosensitive resin composition can be dried, and drying methods include, for example, air drying, heat drying using an oven or hot plate, vacuum drying, and the like. Specifically, when air drying or heat drying is performed, drying can be performed at 20° C. to 200° C. for 1 minute to 1 hour. As described above, a photosensitive resin layer can be formed on the substrate.

(2) Step of exposing the photosensitive resin layer In this step, the photosensitive resin layer formed in the above step (1) is exposed using an exposure device such as a contact aligner, mirror projection, stepper, or the like, using a photomask or a patterned photomask. It is exposed to an ultraviolet light source or the like through a reticle or directly.
Light sources used for exposure include, for example, g-line, h-line, i-line, ghi-line broadband, and KrF excimer laser. The exposure amount is desirably 25 mJ/cm ² to 2000 mJ/cm ² .

After that, for the purpose of improving photosensitivity, etc., post-exposure baking (PEB) and/or pre-development baking may be performed at any combination of temperature and time, if necessary. As for the baking conditions, the temperature is preferably 50° C. to 200° C., and the time is preferably 10 seconds to 600 seconds. is not limited to

(3) Step of developing the exposed photosensitive resin layer to form a relief pattern In this step, the unexposed portion of the exposed photosensitive resin layer is removed by development. As a developing method for developing the photosensitive resin layer after exposure (irradiation), any of conventionally known photoresist developing methods such as a rotary spray method, a paddle method, an immersion method accompanied by ultrasonic treatment, and the like can be used. method can be selected and used. After development, rinsing may be performed for the purpose of removing the developer. Furthermore, for the purpose of adjusting the shape of the relief pattern, etc., post-development baking may be performed at any combination of temperature and time, if necessary.
Organic solvents are preferred as the developer used for development. Examples of organic solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α- Acetyl-γ-butyrolactone and the like are preferred. Moreover, two or more kinds of each solvent can be used, for example, several kinds can be used in combination.
As the rinsing liquid used for rinsing, an organic solvent that is miscible with the developer and has low solubility in the photosensitive resin composition is preferable. Preferred examples of the rinse liquid include methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, toluene, and xylene. Moreover, two or more kinds of each solvent can be used, for example, several kinds can be used in combination.

(4) Step of Heating Relief Pattern to Form Hardened Relief Pattern In this step, the relief pattern obtained by the development is heated and converted into a hardened relief pattern. As the heat-curing method, various methods can be selected, for example, using a hot plate, using an oven, or using a heating oven capable of setting a temperature program. Heating 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 may be used.

Although the thickness of the cured relief pattern is not particularly limited, it is preferably 1 μm to 100 μm, more preferably 2 μm to 50 μm.

(semiconductor device)
Embodiments also provide a semiconductor device comprising a semiconductor element and a cured film provided over or under 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 method for producing a substrate with a cured relief pattern described above.
The present invention can also be applied to a method of manufacturing a semiconductor device using a semiconductor element as a substrate and including the above-described method of manufacturing a substrate with a cured relief pattern as part of the steps. The semiconductor device of the present invention forms a cured relief pattern as a surface protective film, an interlayer insulating film, a rewiring insulating film, a protective film for a flip chip device, a protective film for a semiconductor device having a bump structure, or the like. It can be manufactured by combining with a manufacturing method of a semiconductor device.

(Display device)
In an embodiment, the display device includes a display element and a cured film provided on the display element, wherein the cured film is 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 (for example, the cured relief pattern) may be laminated in direct contact with the display element, or may be laminated with another layer interposed therebetween. For example, the cured film includes a surface protective film, an insulating film, and a flattening film for TFT (Thin Film Transistor) liquid crystal display elements and color filter elements, projections for MVA (Multi-domain Vertical Alignment) type liquid crystal display devices, and A partition wall for an organic EL (Electro-Luminescence) element cathode can be mentioned.

The resin composition of the present invention is useful not only for application to semiconductor devices as described above, but also for applications such as interlayer insulating films for multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, and liquid crystal alignment films. be.

Next, the contents of the present invention will be specifically described with reference to Examples, but the present invention is not limited to these.

The weight-average molecular weight (Mw) shown in the synthesis examples below is the result of measurement by gel permeation chromatography (hereinafter abbreviated as GPC in this specification). For the measurement, a GPC apparatus (HLC-8320GPC (manufactured by Tosoh Corporation)) is used, and the measurement conditions are as follows.
Column: Shodex (registered trademark) KD-805 / Shodex (registered trademark) KD-803 (Showa Denko Co., Ltd.)
・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

The chemical imidization rates shown in the Synthesis Examples below were calculated by the following method. Put 100 mg of polyimide powder in an NMR sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Kagaku Co., Ltd.), deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) mixture) (0 .53 ml) was added thereto, and ultrasonic waves were applied to completely dissolve it.This solution was subjected to proton NMR at 500 MHz using an NMR apparatus (JNM-ECA500) (manufactured by JEOL Ltd.).Chemical imidization rate Determines the proton derived from the structure that does not change before and after imidization as the reference proton, and the proton peak integrated value derived from the NH group of the amic acid appearing around 9.59 ppm to 11.0 ppm. was obtained by the following formula.
Chemical imidization rate (%) = (1-α x/y) x 100
In the above formula, x is the proton peak integrated value derived from the NH group of the amic acid, y is the peak integrated value of the reference proton, and α is one NH group proton of the amic acid in the case of polyamic acid (imidization rate is 0%). is the number ratio of reference protons to

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

<Synthesis Example 2> Synthesis of solvent-soluble polyimide (P-2) Polyamic acid (P-1) 415.9 g obtained in Synthesis Example 1, N-ethyl-2-pyrrolidone 623.84 g, acetic anhydride 32 0.16 g and 5.31 g of triethylamine were added and stirred under 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 then stirred for 10 minutes, and the resulting precipitate was filtered off. After washing the precipitate with 3,770 g of methanol, the obtained precipitate was filtered off. After washing the precipitate again with 3,770 g of methanol, the resulting precipitate was separated by filtration and dried at 50° C. under reduced pressure to obtain a solvent-soluble polyimide (P-2) powder. The chemical imidization rate was 95.3%.

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

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

<Synthesis Example 5> Synthesis of solvent-soluble polyimide (P-5) Polyamic acid (P-4) 1985.1 g obtained in Synthesis Example 4, N-ethyl-2-pyrrolidone 992.6 g, acetic anhydride 105 0.22 g and 17.38 g of triethylamine were added and stirred under air at room temperature for 30 minutes, followed by stirring at 60° C. for 3 hours. Then, 1922 g of the solution diluted by adding 992.6 g of N-ethyl-2-pyrrolidone was taken, slowly added to 4265 g of stirring methanol, and stirred for 10 minutes to obtain The precipitate was filtered off. After washing the precipitate with 1922 g of methanol, the obtained precipitate was filtered off. Further, after the precipitate was washed again with 1922 g of methanol, the resulting precipitate was separated by filtration and dried at 60° C. under reduced pressure to obtain a solvent-soluble polyimide (P-5) powder. The chemical imidization rate was 98.6%.

<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.) in a 2-liter four-necked flask 176.92 g (1.366 mol) of 2-hydroxyethyl methacrylate (manufactured by Sigma-Aldrich Japan GK), 0.74 g (0.007 mol) of hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) and γ-butyrolactone After adding 108.63 g (1.36 mol) of pyridine, the temperature was raised to 50° C. and stirred at 50° C. for 2 hours to obtain a solution containing a compound represented by the following formula: got

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

Main compounds shown in Examples and Comparative Examples are shown below.
・ 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.)

<Example 1>
Powder 1.63 g of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, N-ethyl-2-pyrrolidone 3.80 g, NK ester A-DOD-N 0.49 g as a cross-linking agent, photoradical After mixing and dissolving 0.081 g of IRGACURE [registered trademark] OXE01 as an initiator and 0.024 g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan GK), a polypropylene filter with a pore size of 5 μm was used. A negative photosensitive resin composition was prepared by filtering with a filter.

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

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

<Example 4>
Powder 1.63 g of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, N-ethyl-2-pyrrolidone 3.80 g, NK ester A-DOD-N 0.49 g as a cross-linking agent, photoradical 0.081 g of IRGACURE [registered trademark] OXE01, 0.024 g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan GK), and 1,2,3-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.) as initiators ) was mixed with 0.024 g and dissolved, and filtered using a polypropylene filter having a pore size of 5 μm to prepare a negative photosensitive resin composition.

<Example 5>
Powder 1.63 g of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, N-ethyl-2-pyrrolidone 3.80 g, NK ester A-DOD-N 0.49 g as a cross-linking agent, photoradical As an initiator, 0.081 g of IRGACURE [registered trademark] OXE01, 0.024 g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan GK), and 0.024 g of IRGANOX [registered trademark] 3114 were mixed and dissolved. After that, by filtering using a polypropylene filter having a pore size of 5 μm, a negative photosensitive resin composition was prepared.

<Example 6>
Powder 1.63 g of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, N-ethyl-2-pyrrolidone 3.80 g, NK ester A-DOD-N 0.49 g as a cross-linking agent, photoradical As initiators IRGACURE [registered trademark] OXE01 0.081 g, 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan GK) 0.024 g, and 5-methyl-1H-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd. ) was mixed with 0.024 g and dissolved, and filtered using a polypropylene filter having a pore size of 5 μm to prepare a negative photosensitive resin composition.

<Example 7>
Powder 1.63 g of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, N-ethyl-2-pyrrolidone 3.80 g, NK ester A-DOD-N 0.49 g as a cross-linking agent, photoradical After mixing and dissolving 0.081 g of IRGACURE [registered trademark] OXE01, 0.049 g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan GK), and 0.033 g of KBM-5103 as an initiator, the pore size A negative photosensitive resin composition was prepared by filtering using a 5 μm polypropylene filter.

<Example 8>
Powder 1.63 g of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, N-ethyl-2-pyrrolidone 3.80 g, NK ester A-DOD-N 0.49 g as a cross-linking agent, photoradical As initiators IRGACURE [registered trademark] OXE01 0.081 g, 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan GK) 0.049 g, and 5-methyl-1H-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd. ) was mixed with 0.024 g and dissolved, and filtered using a polypropylene filter having a pore size of 5 μm to prepare a negative photosensitive resin composition.

<Example 9>
Powder 1.63 g of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, N-ethyl-2-pyrrolidone 3.80 g, NK ester A-DOD-N 0.49 g as a cross-linking agent, photoradical As an initiator, 0.081 g of IRGACURE [registered trademark] OXE01, 0.049 g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan GK), and 0.024 g of IRGANOX [registered trademark] 3114 were mixed and dissolved. After that, by filtering using a polypropylene filter having a pore size of 5 μm, a negative photosensitive resin composition was prepared.

<Example 10>
Powder 1.63 g of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, N-ethyl-2-pyrrolidone 3.80 g, NK ester A-DOD-N 0.49 g as a cross-linking agent, photoradical 0.081 g of IRGACURE [registered trademark] OXE01 as an 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. After that, by filtering using a polypropylene filter having a pore size of 5 μm, a negative photosensitive resin composition was prepared.

<Example 11>
Powder 1.63 g of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, N-ethyl-2-pyrrolidone 3.80 g, NK ester A-DOD-N 0.49 g as a cross-linking agent, photoradical 0.081 g of IRGACURE [registered trademark] OXE01 as an initiator and 0.049 g of CBT-SG (a mixture of 4-carboxybenzotriazole and 5-carboxybenzotriazole, manufactured by Johoku Kagaku Kogyo Co., Ltd.) were mixed and dissolved. After that, by filtering using a polypropylene filter having a pore size of 5 μm, a negative photosensitive resin composition was prepared.

<Example 12>
Powder 1.63 g of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, N-ethyl-2-pyrrolidone 3.80 g, NK ester A-DOD-N 0.49 g as a cross-linking agent, photoradical After mixing and dissolving 0.081 g of IRGACURE [registered trademark] OXE01 as an initiator and 0.024 g of CBT-5 (5-carboxybenzotriazole, manufactured by Johoku Chemical Industry Co., Ltd.), a polypropylene filter with a pore size of 5 μm was added. to prepare a negative photosensitive resin composition.

<Example 13>
Powder 1.63 g of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, N-ethyl-2-pyrrolidone 3.80 g, NK ester A-DOD-N 0.49 g as a cross-linking agent, photoradical After mixing and dissolving 0.081 g of IRGACURE [registered trademark] OXE01 as an initiator and 0.049 g of CBT-5 (5-carboxybenzotriazole, manufactured by Johoku Chemical Industry Co., Ltd.), a polypropylene filter with a pore size of 5 μm was added. to prepare a negative photosensitive resin composition.

<Example 14>
NK ester A-DOD-N 2.02 g as a cross-linking agent in 22.44 g of the solution (solid content concentration: 30% by mass) containing the polyamic acid (P-3) obtained in Synthesis Example 3, and IRGACURE as a photoradical initiator. [Registered trademark] 0.34 g of OXE01 and 0.20 g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan GK) are mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5 μm. to prepare a negative photosensitive resin composition.

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

<Example 16>
Powder 6.34 g of polyamic acid ester (P-6) obtained in Synthesis Example 6, N-ethyl-2-pyrrolidone 16.25 g, NK ester A-DOD-N 1.90 g as a cross-linking agent, photoradical initiator 0.317 g of IRGACURE [registered trademark] OXE01 and 0.19 g of 5-carboxybenzotriazole (manufactured by Sigma-Aldrich Japan GK) were mixed and dissolved, and then filtered using a polypropylene filter with a pore size of 5 μm. By doing so, a negative photosensitive resin composition was prepared.

<Comparative Example 1>
Powder 1.63 g of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, N-ethyl-2-pyrrolidone 3.80 g, NK ester A-DOD-N 0.49 g as a cross-linking agent, and light After mixing and dissolving 0.081 g of IRGACURE (registered trademark) OXE01 as a radical initiator, the mixture was filtered using a polypropylene filter having a pore size of 5 μm to prepare a negative photosensitive resin composition.

<Comparative Example 2>
Powder 1.63 g of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, N-ethyl-2-pyrrolidone 3.80 g, NK ester A-DOD-N 0.49 g as a cross-linking agent, photoradical After mixing and dissolving 0.081 g of IRGACURE [registered trademark] OXE01 and 0.033 g of KBM-5103 as initiators, filtering using a polypropylene filter with a pore size of 5 μm gave a negative photosensitive resin composition. was prepared.

<Comparative Example 3>
Powder 1.63 g of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, N-ethyl-2-pyrrolidone 3.80 g, NK ester A-DOD-N 0.49 g as a cross-linking agent, photoradical After mixing and dissolving 0.081 g of IRGACURE [registered trademark] OXE01 and 0.024 g of IRGANOX [registered trademark] 3114 as initiators, filtering using a polypropylene filter with a pore size of 5 μm, negative photosensitive A resin composition was prepared.

<Comparative Example 4>
Powder 1.63 g of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, N-ethyl-2-pyrrolidone 3.80 g, NK ester A-DOD-N 0.49 g as a cross-linking agent, photoradical 0.081 g of IRGACURE [registered trademark] OXE01 as an initiator and 0.024 g of 5-methyl-1H-benzotriazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were mixed and dissolved, and then a polypropylene filter with a pore size of 5 μm was passed through. A negative photosensitive resin composition was prepared by filtering using.

<Comparative Example 5>
Powder 1.63 g of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, N-ethyl-2-pyrrolidone 3.80 g, NK ester A-DOD-N 0.49 g as a cross-linking agent, photoradical After mixing and dissolving 0.081 g of IRGACURE [registered trademark] OXE01 and 0.049 g of 5-methyl-1H-benzotriazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as an initiator, a polypropylene filter with a pore size of 5 μm is passed through the filter. A negative photosensitive resin composition was prepared by filtering using.

<Comparative Example 6>
Powder 1.63 g of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, N-ethyl-2-pyrrolidone 3.80 g, NK ester A-DOD-N 0.49 g as a cross-linking agent, photoradical 0.081 g of IRGACURE [registered trademark] OXE01, 0.024 g of 5-methyl-1H-benzotriazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and 0.24 g of IRGANOX [registered trademark] 3114 are mixed and dissolved as initiators. After that, it was filtered using a polypropylene filter with a pore size of 5 μm to prepare a negative photosensitive resin composition.

<Comparative Example 7>
Powder 1.63 g of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, N-ethyl-2-pyrrolidone 3.80 g, NK ester A-DOD-N 0.49 g as a cross-linking agent, photoradical 0.081 g of IRGACURE [registered trademark] OXE01, 0.049 g of 5-methyl-1H-benzotriazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 0.24 g of IRGANOX [registered trademark] 3114 are mixed and dissolved as initiators. After that, it was filtered using a polypropylene filter with a pore size of 5 μm to prepare a negative photosensitive resin composition.

<Comparative Example 8>
Powder 1.63 g of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, N-ethyl-2-pyrrolidone 3.80 g, NK ester A-DOD-N 0.49 g as a cross-linking agent, photoradical 0.081 g of IRGACURE [registered trademark] OXE01 as an 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. After that, it was filtered using a polypropylene filter with a pore size of 5 μm to prepare a negative photosensitive resin composition.

<Comparative Example 9>
Powder 1.63 g of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, N-ethyl-2-pyrrolidone 3.80 g, NK ester A-DOD-N 0.49 g as a cross-linking agent, photoradical 0.081 g of IRGACURE [registered trademark] OXE01 as an 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. After that, it was filtered using a polypropylene filter with a pore size of 5 μm to prepare a negative photosensitive resin composition.

<Comparative Example 10>
Powder 1.63 g of the solvent-soluble polyimide (P-2) obtained in Synthesis Example 2, N-ethyl-2-pyrrolidone 3.80 g, NK ester A-DOD-N 0.49 g as a cross-linking agent, photoradical 0.081 g of IRGACURE [registered trademark] OXE01 as an initiator and 0.024 g of 6-(dibutylamino)-1,3,5-triazine-2,4-dithiol (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed. After dissolution, a negative photosensitive resin composition was prepared by filtering using a polypropylene filter having a pore size of 5 μm.

[Adhesion evaluation]
An 8-inch silicon wafer on which Cu was evaporated to a thickness of 1.5 μm was cut into 1 cm×1 cm. The silicon wafer was washed with 10% sulfuric acid for 1 minute, washed with pure water for 30 seconds, and then dried. applied. A photosensitive resin film of 22 μm was formed on the substrate (a silicon wafer on which Cu was vapor-deposited) by calcining at 115° C. for 270 seconds. Next, the entire surface was exposed at 500 mJ/cm ² using an i-line aligner (PLA-501, manufactured by Canon Inc.), and then placed in a high-temperature clean oven (CLH-21CD(V)-S, Koyo Thermo Systems Inc.). and sintered at 230° C. for 2 hours in a nitrogen atmosphere. Next, as a reliability test, 125° C./24 hours in air, 30° C./60% humidity, 168 hours, and then, as reflow treatment, 260° C./1 second treatment including temperature rise was performed three times in a nitrogen atmosphere. 192 hours at 130° C., 85% humidity, 230 kPa steam pressure, and a highly accelerated life test (EHS-212MD, manufactured by ESPEC Co., Ltd.). After that, a stud pin with an epoxy adhesive was adhered to the surface of the resin film, and stud pull peel strength was measured using ROMURUS V (Quad Group, USA) to evaluate the adhesion between the Cu surface and the resin film. Separately, substrates (substrates on which a resin film was formed) that had not undergone the reliability test were also prepared, and stud-pull peel strength measurements were similarly conducted on each substrate. Observing the peeling interface after the test, if the peeling occurred due to the cohesive failure of the epoxy adhesive before and after the reliability test, or if the peeling occurred at the interface between the epoxy adhesive and the resin film surface, the adhesive strength was evaluated as "○". , and the case where peeling occurred at the interface between the photosensitive resin film and Cu on either side before and after the reliability test was indicated as "x" as poor adhesion. The results are shown in Tables 1-1 and 1-2.

[Evaluation of antioxidant ability]
A test substrate for evaluation (1 cm × 1 cm) having a base of PI (polyimide) and a Cu wiring having a height of 5 µm and a width of 10 µmL/S was washed with 10% sulfuric acid for 1 minute and then washed with pure water for 30 seconds. 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 calcined at 115°C for 270 seconds. to form a photosensitive resin film.
Next, the entire surface was exposed at 500 mJ/cm ² using an i-line aligner (PLA-501, manufactured by Canon Inc.). Then, using a high-temperature clean oven (CLH-21CD(V)-S, Koyo Thermo Systems Co., Ltd.), it was baked in a nitrogen atmosphere at 230° C. for 2 hours. Next, as a reliability test, 125° C./24 hours, 30° C./60% humidity, 168 hours in air, 260° C./1 second treatment including temperature rise was performed three times as reflow treatment in a nitrogen atmosphere. After treatment with an accelerated life test (EHS-212MD, manufactured by ESPEC Co., Ltd.) at 130 ° C., humidity of 85%, vapor pressure of 230 kPa, and 192 hours, FIB-SEM (manufactured by Japan FI Co., Ltd.) for evaluation. A cut was made on the Cu wiring of the test substrate, and the cross section was observed with an SEM. If the thickness of the oxide film on the Cu wiring formed by the reliability test was thinner than that of Comparative Example 1 (73.7 nm), it was indicated as a good result with "◯", and if it was thicker, it was indicated with "×" as a bad result. . Table 1 shows the results.

[Evaluation of electrical characteristics]
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 coated with an aluminum foil having a thickness of 20 μm, and heated at 115 degrees on a hot plate. C. for 270 seconds to form a photosensitive resin film of about 22 .mu.m on the aluminum foil. Using an i-line aligner (PLA-501, manufactured by Canon Inc.) on the obtained photosensitive resin film, the entire surface of the wafer was exposed at 500 mJ/cm ² , and then a high-temperature clean oven (CLH-21CD (V )-S, manufactured by Koyo Thermo Systems Co., Ltd.) and calcined in a nitrogen atmosphere at 230° C. for 2 hours. Furthermore, the film was obtained by immersing the baked aluminum foil in 6N hydrochloric acid to dissolve the aluminum foil. The obtained film was dried and the dielectric loss tangent at 60 GHz was measured with a split cylinder resonator. The dielectric loss tangent measurement conditions are 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: about 60 GHz
When the dielectric loss tangent value obtained by this measurement was equal to or less than Comparative Example 1 (0.0087), the result was indicated as "Good", and when the value was greater than Comparative Example 1, the result was indicated as "Poor". The results are shown in Tables 1-1 and 1-2.

From the results in Tables 1-1 and 1-2, all the resin films obtained from the negative photosensitive resin compositions of Examples 1 to 16 had good adhesion. Moreover, the resin film obtained from the negative photosensitive resin composition of Comparative Example 1 was formed on the Cu wiring on which the resin film obtained from the negative photosensitive resin composition of Examples 1 to 16 was formed. It was confirmed that the thickness of the oxide film after the reliability test was thinner than that of the Cu wiring, and that the reliability was good. Furthermore, the films obtained from the negative photosensitive resin compositions of Examples 1 to 15 exhibited a dielectric loss tangent lower than that of the film obtained from the negative photosensitive resin composition of Comparative Example 1.

Claims

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 the formula (A), R a represents a hydrogen atom, a hydroxyl group, a methylol group, or an alkyl group having 1 to 30 carbon atoms. R 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. ]
The resin composition according to claim 1, wherein the resin is at least one resin selected from the group consisting of polyimides and precursors thereof.
The resin is a polyimide having a structural unit represented by the following formula (1-a) and the following formula (1-b-1) or represented by the following formula (3) and the following formula (1-b-2) The resin composition according to claim 1, which is a polyimide precursor having structural units.

[In formulas (1-a) and (1-b-1), Ar 1 represents a tetravalent organic group, and X 11 represents a divalent organic group having a photopolymerizable group.
In formulas (3) and (1-b-2), Ar 3 represents a tetravalent organic group, L 1 and L 2 each independently represent a monovalent organic group, and X 12 represents a divalent represents an organic group, and at least one of L 1 , L 2 and X 12 has a photopolymerizable group. ]
The resin composition according to claim 1, 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 represents 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. The resin composition according to claim 4, wherein V 1 in formula (9-a) represents an ester bond and W 1 represents an oxygen atom.
5. The resin composition according to claim 4, wherein R 15 in formula (9-a) represents a 1,2-ethylene group.
The resin composition according to claim 1, wherein Ra in formula (A) represents a hydrogen atom.
The resin composition according to claim 1, wherein m in the formula (A) represents 0.
The resin composition according to claim 1, wherein the compound represented by formula (A) contains at least one of 1H-benzotriazole-5-carboxylic acid and 1H-benzotriazole-4-carboxylic acid.
The resin composition according to claim 1, further comprising a photoradical polymerization initiator.
The resin composition according to claim 1, further comprising a crosslinkable compound.
The resin composition according to claim 1, which is for forming an insulating film.
The resin composition according to claim 1, which is a photosensitive resin composition.
The resin composition according to claim 1, which is a negative photosensitive resin composition.
A resin film which is a baked product of the coating film of the resin composition according to any one of claims 1 to 14.
The resin film according to claim 15, which is an insulating film.
A photosensitive resist film comprising a base film, a photosensitive resin layer formed from the resin composition according to claim 13 or 14, and a cover film.
(1) applying the resin composition according to claim 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;
(4) heat-treating the relief pattern to form a cured relief pattern;
A method of manufacturing a cured relief patterned substrate, comprising:
The method for producing a cured relief patterned substrate according to claim 18, wherein in the step (1), the resin composition is applied to the substrate having metal wiring on its surface.
The method for manufacturing a cured relief patterned substrate according to claim 18, wherein the developer used for the development is an organic solvent.
A substrate with a cured relief pattern manufactured by the method according to claim 18.
A semiconductor device comprising a semiconductor element and a cured film provided above or below the semiconductor element, wherein the cured film is a cured film formed from the resin composition according to any one of claims 1 to 14. A certain semiconductor device.
The resin composition is a photosensitive resin composition,
23. The semiconductor device according to claim 22, wherein said cured film is a cured relief pattern formed from said photosensitive resin composition.