JP2024025724A - Negative photosensitive resin composition, and method of producing cured relief pattern - Google Patents

Abstract

To provide a negative photosensitive resin composition capable of forming a cured relief pattern which not only can achieve low curing shrinkage and make high adhesion compatible with the low curing shrinkage, but also has a high glass transition temperature.SOLUTION: The negative photosensitive resin composition comprises (A) a polyimide precursor comprising a structural unit represented by the general formulas (1) and/or (2), (B) a photoinitiator, and (C) a solvent.SELECTED DRAWING: Figure 1

Description

The present invention relates to a negative photosensitive resin composition, a method for producing a cured relief pattern, and the like.

Conventionally, polyimide resins, polybenzoxazole resins, and phenolic resins, which have excellent heat resistance, electrical properties, and mechanical properties, have been used as insulating materials for electronic components, as well as passivation films, surface protection films, and interlayer insulation films for semiconductor devices. etc. are used. Among these, resins provided in the form of photosensitive resin compositions can easily form relief pattern films with excellent heat resistance by thermal imidization treatment by coating, exposing, developing, and curing the composition. Therefore, by using a photosensitive resin composition, it is easier to shorten the process compared to using a non-photosensitive material.

There are various methods for semiconductor packaging in semiconductor devices. In recent years, a semiconductor chip mounting technology called fan-out wafer level package (hereinafter sometimes referred to as "FOWLP") has been proposed (for example, see Patent Document 1). In this mounting technology, a pre-processed wafer is diced to produce individual chips, the individual chips are reassembled on a support, sealed with mold resin, and after the support is peeled off, a rewiring layer is formed. form. Here, in FOWLP, the rewiring layer is larger than the chip area and formed with a thin film thickness. Therefore, many external connection terminals can be arranged, and the package can be made thinner.

Japanese Patent Application Publication No. 2005-167191 International Publication No. 2018/155639 JP2021-152634A Japanese Patent Application Publication No. 2005-326579

In FOWLP, the rewiring layer has a multilayered structure, and in order to form copper wiring well on each layer, an insulating film (also called an "interlayer insulating film") is used to form the rewiring layer. There was a background in which high flatness was required. As a means of flattening the redistribution layer, a method of suppressing curing shrinkage of the redistribution layer is considered, and methods using polyfunctional (meth)acrylate as a polyimide precursor have been proposed, as in Patent Documents 2 and 3. ing. However, in this method, the polyimide precursor and the polyfunctional (meth)acrylate form a crosslinked structure, resulting in incomplete imide cyclization during curing, and as a result, the insulating film (polyimide resin) and the copper wiring There was a problem that adhesion deteriorated.

Regarding the adhesion with the base material, as in Patent Document 4, a compound having a heterocyclic skeleton as part of its structure is used as a diamine compound forming the polyimide precursor, and the thermal expansion coefficient of the polyimide precursor is reduced. Measures have been proposed. However, this method has the problem of large curing shrinkage due to volatilization of the crosslinkable side chain component of the polymer accompanying imide cyclization, and also has insufficient adhesion to the substrate. As described above, it has been difficult to simultaneously reduce curing shrinkage and improve adhesion to copper.

Furthermore, in recent years, the package size of semiconductor packages for high performance computing (HPC), AI, data centers, etc. has increased as chip size and the number of chips mounted in one package have increased. there were. At this time, if the glass transition temperature of the insulating film forming the rewiring layer is low, there is a problem that cracks occur in the rewiring layer due to stress, warping, and the like.

The present invention was devised in view of these circumstances. That is, the present invention provides a negative photosensitive resin composition that can achieve low curing shrinkage, achieve both low curing shrinkage and high adhesion, and also form a cured relief pattern having a high glass transition temperature. One of the purposes is to provide. Another object of the present invention is to provide a method for manufacturing a cured relief pattern.

｛式中、
Ｘは、それぞれ独立して、４価の有機基であり、
Ｙ_１及びＹ_２は、窒素原子を含む５～６員複素環を有するアミン化合物に由来する基であり、前記アミン化合物中の炭素原子数に対する窒素原子数の割合（窒素原子／炭素原子）は３５％以上５００％以下であり、
Ｒ_１及びＲ_２は、それぞれ独立して、水素原子、又は炭素数１～４０の１価の有機基であり、
Ｒ_１及びＲ_２の少なくとも一つは、エチレン性不飽和結合を有する基であり、そして、
ｍ及びｎは、少なくとも一方が１以上の整数である。｝
で表される構造単位を含むポリイミド前駆体、
（Ｂ）光重合開始剤、及び
（Ｃ）溶媒
を含む、ネガ型感光性樹脂組成物。
［２］ 前記エチレン性不飽和結合を有する基は、下記一般式（３）：

（式中、
Ｒ_３、Ｒ_４、及びＲ_５は、水素原子、又は炭素数１～３の１価の有機基であり、そして、
ｌは、２～１０から選ばれる整数である。）
で表される基である、項目１に記載のネガ型感光性樹脂組成物。
［３］ 前記Ｙ_１及びＹ_２は、下記一般式（４）又は（５）：

（式中、
Ｈｅ_１は、１価の有機基で置換されてよい、テトラゾール環、トリアゾール環、イミダゾール環、ピラゾール環、ピロール環、ピリミジン環、ピリジン環、又はトリアジン環であり、
Ｈｅ_２は、１価の有機基で置換されてよい、イミダゾール環、ピラゾール環、又はピロール環であり、
Ａｒは、１価の有機基で置換されてよい、５～６員芳香族環又は５～６員複素環であり、そして、
ＡｒとＨｅ_２は、縮環構造を形成している。）
で表されるアミン化合物に由来する基である、項目１又は２に記載のネガ型感光性樹脂組成物。
［４］
前記Ｈｅ_１は、１価の有機基で置換されてよい、テトラゾール環、トリアゾール環、イミダゾール環、ピラゾール環、又はピロール環である、項目３に記載のネガ型感光性樹脂組成物。
［５］
前記Ｙ_１及びＹ_２は、下記一般式（６）又は（７）：

（式中、
Ｈｅ_３は、１価の有機基で置換されてよい、トリアゾール環、イミダゾール環、又はピラゾール環であり、
Ｈｅ_４は、１価の有機基で置換されてよい、イミダゾール環、又はピロール環であり、
Ａｒは、１価の有機基で置換されてよい、６員芳香族環又は６員複素環であり、そして、
ＡｒとＨｅ_４は、縮環構造を形成している。）
で表されるアミン化合物に由来する構造である、項目１～４のいずれか１項に記載のネガ型感光性樹脂組成物。
［６］
前記Ｘは、下記一般式（８）～（１１）：

から成る群から選択される少なくとも１種である、項目１～５のいずれか１項に記載のネガ型感光性樹脂組成物。
［７］
前記（Ｂ）光重合開始剤は、下記一般式（１２）：

（式中、
Ｒ_６、Ｒ_７、及びＲ_８は、１価の有機基であり、そして、
Ｒ_６、及びＲ_７は、互いに連結して環構造を形成してよい。）
で表されるオキシムエステル構造を有する、項目１～６のいずれか１項に記載のネガ型感光性樹脂組成物。
［８］
前記（Ｂ）光重合開始剤は、下記一般式（１３）～（１５）：

（式中、
Ｒ_ａは、炭素数１～１０の１価の有機基であり、
Ｒ_ｂは、炭素数１～２０の有機基であり、
Ｒ_ｃは、炭素数１～１０の有機基であり、
Ｒ_ｄは、炭素数１～１０の有機基であり、
ａは、０～２の整数であり、
Ｒ_ｅは、炭素数１～４の有機基であり、
Ｒ_ｅが複数ある場合、その複数のＲ_ｅ同士で環を形成してよく、
Ｒ_ｇは、炭素数１～２０の１価の有機基であり、
Ｒ_ｈは、炭素数１～１０の有機基であり、
Ｒ_ｆは、水素原子又は炭素数１～１０の有機基であり、そして、
Ｒ_ｉ、及びＲ_ｊは、炭素数１～１０の１価の有機基である。）
から成る群から選択される少なくとも１種である、項目１～７のいずれか１項に記載のネガ型感光性樹脂組成物。
［９］
（Ｄ）ラジカル重合性化合物を更に含む、項目１～８のいずれか１項に記載のネガ型感光性樹脂組成物。
［１０］
（Ｅ）熱架橋剤を更に含む、項目１～９のいずれか１項に記載のネガ型感光性樹脂組成物。
［１１］
項目１～１０のいずれか１項に記載のネガ型感光性樹脂組成物を硬化してポリイミドを形成する工程を含む、ポリイミドの製造方法。
［１２］
以下の工程：
（１）項目１～１０のいずれか１項に記載のネガ型感光性樹脂組成物を基板上に塗布して、前記基板上に感光性樹脂層を形成する工程と、
（２）前記感光性樹脂層を露光する工程と、
（３）前記露光後の感光性樹脂層を現像して、レリーフパターンを形成する工程と、
（４）前記レリーフパターンを加熱処理して、硬化レリーフパターンを形成する工程と
を含む、硬化レリーフパターンの製造方法。
［１３］
（Ａ）下記一般式（１）及び／又は（２）：

｛式中、 Ｘは、それぞれ独立して、４価の有機基であり、
Ｙ_１及びＹ_２は、窒素原子を含む５～６員複素環を有するアミン化合物に由来する基であり、
Ｒ_１及びＲ_２は、それぞれ独立して、水素原子、又は炭素数１～４０の１価の有機基であり、
Ｒ_１及びＲ_２の少なくとも一つは、エチレン性不飽和結合を有する基であり、そして、
ｍ及びｎは、少なくとも一方が１以上の整数である。｝
で表される構造単位を含み、
前記一般式（１）で表される構造単位Ｍと、
前記一般式（２）で表される構造単位Ｎと、を
０／１００≦（構造単位Ｍのモル数／構造単位Ｎのモル数）＜１００／０
の割合で含む、ポリイミド前駆体、
（Ｂ）光重合開始剤、及び
（Ｃ）溶媒
を含む、ネガ型感光性樹脂組成物。
［１４］
下記式：
熱重量減少率（％）＝（２３０℃昇温後の重量／２３℃における重量）×１００
で表される熱重量減少率が５％以上２５％未満である、ポリイミド前駆体。
［１５］
テトラカルボン酸二無水物と、アミン化合物と、の重合体である（Ａ）ポリイミド前駆体を含む、ネガ型感光性樹脂組成物であって、
（Ａ）ポリイミド前駆体は側鎖にエチレン性不飽和結合を有し、
前記アミン化合物が有する環の数は、１つ又は２つであり、かつ、
前記環の少なくとも一つは、窒素原子を含む５～６員複素環を含む、
ネガ型感光性樹脂組成物。
［１６］
テトラカルボン酸二無水物と、窒素原子を含む５～６員複素環を有するアミン化合物と、の重合体であるポリイミド前駆体を含む、ネガ型感光性樹脂組成物の製造方法であって、
前記方法は、下記（ｉ）、及び／又は（ｉｉ）：
（ｉ）前記アミン化合物が有する環の数は、１つ又は２つであること
（ｉｉ）前記アミン化合物中の炭素原子数に対する窒素原子数の割合（窒素原子／炭素原子）は、３５％以上５００％以下であること
を満たし、かつ、
テトラカルボン酸二無水物に含まれるカルボキシル基（－ＣＯＯＨ基）と、
前記アミン化合物に含まれる、アミノ基（－ＮＨ_２）又は複素環中の－ＮＨ－と、を反応させ、（Ａ）ポリイミド前駆体を得る工程を含む、ネガ型感光性樹脂組成物の製造方法。
［１７］
テトラカルボン酸二無水物と、窒素原子を含む５～６員複素環を有するアミン化合物と、の重合体であるポリイミド前駆体の製造方法であって、
前記方法は、下記（ｉ）、及び／又は（ｉｉ）：
（ｉ）前記アミン化合物が有する環の数は、１つ又は２つであること
（ｉｉ）前記アミン化合物中の炭素原子数に対する窒素原子数の割合（窒素原子／炭素原子）は、３５％以上５００％以下であること
を満たし、かつ、
テトラカルボン酸二無水物に含まれるカルボキシル基（－ＣＯＯＨ基）と、前記アミン化合物に含まれる、アミノ基（－ＮＨ_２）又は複素環中の－ＮＨ－構造と、を反応させる工程を含む、（Ａ）ポリイミド前駆体の製造方法。 One aspect of the present invention is as follows.
[1]
(A) The following general formula (1) and/or (2):

{During the ceremony,
X is each independently a tetravalent organic group,
Y ₁ and Y ₂ are groups derived from an amine compound having a 5- to 6-membered heterocycle containing a nitrogen atom, and the ratio of the number of nitrogen atoms to the number of carbon atoms in the amine compound (nitrogen atom/carbon atom) is 35% or more and 500% or less,
R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms,
At least one of R ₁ and R ₂ is a group having an ethylenically unsaturated bond, and
At least one of m and n is an integer of 1 or more. }
A polyimide precursor containing a structural unit represented by
A negative photosensitive resin composition containing (B) a photopolymerization initiator and (C) a solvent.
[2] The group having an ethylenically unsaturated bond has the following general formula (3):

(In the formula,
R ₃ , R ₄ and R ₅ are a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and
l is an integer selected from 2 to 10. )
The negative photosensitive resin composition according to item 1, which is a group represented by:
[3] Y ₁ and Y ₂ are represented by the following general formula (4) or (5):

(In the formula,
He ₁ is a tetrazole ring, triazole ring, imidazole ring, pyrazole ring, pyrrole ring, pyrimidine ring, pyridine ring, or triazine ring, which may be substituted with a monovalent organic group,
_He2 is an imidazole ring, pyrazole ring, or pyrrole ring, which may be substituted with a monovalent organic group,
Ar is a 5- to 6-membered aromatic ring or a 5- to 6-membered heterocycle, which may be substituted with a monovalent organic group, and
Ar and He ₂ form a condensed ring structure. )
The negative photosensitive resin composition according to item 1 or 2, which is a group derived from an amine compound represented by:
[4]
The negative photosensitive resin composition according to item 3, wherein the He ₁ is a tetrazole ring, triazole ring, imidazole ring, pyrazole ring, or pyrrole ring, which may be substituted with a monovalent organic group.
[5]
The above Y ₁ and Y ₂ are represented by the following general formula (6) or (7):

(In the formula,
He ₃ is a triazole ring, imidazole ring, or pyrazole ring that may be substituted with a monovalent organic group,
He ₄ is an imidazole ring or a pyrrole ring, which may be substituted with a monovalent organic group,
Ar is a 6-membered aromatic ring or a 6-membered heterocycle which may be substituted with a monovalent organic group, and
Ar and He ₄ form a condensed ring structure. )
The negative photosensitive resin composition according to any one of items 1 to 4, which has a structure derived from an amine compound represented by:
[6]
The above X represents the following general formulas (8) to (11):

The negative photosensitive resin composition according to any one of items 1 to 5, which is at least one selected from the group consisting of.
[7]
The photopolymerization initiator (B) has the following general formula (12):

(In the formula,
R ₆ , R ₇ , and R ₈ are monovalent organic groups, and
R ₆ and R ₇ may be linked to each other to form a ring structure. )
The negative photosensitive resin composition according to any one of items 1 to 6, which has an oxime ester structure represented by:
[8]
The photopolymerization initiator (B) has the following general formulas (13) to (15):

(In the formula,
R _a is a monovalent organic group having 1 to 10 carbon atoms,
R _b is an organic group having 1 to 20 carbon atoms,
R _c is an organic group having 1 to 10 carbon atoms,
R _d is an organic group having 1 to 10 carbon atoms,
a is an integer from 0 to 2,
R _e is an organic group having 1 to 4 carbon atoms,
When there is a plurality of R _e , the plurality of R _e may form a ring,
R _g is a monovalent organic group having 1 to 20 carbon atoms,
R _h is an organic group having 1 to 10 carbon atoms,
R _f is a hydrogen atom or an organic group having 1 to 10 carbon atoms, and
R _i and R _j are monovalent organic groups having 1 to 10 carbon atoms. )
The negative photosensitive resin composition according to any one of items 1 to 7, which is at least one selected from the group consisting of.
[9]
(D) The negative photosensitive resin composition according to any one of items 1 to 8, further comprising a radically polymerizable compound.
[10]
(E) The negative photosensitive resin composition according to any one of items 1 to 9, further comprising a thermal crosslinking agent.
[11]
A method for producing polyimide, comprising the step of curing the negative photosensitive resin composition according to any one of items 1 to 10 to form polyimide.
[12]
The following steps:
(1) applying the negative photosensitive resin composition according to any one of items 1 to 10 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) A method for producing a cured relief pattern, including the step of heat-treating the relief pattern to form a cured relief pattern.
[13]
(A) The following general formula (1) and/or (2):

{In the formula, each X is independently a tetravalent organic group,
Y ₁ and Y ₂ are groups derived from an amine compound having a 5- to 6-membered heterocycle containing a nitrogen atom,
R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms,
At least one of R ₁ and R ₂ is a group having an ethylenically unsaturated bond, and
At least one of m and n is an integer of 1 or more. }
Contains the structural unit represented by
A structural unit M represented by the general formula (1),
The structural unit N represented by the general formula (2) is 0/100≦(number of moles of structural unit M/number of moles of structural unit N)<100/0
a polyimide precursor containing in a proportion of
A negative photosensitive resin composition containing (B) a photopolymerization initiator and (C) a solvent.
[14]
The following formula:
Thermogravimetric reduction rate (%) = (Weight after heating to 230°C/Weight at 23°C) x 100
A polyimide precursor having a thermogravimetric reduction rate expressed by 5% or more and less than 25%.
[15]
A negative photosensitive resin composition comprising (A) a polyimide precursor that is a polymer of tetracarboxylic dianhydride and an amine compound,
(A) The polyimide precursor has an ethylenically unsaturated bond in the side chain,
The number of rings that the amine compound has is one or two, and
At least one of the rings includes a 5- to 6-membered heterocycle containing a nitrogen atom,
Negative photosensitive resin composition.
[16]
A method for producing a negative photosensitive resin composition comprising a polyimide precursor that is a polymer of tetracarboxylic dianhydride and an amine compound having a 5- to 6-membered heterocycle containing a nitrogen atom, the method comprising:
The method includes the following (i) and/or (ii):
(i) The number of rings that the amine compound has is one or two. (ii) The ratio of the number of nitrogen atoms to the number of carbon atoms in the amine compound (nitrogen atoms/carbon atoms) is 35% or more. 500% or less, and
A carboxyl group (-COOH group) contained in tetracarboxylic dianhydride,
A method for producing a negative photosensitive resin composition, comprising a step of reacting an amino group (-NH ₂ ) or -NH- in a heterocycle contained in the amine compound to obtain (A) a polyimide precursor. .
[17]
A method for producing a polyimide precursor that is a polymer of tetracarboxylic dianhydride and an amine compound having a 5- to 6-membered heterocycle containing a nitrogen atom, comprising:
The method includes the following (i) and/or (ii):
(i) The number of rings that the amine compound has is one or two. (ii) The ratio of the number of nitrogen atoms to the number of carbon atoms in the amine compound (nitrogen atoms/carbon atoms) is 35% or more. 500% or less, and
A step of reacting the carboxyl group (-COOH group) contained in the tetracarboxylic dianhydride with the amino group (-NH ₂ ) or the -NH- structure in the heterocycle contained in the amine compound, (A) Method for producing polyimide precursor.

｛式中、
Ｘは、それぞれ独立して、４価の有機基であり、
Ｙ_１及びＹ_２は、窒素原子を含む５～６員複素環を有するアミン化合物に由来する基であり、前記アミン化合物中の炭素原子数に対する窒素原子数の割合（窒素原子／炭素原子）は３５％以上５００％以下であり、
Ｒ_１及びＲ_２は、それぞれ独立して、水素原子、又は炭素数１～４０の１価の有機基であり、
Ｒ_１及びＲ_２の少なくとも一つは、エチレン性不飽和結合を有する基であり、そして、
ｍ及びｎは、少なくとも一方が１以上の整数である。｝
で表される構造単位を含むポリイミド前駆体、
（Ｂ）光重合開始剤、及び
（Ｃ）溶媒
を含む、ネガ型感光性樹脂組成物。
［３Ａ］
前記エチレン性不飽和結合を有する基は、下記一般式（３）：

（式中、
Ｒ_３、Ｒ_４、及びＲ_５は、水素原子、又は炭素数１～３の１価の有機基であり、そして、
ｌは、２～１０から選ばれる整数である。）
で表される基である、項目２Ａに記載のネガ型感光性樹脂組成物。
［４Ａ］
前記Ｙ_１及びＹ_２は、下記一般式（４）又は（５）：

（式中、
Ｈｅ_１は、１価の有機基で置換されてよい、テトラゾール環、トリアゾール環、イミダゾール環、ピラゾール環、ピロール環、ピリミジン環、ピリジン環、又はトリアジン環であり、
Ｈｅ_２は、１価の有機基で置換されてよい、イミダゾール環、ピラゾール環、又はピロール環であり、
Ａｒは、１価の有機基で置換されてよい、５～６員芳香族環又は５～６員複素環であり、そして、
ＡｒとＨｅ_２は、縮環構造を形成している。）
で表されるアミン化合物に由来する基である、項目２Ａ又は３Ａに記載のネガ型感光性樹脂組成物。
［５Ａ］
前記Ｙ_１及びＹ_２は、下記一般式（６）又は（７）：

（式中、
Ｈｅ_３は、１価の有機基で置換されてよい、トリアゾール環、イミダゾール環、又はピラゾール環であり、
Ｈｅ_４は、１価の有機基で置換されてよい、イミダゾール環、又はピロール環であり、
Ａｒは、１価の有機基で置換されてよい、６員芳香族環又は６員複素環であり、そして、
ＡｒとＨｅ_４は、縮環構造を形成している。）
で表されるアミン化合物に由来する構造である、項目２Ａ～４Ａのいずれか１項に記載のネガ型感光性樹脂組成物。
［６Ａ］
前記Ｘは、下記一般式（８）～（１１）：

から成る群から選択される少なくとも１種である、項目２Ａ～５Ａのいずれか１項に記載のネガ型感光性樹脂組成物。
［７Ａ］
前記（Ｂ）光重合開始剤は、下記一般式（１２）：

（式中、
Ｒ_６、Ｒ_７、及びＲ_８は、１価の有機基であり、そして、
Ｒ_６、及びＲ_７は、互いに連結して環構造を形成してよい。）
で表されるオキシムエステル構造を有する、項目２Ａ～６Ａのいずれか１項に記載のネガ型感光性樹脂組成物。
［８Ａ］
前記（Ｂ）光重合開始剤は、下記一般式（１３）～（１５）：

（式中、
Ｒ_ａは、炭素数１～１０の１価の有機基であり、
Ｒ_ｂは、炭素数１～２０の有機基であり、
Ｒ_ｃは、炭素数１～１０の有機基であり、
Ｒ_ｄは、炭素数１～１０の有機基であり、
ａは、０～２の整数であり、
Ｒ_ｅは、炭素数１～４の有機基であり、
Ｒ_ｅが複数ある場合、その複数のＲ_ｅ同士で環を形成してよく、
Ｒ_ｇは、炭素数１～２０の１価の有機基であり、
Ｒ_ｈは、炭素数１～１０の有機基であり、
Ｒ_ｆは、水素原子又は炭素数１～１０の有機基であり、そして、
Ｒ_ｉ、及びＲ_ｊは、炭素数１～１０の１価の有機基である。）
から成る群から選択される少なくとも１種である、項目２Ａ～７Ａのいずれか１項に記載のネガ型感光性樹脂組成物。
［９Ａ］
（Ｄ）ラジカル重合性化合物を更に含む、項目２Ａ～８Ａのいずれか１項に記載のネガ型感光性樹脂組成物。
［１０Ａ］
（Ｅ）熱架橋剤を更に含む、項目２Ａ～９Ａのいずれか１項に記載のネガ型感光性樹脂組成物。
［１１Ａ］
項目１Ａ～１０Ａのいずれか１項に記載のネガ型感光性樹脂組成物を硬化してポリイミドを形成する工程を含む、ポリイミドの製造方法。
［１２Ａ］
以下の工程：
（１）項目１Ａ～１０Ａのいずれか１項に記載のネガ型感光性樹脂組成物を基板上に塗布して、前記基板上に感光性樹脂層を形成する工程と、
（２）前記感光性樹脂層を露光する工程と、
（３）前記露光後の感光性樹脂層を現像して、レリーフパターンを形成する工程と、
（４）前記レリーフパターンを加熱処理して、硬化レリーフパターンを形成する工程と
を含む、硬化レリーフパターンの製造方法。
［１３Ａ］
（Ａ）下記一般式（１）及び／又は（２）：

｛式中、Ｘは、それぞれ独立して、４価の有機基であり、
Ｙ_１及びＹ_２は、窒素原子を含む５～６員複素環を有するアミン化合物に由来する基であり、
Ｒ_１及びＲ_２は、それぞれ独立して、水素原子、又は炭素数１～４０の１価の有機基であり、
Ｒ_１及びＲ_２の少なくとも一つは、エチレン性不飽和結合を有する基であり、そして、
ｍ及びｎは、少なくとも一方が１以上の整数である。｝
で表される構造単位を含み、
前記一般式（１）で表される構造単位Ｍと、
前記一般式（２）で表される構造単位Ｎと、を
０／１００≦（構造単位Ｍのモル数／構造単位Ｎのモル数）＜１００／０
の割合で含む、ポリイミド前駆体、
（Ｂ）光重合開始剤、及び
（Ｃ）溶媒
を含む、ネガ型感光性樹脂組成物。
［１４Ａ］
下記式：
熱重量減少率（％）＝（２３０℃昇温後の重量／２３℃における重量）×１００
で表される熱重量減少率が５％以上２５％未満である、ポリイミド前駆体。
［１５Ａ］
テトラカルボン酸二無水物と、アミン化合物と、の重合体であるポリイミド前駆体を含む、ネガ型感光性樹脂組成物の製造方法であって、
前記方法は、下記（ｉ）、及び／又は（ｉｉ）：
（ｉ）前記アミン化合物が有する環の数は、１つ又は２つであること
（ｉｉ）前記アミン化合物中の炭素原子数に対する窒素原子数の割合（窒素原子／炭素原子）は、３５％以上５００％以下であること
を満たし、かつ、
テトラカルボン酸二無水物に含まれるカルボキシル基（－ＣＯＯＨ基）と、
前記アミン化合物に含まれる、アミノ基（－ＮＨ_２）又は複素環中の－ＮＨ－と、を反応させ、（Ａ）ポリイミド前駆体を得る工程を含む、ネガ型感光性樹脂組成物の製造方法。
［１６Ａ］
テトラカルボン酸二無水物と、アミン化合物と、の重合体であるポリイミド前駆体の製造方法であって、
前記方法は、下記（ｉ）、及び／又は（ｉｉ）：
（ｉ）前記アミン化合物が有する環の数は、１つ又は２つであること
（ｉｉ）前記アミン化合物中の炭素原子数に対する窒素原子数の割合（窒素原子／炭素原子）は、３５％以上５００％以下であること
を満たし、かつ、
テトラカルボン酸二無水物に含まれるカルボキシル基（－ＣＯＯＨ基）と、前記アミン化合物に含まれる、アミノ基（－ＮＨ_２）又は複素環中の－ＮＨ－構造と、を反応させる工程を含む、（Ａ）ポリイミド前駆体の製造方法。 Note that aspects related to the present disclosure are as follows.
[1A]
A negative photosensitive resin composition comprising (A) a polyimide precursor that is a polymer of tetracarboxylic dianhydride and an amine compound,
The number of rings that the amine compound has is one or two, and
At least one of the rings includes a 5- to 6-membered heterocycle containing a nitrogen atom,
Negative photosensitive resin composition.
[2A]
(A) The following general formula (1) and/or (2):

{During the ceremony,
X is each independently a tetravalent organic group,
Y ₁ and Y ₂ are groups derived from an amine compound having a 5- to 6-membered heterocycle containing a nitrogen atom, and the ratio of the number of nitrogen atoms to the number of carbon atoms in the amine compound (nitrogen atom/carbon atom) is 35% or more and 500% or less,
R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms,
At least one of R ₁ and R ₂ is a group having an ethylenically unsaturated bond, and
At least one of m and n is an integer of 1 or more. }
A polyimide precursor containing a structural unit represented by
A negative photosensitive resin composition containing (B) a photopolymerization initiator and (C) a solvent.
[3A]
The group having an ethylenically unsaturated bond has the following general formula (3):

(In the formula,
R ₃ , R ₄ and R ₅ are a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and
l is an integer selected from 2 to 10. )
The negative photosensitive resin composition according to item 2A, which is a group represented by:
[4A]
The above Y ₁ and Y ₂ are represented by the following general formula (4) or (5):

(In the formula,
He ₁ is a tetrazole ring, triazole ring, imidazole ring, pyrazole ring, pyrrole ring, pyrimidine ring, pyridine ring, or triazine ring, which may be substituted with a monovalent organic group,
_He2 is an imidazole ring, pyrazole ring, or pyrrole ring, which may be substituted with a monovalent organic group,
Ar is a 5- to 6-membered aromatic ring or a 5- to 6-membered heterocycle, which may be substituted with a monovalent organic group, and
Ar and He ₂ form a condensed ring structure. )
The negative photosensitive resin composition according to item 2A or 3A, which is a group derived from an amine compound represented by:
[5A]
The above Y ₁ and Y ₂ are represented by the following general formula (6) or (7):

(In the formula,
He ₃ is a triazole ring, imidazole ring, or pyrazole ring that may be substituted with a monovalent organic group,
He ₄ is an imidazole ring or a pyrrole ring, which may be substituted with a monovalent organic group,
Ar is a 6-membered aromatic ring or a 6-membered heterocycle which may be substituted with a monovalent organic group, and
Ar and He ₄ form a condensed ring structure. )
The negative photosensitive resin composition according to any one of items 2A to 4A, which has a structure derived from an amine compound represented by:
[6A]
The above X represents the following general formulas (8) to (11):

The negative photosensitive resin composition according to any one of items 2A to 5A, which is at least one selected from the group consisting of:
[7A]
The photopolymerization initiator (B) has the following general formula (12):

(In the formula,
R ₆ , R ₇ , and R ₈ are monovalent organic groups, and
R ₆ and R ₇ may be linked to each other to form a ring structure. )
The negative photosensitive resin composition according to any one of items 2A to 6A, which has an oxime ester structure represented by:
[8A]
The photopolymerization initiator (B) has the following general formulas (13) to (15):

(In the formula,
R _a is a monovalent organic group having 1 to 10 carbon atoms,
R _b is an organic group having 1 to 20 carbon atoms,
R _c is an organic group having 1 to 10 carbon atoms,
R _d is an organic group having 1 to 10 carbon atoms,
a is an integer from 0 to 2,
R _e is an organic group having 1 to 4 carbon atoms,
When there is a plurality of R _e , the plurality of R _e may form a ring,
R _g is a monovalent organic group having 1 to 20 carbon atoms,
R _h is an organic group having 1 to 10 carbon atoms,
R _f is a hydrogen atom or an organic group having 1 to 10 carbon atoms, and
R _i and R _j are monovalent organic groups having 1 to 10 carbon atoms. )
The negative photosensitive resin composition according to any one of items 2A to 7A, which is at least one selected from the group consisting of:
[9A]
(D) The negative photosensitive resin composition according to any one of items 2A to 8A, further comprising a radically polymerizable compound.
[10A]
(E) The negative photosensitive resin composition according to any one of items 2A to 9A, further comprising a thermal crosslinking agent.
[11A]
A method for producing polyimide, comprising the step of curing the negative photosensitive resin composition according to any one of items 1A to 10A to form polyimide.
[12A]
The following steps:
(1) applying the negative photosensitive resin composition according to any one of items 1A to 10A 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) A method for producing a cured relief pattern, including the step of heat-treating the relief pattern to form a cured relief pattern.
[13A]
(A) The following general formula (1) and/or (2):

{In the formula, each X is independently a tetravalent organic group,
Y ₁ and Y ₂ are groups derived from an amine compound having a 5- to 6-membered heterocycle containing a nitrogen atom,
R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms,
At least one of R ₁ and R ₂ is a group having an ethylenically unsaturated bond, and
At least one of m and n is an integer of 1 or more. }
Contains the structural unit represented by
A structural unit M represented by the general formula (1),
The structural unit N represented by the general formula (2) is 0/100≦(number of moles of structural unit M/number of moles of structural unit N)<100/0
a polyimide precursor containing in a proportion of
A negative photosensitive resin composition containing (B) a photopolymerization initiator and (C) a solvent.
[14A]
The following formula:
Thermogravimetric reduction rate (%) = (Weight after heating to 230°C/Weight at 23°C) x 100
A polyimide precursor having a thermogravimetric reduction rate expressed by 5% or more and less than 25%.
[15A]
A method for producing a negative photosensitive resin composition comprising a polyimide precursor that is a polymer of tetracarboxylic dianhydride and an amine compound,
The method includes the following (i) and/or (ii):
(i) The number of rings that the amine compound has is one or two. (ii) The ratio of the number of nitrogen atoms to the number of carbon atoms in the amine compound (nitrogen atoms/carbon atoms) is 35% or more. 500% or less, and
A carboxyl group (-COOH group) contained in tetracarboxylic dianhydride,
A method for producing a negative photosensitive resin composition, comprising a step of reacting an amino group (-NH ₂ ) or -NH- in a heterocycle contained in the amine compound to obtain (A) a polyimide precursor. .
[16A]
A method for producing a polyimide precursor that is a polymer of tetracarboxylic dianhydride and an amine compound, the method comprising:
The method includes the following (i) and/or (ii):
(i) The number of rings that the amine compound has is one or two. (ii) The ratio of the number of nitrogen atoms to the number of carbon atoms in the amine compound (nitrogen atoms/carbon atoms) is 35% or more. 500% or less, and
A step of reacting the carboxyl group (-COOH group) contained in the tetracarboxylic dianhydride with the amino group (-NH ₂ ) or the -NH- structure in the heterocycle contained in the amine compound, (A) Method for producing polyimide precursor.

According to the present invention, a negative photosensitive resin composition that can achieve low curing shrinkage, achieve both low curing shrinkage and high adhesion, and also form a cured relief pattern having a high glass transition temperature. can be provided.
Further, according to the present invention, a method for producing a cured relief pattern, etc. (including a method for producing the above-mentioned negative photosensitive resin composition, a polyimide precursor related to the above-mentioned negative photosensitive resin composition, a method for producing a cured relief pattern), etc. , polyimide manufacturing method, polyimide, polyimide manufacturing method, and semiconductor device).

FIG. 1 is a schematic cross-sectional view showing a configuration example of a semiconductor device according to the present embodiment. FIG. 1 is a schematic plan view showing a configuration example of a semiconductor device according to the present embodiment. FIG. 3 is a process diagram showing an example of manufacturing a semiconductor device according to the present embodiment.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail. The present invention is not limited to the following embodiment, and can be implemented with various modifications within the scope of the gist.
In this specification, "(meth)acrylic" means "methacrylic" and/or "acrylic". As used herein, "organic group" means a hydrocarbon group consisting of carbon and hydrogen, and derivatives thereof. The derivatives may contain atoms other than carbon and hydrogen (eg, nitrogen, oxygen, sulfur, silicon). In this specification, the structures of moieties represented by the same symbol in the formulas may be the same or different from each other when a plurality of moieties are present in the molecule. In this specification, in numerical ranges described in stages, the upper limit or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. In this specification, the upper limit value or lower limit value described in a certain numerical range may be replaced with the value described in the Examples. In this specification, the word "step" is included not only in an independent step but also in the term even if it cannot be clearly distinguished from other steps, as long as the function of the step is achieved. In the drawings, the scale, shape, and length may be exaggerated for clarity.

[First aspect]
《Negative photosensitive resin composition》
In one aspect, the negative photosensitive resin composition of the present embodiment (hereinafter also simply referred to as "photosensitive resin composition"):
A photosensitive resin composition comprising (A) a polyimide precursor that is a polymer of tetracarboxylic dianhydride and an amine compound,
The polyimide precursor (A) has an ethylenically unsaturated bond in its side chain,
The number of rings that the amine compound has is one or two, and
At least one of the rings includes a 5- to 6-membered heterocycle containing a nitrogen atom.
According to this, there is provided a photosensitive resin composition that can achieve low curing shrinkage, achieve both low curing shrinkage and high adhesion, and also form a cured relief pattern having a high glass transition temperature. be able to.

｛式中、
Ｘは、それぞれ独立して、４価の有機基であり、
Ｙ_１及びＹ_２は、窒素原子を含む５～６員複素環を有するアミン化合物に由来する基であり、上記アミン化合物中の炭素原子数に対する窒素原子数の割合（窒素原子／炭素原子）は３５％以上５００％以下であり、
Ｒ_１及びＲ_２は、それぞれ独立して、水素原子、又は炭素数１～４０の１価の有機基であり、
Ｒ_１及びＲ_２の少なくとも一つは、エチレン性不飽和結合を有する基であり、そして、
ｍ及びｎは、少なくとも一方が１以上の整数である。｝
で表される構造単位を含むポリイミド前駆体、
（Ｂ）光重合開始剤、及び
（Ｃ）溶媒
を含む。
これによれば、低硬化収縮を実現できるうえ、低硬化収縮と高い密着性とを両立でき、更に、高いガラス転位温度をも有する硬化レリーフパターンを形成可能な、感光性樹脂組成物を提供することができる。 In particular, in one aspect of the photosensitive resin composition of this embodiment,
(A) The following general formula (1) and/or (2):

{During the ceremony,
X is each independently a tetravalent organic group,
Y ₁ and Y ₂ are groups derived from an amine compound having a 5- to 6-membered heterocycle containing a nitrogen atom, and the ratio of the number of nitrogen atoms to the number of carbon atoms in the amine compound (nitrogen atom/carbon atom) is 35% or more and 500% or less,
R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms,
At least one of R ₁ and R ₂ is a group having an ethylenically unsaturated bond, and
At least one of m and n is an integer of 1 or more. }
A polyimide precursor containing a structural unit represented by
Contains (B) a photopolymerization initiator and (C) a solvent.
According to this, there is provided a photosensitive resin composition which can achieve low curing shrinkage, achieve both low curing shrinkage and high adhesion, and also form a cured relief pattern having a high glass transition temperature. be able to.

The photosensitive resin composition of this embodiment includes the following (i) and/or (ii):
(i) The number of rings that the amine compound has is one or two. (ii) The ratio of the number of nitrogen atoms to the number of carbon atoms in the amine compound (nitrogen atoms/carbon atoms) is 35% or more. 500% or less may be satisfied, and from the viewpoint of easily achieving the effects of the present invention, preferably both are satisfied.
That is, in this embodiment,
An embodiment in which it is optional whether or not to satisfy (ii) after satisfying (i);
An embodiment in which it is optional whether or not to satisfy (i) after satisfying (ii);
An aspect that satisfies both (i) and (ii);
Any aspect of the above is also included.

｛式中、Ｘは、それぞれ独立して、４価の有機基であり、
Ｙ_１及びＹ_２は、窒素原子を含む５～６員複素環を有するアミン化合物に由来する基であり、
Ｒ_１及びＲ_２は、それぞれ独立して、水素原子、又は炭素数１～４０の１価の有機基であり、
Ｒ_１及びＲ_２の少なくとも一つは、エチレン性不飽和結合を有する基であり、そして、
ｍ及びｎは、少なくとも一方が１以上の整数である。｝
で表される構造単位を含み、
一般式（１）で表される構造単位Ｍと、
一般式（２）で表される構造単位Ｎと、を
０／１００≦（構造単位Ｍのモル数／構造単位Ｎのモル数）＜１００／０
の割合で含む、ポリイミド前駆体、
（Ｂ）光重合開始剤、及び
（Ｃ）溶媒
を含む。
かかる樹脂組成物によっても、低硬化収縮を実現できるうえ、低硬化収縮と高い密着性とを両立でき、更に、高いガラス転位温度をも有する硬化レリーフパターンを形成可能である。 In one embodiment, the photosensitive resin composition includes:
(A) The following general formula (1) and/or (2):

{In the formula, each X is independently a tetravalent organic group,
Y ₁ and Y ₂ are groups derived from an amine compound having a 5- to 6-membered heterocycle containing a nitrogen atom,
R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms,
At least one of R ₁ and R ₂ is a group having an ethylenically unsaturated bond, and
At least one of m and n is an integer of 1 or more. }
Contains the structural unit represented by
A structural unit M represented by general formula (1),
The structural unit N represented by general formula (2) is 0/100≦(number of moles of structural unit M/number of moles of structural unit N)<100/0
a polyimide precursor containing in a proportion of
Contains (B) a photopolymerization initiator and (C) a solvent.
With such a resin composition, it is possible to achieve low curing shrinkage, achieve both low curing shrinkage and high adhesion, and furthermore, it is possible to form a cured relief pattern having a high glass transition temperature.

The above ratio (number of moles of structural unit M/number of moles of structural unit N) is preferably 0/100≦(number of moles of structural unit M/number of moles of structural unit N)≦75/25, and 0/100≦( More preferably, 0/100≦(number of moles of structural unit M/number of moles of structural unit N)≦25/75 (number of moles of structural unit M/number of moles of structural unit N). A photosensitive resin composition in which the above ratio is controlled within a predetermined range is likely to exhibit the effects of the present invention. Further, the above ratio (number of moles of structural unit M/number of moles of structural unit N) may be 0/100<the above ratio (number of moles of structural unit M/number of moles of structural unit N), and 5/95≦the above ratio. The ratio (number of moles of structural unit M/number of moles of structural unit N) may be used.

<(A) Polyimide precursor>
(A) In one embodiment, the polyimide precursor includes a structural unit represented by formula (1) and/or (2). (A) At least a portion of the polyimide precursor is cyclized (imidized) by heating.

（式中、
Ｒ_３、Ｒ_４及びＲ_５は、水素原子、又は炭素数１～３の１価の有機基であり、そして、
ｌは、２～１０から選ばれる整数である。）
で表される基であることが感光特性の観点から好ましい。 In the formula, the group having an ethylenically unsaturated bond has the following general formula (3):

(In the formula,
R ₃ , R ₄ and R ₅ are a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and
l is an integer selected from 2 to 10. )
A group represented by is preferable from the viewpoint of photosensitive characteristics.

In the formula, the proportion of R ₁ and R ₂ as hydrogen atoms may be 0% or more, preferably 10% or less, more preferably 5% or less, based on the total number of moles of R ₁ and R ₂ , More preferably, it is 1% or less. In the formula, the ratio of R ₁ and R ₂ to the group represented by the above formula (3) may be 100% or less, and preferably 70% or more, based on the total number of moles of R ₁ and R ₂ . , more preferably 80% or more, and still more preferably 90% or more.
It is preferable that the proportion of hydrogen atoms and/or the proportion of organic groups of formula (3) be within the above ranges from the viewpoint of photosensitivity and storage stability.

In the formula, at least one of m and n is an integer of 1 or more.
(A) When the polyimide precursor contains the structural unit represented by formula (1), m may be an integer of 1 or more, and n may be 0 or more (0 or 1 or more).
(A) When the polyimide precursor contains the structural unit represented by formula (2), n may be an integer of 1 or more, and m may be 0 or more (0 or 1 or more). m and n may be an integer of 150 or less, preferably an integer of 100 or less, more preferably an integer of 70 or less, from the viewpoint of the photosensitive characteristics of the photosensitive resin composition. m and n may be the same, m may be larger than n, and n may be larger than m.

（式中、Ｒ_６は、それぞれ独立に、水素原子、フッ素原子、炭素数１～１０の１価の炭化水素基、及び炭素数１～１０の１価の含フッ素炭化水素基から成る群から選択される少なくとも１つであり、ｌは、それぞれ独立に０～２から選ばれる整数であり、ｍは、それぞれ独立に、０～３から選ばれる整数であり、そしてｎは、それぞれ独立に、０～４から選ばれる整数である。）から成る群から選択される構造を有する基が挙げられる。上記式（Ｉ）で表される構造を有するＸは、耐熱性と感光特性とを両立する観点から特に好ましい。Ｘは、１種でも２種以上の組み合わせでもよい。 (X: group derived from tetracarboxylic dianhydride)
In the formula, X is a group derived from tetracarboxylic dianhydride, which is a raw material for the polyimide precursor (A). From the viewpoint of achieving both heat resistance and photosensitivity, X is preferably an organic group having 6 to 40 carbon atoms, more preferably -COOR ₁ group, -COOR ₂ group and -CONH- group are in the ortho position to each other. It is an aromatic group or an alicyclic aliphatic group. X is an organic group containing an aromatic ring and having 6 to 40 carbon atoms, such as the following general formula (I):

(In the formula, R ₆ is each independently selected from the group consisting of a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a monovalent fluorinated hydrocarbon group having 1 to 10 carbon atoms. l is each independently an integer selected from 0 to 2, m is each independently an integer selected from 0 to 3, and n is each independently selected from is an integer selected from 0 to 4). X having the structure represented by the above formula (I) is particularly preferable from the viewpoint of achieving both heat resistance and photosensitivity. X may be one type or a combination of two or more types.

｛式中、Ｒ_６、ｌ、ｍ及びｎは、上記式（Ｉ）中のＲ_６、ｌ、ｍ、及びｎと同じである。｝から成る群から選択される少なくとも１種が、機械特性、銅密着性、及び耐薬品性の観点から好ましい。 Among them, X is the following general formula:

{In the formula, R _6, l, m and n are the same as R _6, l, m and n in the above formula (I). } is preferred from the viewpoint of mechanical properties, copper adhesion, and chemical resistance.

から成る群から選択される少なくとも１種であることが、本発明の効果を奏し易い観点から好ましい。 Furthermore, X is represented by the following formulas (8) to (11):

At least one type selected from the group consisting of is preferred from the viewpoint of easily achieving the effects of the present invention.

(Y: group derived from an amine compound)
In the formula, Y ₁ and Y ₂ are groups derived from an amine compound having a 5- to 6-membered heterocycle containing a nitrogen atom.
In one embodiment, (i) the amine compound has one or two rings. According to this, it is possible to achieve both low curing shrinkage and high adhesion to copper. In the present specification, the "ring" in "the number of rings an amine compound has" means an alicyclic ring that may be substituted, an aromatic ring that may be substituted, and a heterocycle that may be substituted, which are contained in the amine compound. do. The "ring" is introduced into the polymer skeleton when the amine compound is used to prepare a polyimide precursor.
Further, in one embodiment, (ii) the ratio of the number of nitrogen atoms to the number of carbon atoms in the amine compound (nitrogen atoms/carbon atoms) is 35% or more and 500% or less.
According to the above, not only can low curing shrinkage be achieved, but also low curing shrinkage and high adhesion to copper can be achieved at the same time.

Regarding the effects of the present invention, without being bound by theory, it is believed that by realizing (i) and/or (ii) in the above amine compound, the nucleophilicity of the amide moiety in the polyimide precursor is reduced. . It is thought that this suppresses excessive imide cyclization during the curing process and reduces curing shrinkage. Furthermore, by introducing a 5- to 6-membered heterocyclic structure containing a nitrogen atom into the main chain skeleton of the polymer, the heterocyclic moiety causes interaction with copper, and despite relatively insufficient imide cyclization. , it is thought that high adhesion can be expressed.

In the formula, the ratio (nitrogen atom/carbon atom) is preferably 75% or more, more preferably 100% or more, and still more preferably 150% or more from the viewpoint of suppressing curing shrinkage and adhesion. The above ratio (nitrogen atom/carbon atom) may be 400% or less, or 300% or less.

（式中、
Ｈｅ_１は、１価の有機基で置換されてよい、テトラゾール環、トリアゾール環、イミダゾール環、ピラゾール環、ピロール環、ピリミジン環、ピリジン環、又はトリアジン環であり、
Ｈｅ_２は、１価の有機基で置換されてよい、イミダゾール環、ピラゾール環、又はピロール環であり、
Ａｒは、１価の有機基で置換されてよい、５～６員芳香族環又は５～６員複素環であり、そして、
ＡｒとＨｅ_２は、縮環構造を形成している。）
で表されるアミン化合物に由来する基であることが好ましい。
このようなＹ_１及びＹ_２は、上記（ｉ）、及び／又は（ｉｉ）を満たすアミン化合物によって導入し易く、よって、本発明の効果を奏し易い。同様の観点から、特に、Ｈｅ_１については、１価の有機基で置換されてよい、テトラゾール環、トリアゾール環、イミダゾール環、ピラゾール環、又はピロール環であることが好ましい。 In the formula, Y ₁ and Y ₂ are the following general formula (4) or (5):

(In the formula,
He ₁ is a tetrazole ring, triazole ring, imidazole ring, pyrazole ring, pyrrole ring, pyrimidine ring, pyridine ring, or triazine ring, which may be substituted with a monovalent organic group,
_He2 is an imidazole ring, pyrazole ring, or pyrrole ring, which may be substituted with a monovalent organic group,
Ar is a 5- to 6-membered aromatic ring or a 5- to 6-membered heterocycle, which may be substituted with a monovalent organic group, and
Ar and He ₂ form a condensed ring structure. )
A group derived from an amine compound represented by is preferable.
Such Y ₁ and Y ₂ can be easily introduced using an amine compound that satisfies (i) and/or (ii) above, and therefore can easily exhibit the effects of the present invention. From the same viewpoint, He ₁ is preferably a tetrazole ring, triazole ring, imidazole ring, pyrazole ring, or pyrrole ring, which may be substituted with a monovalent organic group.

In the formula, He ₁ and He ₂ may each be substituted with a monovalent organic group. Since the "monovalent organic group" here includes an amino group (-NH ₂ ), formulas (4) and (5) each include embodiments having a plurality of amino groups (-NH ₂ ). .

In the formula, the organic group in He ₁ and He ₂ that may be substituted with a monovalent organic group (excluding the above amino group) is such that the bonding site between the ring part and the substituent part does not undergo a decomposition reaction in the curing process. Groups that are easily formed are preferred from the viewpoints of copper adhesion and glass transition temperature. Specifically, the preferred organic group is at least one selected from the group consisting of a urea group, a urethane group, a tert-butoxycarbonyl group, a benzyloxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, and a phthaloyl group. Examples include groups that can provide one structure to a substituent moiety. When He ₁ and He ₂ have a monovalent organic group, the organic group is preferably bonded to the nitrogen atom in the ring portion from the viewpoint of degradability of the bonding site between the ring portion and the substituent portion.

Examples of the compound represented by formula (4) include 5-aminotetrazole, 3,5-diamino-1,2,4-triazole, 4,5-diamino-1H-1,2,3-triazole, 5-amino -1H-1,2,4-triazole, 5-amino-1H-1,2,3-triazole, 2,5-diamino-1H-imidazole, 3,5-diamino-1H-pyrazole, 3,4-diamino -1H-pyrazole, 3-aminopyrazole, 4-aminopyrazole, 2-amino-1H-imidazole, 5-amino-1H-imidazole, 2,5-diamino-1H-pyrrole, 2,4-diamino-1H-pyrrole , 2,3-diamino-1H-pyrrole, 3,4-diamino-1H-pyrrole, 3-amino-1H-pyrrole, 4,6-diaminopyrimidine, 2,6-diaminopyridine, 2,4-diaminopyrimidine, 2, Examples include 5-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,4-diamino-6-methyl-1,3,5-triazine, and benzoguanamine.

Examples of the compound represented by formula (5) include 5-aminoindazole, 5-aminobenzimidazole, 2,6-diamino-1H-benzimidazole, 5-aminopurine, adenine, 6,8-diamino-9H-purine. , 4-aminopyrazolo[3,4-d]pyrimidine, 2,6-diaminopurine, 6-amino-7-deazapurine, 8-azaadenine and the like.

（式中、
Ｈｅ_３は、１価の有機基で置換されてよい、トリアゾール環、イミダゾール環、又はピラゾール環であり、
Ｈｅ_４は、１価の有機基で置換されてよい、イミダゾール環、又はピロール環であり、
Ａｒは、１価の有機基で置換されてよい、６員芳香族環又は６員複素環であり、そして、
ＡｒとＨｅ_４は、縮環構造を形成している。）
で表されるアミン化合物に由来する基であることが好ましい。
このようなＹ_１及びＹ_２は、上記（ｉ）、及び／又は（ｉｉ）を満たすアミン化合物によって導入し易く、よって、本発明の効果を奏し易い。また、このようなＹ_１及びＹ_２を有することは、銅との密着性、及びガラス転位温度の観点から好ましい。 In the formula, Y ₁ and Y ₂ are the following general formula (6) or (7):

(In the formula,
He ₃ is a triazole ring, imidazole ring, or pyrazole ring that may be substituted with a monovalent organic group,
He ₄ is an imidazole ring or a pyrrole ring, which may be substituted with a monovalent organic group,
Ar is a 6-membered aromatic ring or a 6-membered heterocycle which may be substituted with a monovalent organic group, and
Ar and He ₄ form a condensed ring structure. )
A group derived from an amine compound represented by the following is preferable.
Such Y ₁ and Y ₂ can be easily introduced using an amine compound that satisfies (i) and/or (ii) above, and therefore can easily exhibit the effects of the present invention. Moreover, having such Y ₁ and Y ₂ is preferable from the viewpoint of adhesion with copper and glass transition temperature.

Among the compounds represented by formula (6), 3,5-diamino-1,2,4-triazole, 3,5-diamino-1H- Pyrazole is preferred.

Among the compounds represented by formula (7), 2,6-diamino-1H-benzimidazole and 6,8-diamino-9H-purine are preferred from the viewpoint of adhesion between the polymer and copper and glass transition temperature. .

｛式中、
Ｘ、Ｒ_１及びＲ_２は、式（１）及び（２）における場合と同様であり、
Ｙ_３は、式（６）におけるＨｅ_３と同様であり、
Ｙ_４は、式（７）における、Ａｒ及びＨｅ_４の縮環構造と同様である。｝
で表される構造を有するポリイミド前駆体を得ることができ、これにより、高い密着性と高いガラス転位温度を有する硬化膜を実現し易い。
上記効果は理論に拘束されないが、式（１Ａ）における、Ｙ_３で表される複素環中の－ＮＨ－構造、及び／又は、式（１Ｂ）における、Ｙ_４と結合するアミノ基（－ＮＨ_２）が、銅界面と相互作用を形成し易く、よって、特に高い密着性を発現し易いと考えられる。更に、硬化工程において、上記－ＮＨ－構造、及び／又は上記アミノ基が、ポリマー中の末端カルボニル基等と反応することで、３次元的な架橋構造を形成すると考えられ、この場合、硬化膜のガラス転位温度を上昇させると考えられる。 By using the above amine compound, for example, the following general formula (1A) and/or (2A):

{During the ceremony,
X, R ₁ and R ₂ are the same as in formulas (1) and (2),
Y ₃ is the same as He ₃ in formula (6),
Y ₄ is the same as the condensed ring structure of Ar and He ₄ in formula (7). }
It is possible to obtain a polyimide precursor having the structure represented by the following, and thereby it is easy to realize a cured film having high adhesiveness and a high glass transition temperature.
Although the above effects are not limited by theory, the -NH- structure in the heterocycle represented by Y ₃ in formula (1A) and/or the amino group (-NH) bonded to Y ₄ in formula (1B) ₂ ) is likely to easily form an interaction with the copper interface, and therefore, is likely to exhibit particularly high adhesion. Furthermore, in the curing process, the -NH- structure and/or the amino group are thought to form a three-dimensional crosslinked structure by reacting with the terminal carbonyl group in the polymer, and in this case, the cured film It is thought that this increases the glass transition temperature of the glass.

(Other groups)
Within one aspect of the invention,
As X, a structure other than X exemplified above;
Structures other than Y ₁ and Y ₂ exemplified above as Y ₁ and Y ₂ ;
may be included as other structures.

（式中、Ｒ_６は、それぞれ独立に、水素原子、フッ素原子、炭素数１～１０の１価の炭化水素基、及び炭素数１～１０の１価の含フッ素炭化水素基から成る群から選ばれる少なくとも１つであり、ｎは、それぞれ独立に０～４から選ばれる整数であり、そして、pは、１～２０から選ばれる整数である。）
で表される構造（他の構造）を含んでよい。 In the formula, the divalent organic group represented by Y ₁ is, for example, the following general formula (II) and (II-1):

(In the formula, R ₆ is each independently selected from the group consisting of a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a monovalent fluorinated hydrocarbon group having 1 to 10 carbon atoms. (n is an integer independently selected from 0 to 4, and p is an integer selected from 1 to 20.)
(other structures) may be included.

（式中、Ｒ_ｘは、それぞれ独立に、炭素数１～１０の１価の有機基であり、ａは、それぞれ独立に、０～４の整数であり、Ａは、メチル基、酸素原子又は硫黄原子であり、Ｂは、それぞれ独立に、酸素原子又は硫黄原子であり、Ｃは、下記式：

から成る群から選択される少なくとも１種である。）
から成る群から選択される少なくとも１種であることが、耐熱性、耐薬品性、解像性の観点から好ましい。 In particular, when the divalent organic group represented by Y ₁ contains other structures, such other structures have the following general formulas (16) to (19):

(In the formula, R _x is each independently a monovalent organic group having 1 to 10 carbon atoms, a is each independently an integer of 0 to 4, and A is a methyl group, an oxygen atom, or is a sulfur atom, B is each independently an oxygen atom or a sulfur atom, and C is the following formula:

At least one member selected from the group consisting of: )
At least one selected from the group consisting of is preferable from the viewpoint of heat resistance, chemical resistance, and resolution.

In formula (1 ₎ , when Y ₁ includes a structure represented by the above formula (II) or (II-1), the above formula ( _II ) or (II- The proportion of the compound derived from 1) is preferably 75% by mass or less, more preferably 50% by mass or less, particularly preferably 25% by mass or less.

<Other polyimide precursors>
Within one embodiment of the present invention, the photosensitive resin composition includes:
As X, a structure other than X exemplified above;
Structures other than Y ₁ and Y ₂ exemplified above as Y ₁ and Y ₂ ;
(other polyimide precursors).
In the photosensitive resin composition, the total amount of other polyimide precursors may be 50% by mass or less, 30% by mass or less, 15% by mass or less, based on the total amount of the polyimide precursor (A), and may be substantially Generally, 0% by mass is sufficient.

<(B) Photopolymerization initiator>
As the photopolymerization initiator, a radical photopolymerization initiator is preferable,
Benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, fluorenone;
Acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone;
Thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone;
benzyl, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal and other benzyl derivatives;
Benzoin derivatives such as benzoin and benzoin methyl ether;
1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propane Dione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, Oximes such as 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime;
N-arylglycines such as N-phenylglycine;
Peroxides such as benzoyl perchloride;
Aromatic biimidazoles, titanocenes;
Photoacid generators such as α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide;
are preferred. Among these, oximes are more preferred from the viewpoint of photosensitivity.

（式中、Ｒ_６、Ｒ_７、及びＲ_８は、１価の有機基であり、Ｒ_６、及びＲ_７は、互いに連結して環構造を形成してよい。）
で表される構造（オキシムエステル構造）を有することが好ましい。 From the viewpoint of photosensitivity, the oxime photopolymerization initiator has the following general formula (12):

(In the formula, R ₆ , R ₇ , and R ₈ are monovalent organic groups, and R ₆ and R ₇ may be linked to each other to form a ring structure.)
It is preferable to have a structure represented by (oxime ester structure).

（式中、
Ｒ_ａは、炭素数１～１０の１価の有機基であり、
Ｒ_ｂは、炭素数１～２０の有機基であり、
Ｒ_ｃは、炭素数１～１０の有機基であり、
Ｒ_ｄは、炭素数１～１０の有機基であり、
ａは、０～２の整数であり、
Ｒ_ｅは、炭素数１～４の有機基であり、
Ｒ_ｅが複数ある場合、その複数のＲ_ｅ同士で環を形成してよく、
Ｒ_ｇは、炭素数１～２０の１価の有機基であり、
Ｒ_ｈは、炭素数１～１０の有機基であり、
Ｒ_ｆは、水素原子又は炭素数１～１０の有機基であり、そして、
Ｒ_ｉ、及びＲ_ｊは、炭素数１～１０の１価の有機基である。）
から成る群から選択される少なくとも１種であることが好ましい。 Among them, from the viewpoint of photosensitivity, oxime photopolymerization initiators have the following general formulas (13) to (15):

(In the formula,
R _a is a monovalent organic group having 1 to 10 carbon atoms,
R _b is an organic group having 1 to 20 carbon atoms,
R _c is an organic group having 1 to 10 carbon atoms,
R _d is an organic group having 1 to 10 carbon atoms,
a is an integer from 0 to 2,
R _e is an organic group having 1 to 4 carbon atoms,
When there is a plurality of R _e , the plurality of R _e may form a ring,
R _g is a monovalent organic group having 1 to 20 carbon atoms,
R _h is an organic group having 1 to 10 carbon atoms,
R _f is a hydrogen atom or an organic group having 1 to 10 carbon atoms, and
R _i and R _j are monovalent organic groups having 1 to 10 carbon atoms. )
It is preferable that it is at least one selected from the group consisting of.

（式中、
Ｒ_９は、メチル基又はフェニル基であり、Ｒ_１０は、水素原子又は炭素数１～１２の１価の有機基であり、Ｒ_１１は、炭素数１～５のアルキル基、炭素数１～５のアルコキシ基、又はフェニル基であり、
Ｚは、イオウ又は酸素原子であり、Ｒ_１２は、メチル基、フェニル基であり、Ｒ_１３～Ｒ_１５は、水素原子又は１価の有機基であり、
Ｒ_１６は、１価の有機基であり、Ｒ_１７は、炭素数１～５のアルキル基であり、Ｒ_１８は、炭素数１～４のアルキル基又は炭素数３～１０の飽和脂環構造を有する１価の有機基であり、Ｒ_１９は、メチル基、エチル基、プロピル基、又はフェニル基である。）
から成る群から選択される少なくとも１つの構造を有することがより好ましい。 In particular, from the viewpoint of photosensitivity, oxime photopolymerization initiators have the following general formulas (18A) to (18C):

(In the formula,
R ₉ is a methyl group or a phenyl group, R ₁₀ is a hydrogen atom or a monovalent organic group having 1 to 12 carbon atoms, and R ₁₁ is an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms; 5 is an alkoxy group or a phenyl group,
Z is a sulfur or oxygen atom, R ₁₂ is a methyl group or a phenyl group, R ₁₃ to R ₁₅ are a hydrogen atom or a monovalent organic group,
R ₁₆ is a monovalent organic group, R ₁₇ is an alkyl group having 1 to 5 carbon atoms, and R ₁₈ is an alkyl group having 1 to 4 carbon atoms or a saturated alicyclic structure having 3 to 10 carbon atoms. R ₁₉ is a monovalent organic group having a methyl group, an ethyl group, a propyl group, or a phenyl group. )
More preferably, it has at least one structure selected from the group consisting of:

The content of the photopolymerization initiator (B) is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the polyimide precursor (A) from the viewpoint of high sensitivity and high resolution. (B) The photopolymerization initiator may be used alone or in combination of two or more.

<(C) Solvent>
Examples of the solvent include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and alcohols.
That is, examples of the solvent include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and methyl acetate. , ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, ethyl acetoacetate, dimethyl succinate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydro Furfuryl alcohol, ε-caprolactone, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dimethyl malonate, dichloromethane, 3-methoxy-N,N-dimethylpropanamide, 1,2-dichloroethane, 1,4-dichlorobutane , chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene.

Among them, from the viewpoint of resin solubility, stability of the resin composition, and adhesion to the substrate, N-methyl-2-pyrrolidone, tetramethylurea, butyl acetate, ethyl lactate, and γ-butyrolactone are used as solvents. , dimethyl succinate, ε-caprolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, 3-methoxy-N,N-dimethylpropanamide, benzyl alcohol, dimethyl malonate, phenyl glycol, ethyl acetoacetate, and Tetrahydrofurfuryl alcohol is preferred.

In addition to the above solvents, at least one solvent selected from the group consisting of 1-methylimidazole, dimethylimidazolidinone, dimethyl sulfoxide, and tetramethylene sulfoxide may be included as a cosolvent. Including these solvents may improve the storage stability of the resin composition and the adhesion to the substrate.

In the polyimide precursor, the amount of the solvent used is preferably 100 to 1000 parts by weight, more preferably 120 to 700 parts by weight, and still more preferably 125 to 500 parts by weight, based on 100 parts by weight of the polyimide precursor. (C) The solvent may be used alone or in combination of two or more.

<(D) Radical polymerizable compound (polymerizable monomer)>
The photosensitive resin composition may further contain a radically polymerizable compound. A radically polymerizable compound is a monomer that has a radically polymerizable unsaturated bond and can assist in crosslinking of a polyimide precursor upon exposure to light. As such a monomer, a (meth)acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferable. Examples of the radically polymerizable compound include diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and the like.

That is, examples of radically polymerizable compounds include mono- or di-(meth)acrylates of ethylene glycol or polyethylene glycol, mono- or di-(meth)acrylates of propylene glycol or polypropylene glycol, and mono-, di- or tri(meth)acrylates of glycerol. , cyclohexane di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, bisphenol A mono- or di- (meth)acrylate, benzene tri(meth)acrylate, isobornyl(meth)acrylate, (meth)acrylamide and its derivatives, trimethylolpropane tri(meth)acrylate, glycerol di- or tri(meth)acrylate, pentaerythritol di, Mention may be made of tri- or tetra(meth)acrylates and ethylene oxide or propylene oxide adducts of these compounds. Among these radically polymerizable compounds, it is preferable to have three or more radically polymerizable groups from the viewpoint of suppressing curing shrinkage. Further, these monomers may be used alone or in a mixture of two or more.

When the polyimide precursor contains the above monomer having a radically polymerizable unsaturated bond, the amount of the monomer having a radically polymerizable unsaturated bond is 1 to 80 parts by weight per 100 parts by weight of the polyimide precursor. part is preferred. When the amount is 1 part by mass or more, good sensitivity during exposure is likely to be obtained, and when the amount is 80 parts by mass or less, the in-plane uniformity of the coating film is likely to be excellent. The blending amount of the monomer having a photopolymerizable unsaturated bond is more preferably 20 to 80 parts by mass based on 100 parts by mass of the polyimide precursor, from the viewpoint of suppressing changes in film thickness during curing.

<(E) Thermal crosslinking agent>
The photosensitive resin composition may further include (E) a thermal crosslinking agent. Thereby, it is easy to suppress curing shrinkage and improve the glass transition temperature. Although not bound by theory, this is because a part of the -NH- structure in the 5- to 6-membered heterocycle containing a nitrogen atom and/or a part of the substituted amino group in the polymer is a thermal crosslinking agent. This is thought to be due to the reaction and formation of a three-dimensional network structure.

(E) Thermal crosslinking agent means a compound that causes addition reaction or condensation polymerization reaction by heat. These reactions tend to occur between (A) the polyimide precursor and (E) the thermal crosslinking agent, and between the (E) thermal crosslinking agents, and the reaction temperature is preferably 150° C. or higher.

(E) Examples of the thermal crosslinking agent include alkoxymethyl compounds, epoxy compounds, oxetane compounds, bismaleimide compounds, allyl compounds, and blocked isocyanate compounds.

Examples of alkoxymethyl compounds include the following compounds.

Examples of the epoxy compound include epoxy compounds containing bisphenol A type groups and hydrogenated bisphenol A diglycidyl ether (for example, Epolite 4000 manufactured by Kyoeisha Chemical Co., Ltd.).

Oxetane compounds include 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, bis[1-ethyl(3-oxetanyl)]methyl ether, 4,4'-bis[(3 -ethyl-3-oxetanyl)methyl]biphenyl, 4,4'-bis(3-ethyl-3-oxetanylmethoxy)biphenyl, ethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, diethylene glycol bis(3-ethyl) -3-oxetanylmethyl) ether, bis(3-ethyl-3-oxetanylmethyl) diphenoate, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) Ether, poly[[3-[(3-ethyl-3-oxetanyl)methoxy]propyl]silasesquioxane] derivative, oxetanyl silicate, phenol novolac type oxetane, 1,3-bis[(3-ethyloxetan-3-yl) ) methoxy]benzene, OXT121 (manufactured by Toagosei Co., Ltd., trade name), OXT221 (manufactured by Toagosei Co., Ltd., trade name), and the like.

Examples of bismaleimide compounds include 1,2-bis(maleimido)ethane, 1,3-bis(maleimido)propane, 1,4-bis(maleimido)butane, 1,5-bis(maleimido)pentane, 1,6- Bis(maleimido)hexane, 2,2,4-trimethyl-1,6-bis(maleimido)hexane, N,N'-1,3-phenylenebis(maleimide), 4-methyl-N,N'-1, 3-phenylenebis(maleimide), N,N'-1,4-phenylenebis(maleimide), 3-methyl-N,N'-1,4-phenylenebis(maleimide), 4,4'-bis(maleimide) ) diphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-bis(maleimido)diphenylmethane, or 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane.

Allyl compounds include allyl alcohol, allyl anisole, allyl benzoate, allyl cinnamic acid ester, N-allyloxyphthalimide, allylphenol, allyl phenyl sulfone, allyl urea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, and maleic acid. Examples include diallyl, diallyl isocyanurate, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallylamine, triallyl 1,3,5-benzenetricarboxylate, triallyl trimellitate, triallyl phosphate, triallylphosphite, triallyl citrate, etc. It will be done.

As the blocked isocyanate compound, hexamethylene diisocyanate-based blocked isocyanate (for example, Asahi Kasei Corporation Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF -K60B and WM44-L70G, Takenate B-882N manufactured by Mitsui Chemicals, 7960, 7961, 7982, 7991, and 7992 manufactured by Baxenden, etc.), tolylene diisocyanate-based block isocyanate (for example, manufactured by Mitsui Chemicals, Inc.) Takenate B-830, etc.), 4,4'-diphenylmethane diisocyanate block isocyanates (for example, Takenate B-815N manufactured by Mitsui Chemicals, Bronate PMD-OA01 manufactured by Taiei Sangyo Co., Ltd., and PMD- MA01, etc.), 1,3-bis(isocyanatomethyl)cyclohexane block isocyanate (for example, Takenate B-846N manufactured by Mitsui Chemicals, Coronate BI-301, 2507, and 2554 manufactured by Tosoh Corporation), isophorone diisocyanate Examples include block isocyanates (for example, 7950, 7951, and 7990 manufactured by Baxenden), and the like.

Among these, alkoxymethyl compounds and blocked isocyanate compounds are preferred from the viewpoints of storage stability of the photosensitive resin composition, inhibition of curing shrinkage, and improvement of the glass transition temperature of the cured film. (E) The thermal crosslinking agent may be used alone or in combination of two or more.

<Other compounds>
The photosensitive resin composition may further contain compounds other than those mentioned above (other compounds). Other compounds will be exemplified below.

(thermal base generator)
The photosensitive resin composition may contain a base generator. A base generator refers to a compound that generates a base when heated. By containing a thermal base generator, it is easier to further promote imidization of the polyimide precursor.

Examples of the thermal base generator include an amine compound protected by a tert-butoxycarbonyl group, a thermal base generator disclosed in International Publication No. 2017/038598, and the like. In addition, known thermal base generators can be used.

Examples of amine compounds protected by a tert-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, and 4-amino-1-butanol. , 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1 , 2-propanediol, 2-amino-1,3-propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4 -Aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[ 2-(Methylamino)ethyl]benzyl alcohol, diethanolamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3- hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidyl)-2-propanol, 1,4-butanol bis(3 -aminopropyl) ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza -15-crown 5-ether, diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxaundecane, or the amino group of an amino acid and its derivatives by a tert-butoxycarbonyl group. protected compounds.

The blending amount of the thermal base generator is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, based on 100 parts by mass of the polyimide precursor (A). The above blending amount is preferably 0.1 parts by mass or more from the viewpoint of imidization promoting effect, and 20 parts by mass or less from the viewpoint of physical properties of the photosensitive resin layer after curing of the polyimide precursor. The thermal base generator may be used alone or in combination of two or more.

(Nitrogen-containing heterocyclic compound)
When forming a cured film on a substrate made of copper or a copper alloy using a polyimide precursor, the photosensitive resin composition may optionally contain a nitrogen-containing heterocyclic compound in order to suppress discoloration on the copper. . Examples of nitrogen-containing heterocyclic compounds include azole compounds and purine derivatives.

Examples of azole compounds include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl -5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, Hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3, 5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl -2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, Hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5- Examples include methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, and 1-methyl-1H-tetrazole.

Among these, preferred are tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, and 5-amino-1H-tetrazole. These azole compounds may be used alone or in a mixture of two or more.

Specific examples of purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyl Adenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-amino Adenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3- Examples include chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthin, 8-azahypoxanthine, and derivatives thereof. It will be done.

When the photosensitive resin composition contains the azole compound or purine derivative, the blending amount is preferably 0.1 to 20 parts by mass based on 100 parts by mass of (A) polyimide precursor, and from the viewpoint of photosensitivity characteristics, More preferably 0.5 to 5 parts by mass. When the blending amount of the azole compound per 100 parts by mass of (A) polyimide precursor is 0.1 part by mass or more, when the polyimide precursor is formed on copper or copper alloy, discoloration of the surface of copper or copper alloy is suppressed. On the other hand, if the amount is 20 parts by mass or less, it tends to have excellent photosensitivity. The nitrogen-containing heterocyclic compound may be used alone or in combination of two or more.

(F) Hindered Phenol Compound In order to suppress discoloration on the copper surface, the photosensitive resin composition may contain (F) a hindered phenol compound. Examples of hindered phenol compounds include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, and octadecyl-3-(3,5-di-t-butyl-4-methylphenol). -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-hydrocin) namamide), 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- Examples include trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene.

As a hindered phenol compound, 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-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H, 3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H, 5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H, 3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6 -(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4 ,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3 ,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5 -triazine-2,4,6-(1H,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.
Among them, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H) - Trion is particularly preferred.

The amount of the hindered phenol compound (F) to be blended is preferably 0.1 to 20 parts by weight, and from the viewpoint of photosensitivity characteristics, 0.5 to 10 parts by weight based on 100 parts by weight of the polyimide precursor (A). More preferred. When the amount of the hindered phenol compound added to 100 parts by mass of (A) polyimide precursor is 0.1 parts by mass or more, when the polyimide precursor is formed on copper or copper alloy, discoloration of copper or copper alloy may occur. It is easy to prevent corrosion, and on the other hand, when it is 20 parts by mass or less, it tends to have excellent photosensitivity. (F) The hindered phenol compound may be used alone or in combination of two or more.

(Organic titanium compound)
The photosensitive resin composition may contain an organic titanium compound. By containing the organic titanium compound, it is easy to form a photosensitive resin layer that has excellent chemical resistance even when cured at a low temperature.

Examples of organic titanium compounds that can be used include those in which an organic chemical substance is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organic titanium compounds are shown in I) to VII) below:
I) Titanium chelate compound: Among these, a titanium chelate having two or more alkoxy groups is more preferable because it provides storage stability of the polyimide precursor and provides a good pattern. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate, titanium diisopropoxide bis(2,4-pentanedionate) titanium diisopropoxide bis(tetramethylheptanedionate), and titanium diisopropoxide bis(ethyl acetoacetate).
II) Tetraalkoxytitanium compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide , titanium tetramethoxypropoxide, titanium tetramethyl phenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)] butoxide}].
III) Titanocene compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2, 4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and the like.
IV) Monoalkoxytitanium compounds: for example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide.
V) Titanium oxide compound: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide.
VI) Titanium tetraacetylacetonate compound: for example titanium tetraacetylacetonate.
VII) Titanate coupling agent: for example isopropyl tridodecylbenzenesulfonyl titanate.

Among them, at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds is preferred from the viewpoint of exhibiting better chemical resistance. preferable. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H -pyrrol-1-yl)phenyl)titanium is preferred.

When blending an organic titanium compound, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the polyimide precursor (A). When the amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are likely to be exhibited, while when it is 10 parts by mass or less, storage stability is likely to be excellent. The organic titanium compounds may be used alone or in combination of two or more.

(adhesion aid)
In order to improve the adhesion between the film formed using the polyimide precursor and the substrate, the photosensitive resin composition may contain an adhesion aid. As adhesive aids, γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3- Methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide , N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1, 4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyl Silane coupling agents such as trimethoxysilane, 3-ureidopropyltriethoxysilane, 3-(trialkoxysilyl)propyl succinic anhydride, and aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetonate), ethyl Examples include aluminum-based adhesion aids such as acetoacetate aluminum diisopropylate.

When the photosensitive resin composition contains an adhesion aid, the amount of the adhesion aid added is preferably 0.5 to 25 parts by mass based on 100 parts by mass of the polyimide precursor (A). The adhesion aids may be used alone or in combination of two or more.

The adhesion aid is preferably a silane coupling agent from the viewpoint of adhesive strength. Examples of silane coupling agents include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM803; manufactured by Chisso Corporation: trade name Sila Ace S810), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Corporation: Product name SIM6475.0), 3-Mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: product name LS1375, product name manufactured by Azmax Corporation: product name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Corporation: product name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Corporation: product name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3 -Mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane , 2-mercaptoethyl ethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyl ethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane , 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, and 4-mercaptobutyltripropoxysilane.

In addition, as the silane coupling agent, N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS3610, manufactured by Azmax Corporation: trade name SIU9055.0), N-(3-triethoxysilylpropyl) methoxysilylpropyl)urea (manufactured by Azmax Corporation: trade name SIU9058.0), N-(3-diethoxymethoxysilylpropyl)urea, N-(3-ethoxydimethoxysilylpropyl)urea, N-(3-tripropoxy silylpropyl)urea, N-(3-diethoxypropoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-dimethoxypropoxysilylpropyl)urea, N-(3-methoxydipropyl)urea, propoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea, N-(3-ethoxydimethoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-tripropoxysilyl) ethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilyl) butyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-tripropoxysilylbutyl)urea, 3-(m-aminophenoxy)propyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0598. 0), m-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.1), aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.1), Company-made product name: SLA0599.2).

In addition, as the silane coupling agent, 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax Corporation: trade name SIT8396.0), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine , 2-(diethoxysilylmethylethyl)pyridine, (3-triethoxysilylpropyl)-t-butylcarbamate, (3-glycidoxypropyl)triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n- Propoxysilane, Tetra-i-propoxysilane, Tetra-n-butoxysilane, Tetra-i-butoxysilane, Tetra-t-butoxysilane, Tetrakis(methoxyethoxysilane), Tetrakis(methoxy-n-propoxysilane), Tetrakis( ethoxyethoxysilane), tetrakis(methoxyethoxyethoxysilane), bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane, bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl) ) ethylene, bis(triethoxysilyl)octane, bis(triethoxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide, bis[3-(triethoxysilyl)propyl]tetrasulfide, di-t- Butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylsiphenylsilanediol, Isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n- Butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenyl Examples include silanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, and triphenylsilanol.

で表される構造を有するシランカップリング剤が好ましい。 Among them, from the viewpoint of storage stability, phenylsilane triol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and the following formula:

A silane coupling agent having a structure represented by is preferred.

The amount of the silane coupling agent used is preferably 0.01 to 20 parts by weight based on 100 parts by weight of the polyimide precursor (A). The silane coupling agent may be used alone or in combination of two or more.

(sensitizer)
The photosensitive resin composition may contain a sensitizer to improve photosensitivity. As a sensitizer, 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-dimethylaminocinnamylidenein Danone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole , 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl -7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole , 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl) naphtho Examples include (1,2-d)thiazole and 2-(p-dimethylaminobenzoyl)styrene.

The amount of the sensitizer to be blended is preferably 0.1 to 25 parts by weight based on 100 parts by weight of the polyimide precursor (A). The sensitizers may be used alone or in combination of two or more.

(Polymerization inhibitor)
The photosensitive resin composition may contain a polymerization inhibitor, particularly in order to improve the stability of the viscosity and photosensitivity of the polyimide precursor during storage in a solution containing a solvent. Examples of polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6- Di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfonate) Examples include propylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, and the like. The polymerization inhibitors may be used alone or in combination of two or more.

《Production method of photosensitive resin composition》
One aspect of this embodiment is
A method for producing a negative photosensitive resin composition comprising a polyimide precursor that is a polymer of tetracarboxylic dianhydride and an amine compound having a 5- to 6-membered heterocycle containing a nitrogen atom, the method comprising:
The above method includes the following (i) and/or (ii):
(i) The number of rings that the amine compound has is one or two. (ii) The ratio of the number of nitrogen atoms to the number of carbon atoms in the amine compound (nitrogen atoms/carbon atoms) is 35% or more and 500%. satisfies the following, and
Reacting the carboxyl group (-COOH group) contained in the tetracarboxylic dianhydride with the amino group (-NH ₂ ) contained in the amine compound or the -NH- structure in the heterocycle contained in the amine compound, The method includes a step of obtaining a polyimide precursor.

The above manufacturing method may include a step of mixing (A) a polyimide precursor, (B) a photopolymerization initiator, (C) a solvent, and, if necessary, a further arbitrary compound by a conventional method.

<(A) Method for preparing polyimide precursor>
First, a tetracarboxylic dianhydride containing a tetravalent organic group X, an alcohol having a photopolymerizable unsaturated bond (hereinafter also referred to as "unsaturated double bond"), and optionally another alcohol (for example, alcohols having no unsaturated double bonds). In this way, a partially esterified tetracarboxylic acid (hereinafter also referred to as "acid/ester") is prepared. By using an alcohol having a photopolymerizable unsaturated double bond in the above reaction, a photosensitive group (for example, ethylenic unsaturated double bond groups) are introduced.

Thereafter, the partially esterified tetracarboxylic acid and the amine compound containing Y ₁ and/or Y ₂ are subjected to amide polycondensation. In particular, in the method of the present embodiment, the carboxyl group contained in the tetracarboxylic dianhydride, the amino group (-NH ₂ ) contained in the amine compound or the -NH- structure in the heterocycle contained in the amine compound, react. Thereby, the polyimide precursor (A) can be suitably obtained.
Here, in an amine compound containing both an amino group (-NH ₂ ) and an -NH- structure, the amino group (-NH ₂ ) and the carboxyl group react, and the -NH- structure and the carboxyl group react. On the other hand, in an amine compound in which the -NH- structure in the heterocycle is protected, the amino group (-NH ₂ ) and the carboxyl group react.

(Preparation of acid/ester form)
Examples of the tetracarboxylic dianhydride containing a tetravalent organic group X used in this embodiment include tetracarboxylic dianhydride having the structure represented by the above formula (I), pyromellitic anhydride, and diphenyl ether. -3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetra Carboxylic dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis (3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc., preferably pyromellitic anhydride. , diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4' -Tetracarboxylic dianhydride and the like. These may be used alone or in combination of two or more.

Examples of alcohols having a photopolymerizable unsaturated double bond used in this embodiment include 2-(meth)acryloyloxyethyl alcohol, 1-(meth)acryloyloxy-3-propyl alcohol, and 2-(meth)acryloyloxyethyl alcohol. ) Acrylamide ethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxyethyl (meth)acrylate, 2-hydroxy-3-methoxypropyl (meth)acrylate, 2-hydroxy-3-butoxypropyl (meth)acrylate , 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-butoxypropyl (meth)acrylate, 2-hydroxy-3-t-butoxypropyl (meth)acrylate, 2-hydroxy-3-cyclohexyloxy Examples include propyl (meth)acrylate.

The photopolymerizable alcohols having unsaturated double bonds may be mixed with other alcohols (for example, alcohols having no unsaturated double bonds). Examples of other alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, Examples include benzyl alcohol.

As the polyimide precursor, a non-photosensitive polyimide precursor prepared only from alcohols having no unsaturated double bonds may be mixed with the photosensitive polyimide precursor. From the viewpoint of resolution, the non-photosensitive polyimide precursor is preferably 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor.

By stirring, dissolving and mixing tetracarboxylic dianhydride and alcohol in a solvent as described below in the presence of a basic catalyst, the esterification reaction of the acid anhydride proceeds and the desired acid/ester is produced. You can get a body. The stirring dissolution and mixing are preferably carried out at a temperature of 20 to 50° C. for 4 to 24 hours, for example.

(Preparation of polyimide precursor)
The acid moiety of the above acid/ester compound (typically present as a solution in a solvent described below) can be converted to acid chloride using thionyl chloride or the like under ice cooling. An amine compound containing Y ₁ and/or Y ₂ separately dissolved or dispersed in a solvent is added dropwise to the obtained acid chloride in the presence of a base such as pyridine, and amide polycondensation is carried out to form a polyimide precursor. can be obtained. Alternatively, a suitable dehydration condensation agent such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy may be added to the above acid/ester under ice cooling. -Di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, etc. can be added and mixed to convert the acid/ester form into a polyacid anhydride. A polyimide precursor can be obtained by dropping an amine compound containing Y ₁ or Y ₂ separately dissolved or dispersed in a solvent into the obtained polyacid anhydride and carrying out amide polycondensation.

Amine compounds containing Y ₁ and/or Y ₂ include 5-aminotetrazole, 3,5-diamino-1,2,4-triazole, 4,5-diamino-1H-1,2,3-triazole, 5 -amino-1H-1,2,4-triazole, 5-amino-1H-1,2,3-triazole, 2,5-diamino-1H-imidazole, 3,5-diamino-1H-pyrazole, 3,4 -Diamino-1H-pyrazole, 3-aminopyrazole, 4-aminopyrazole, 2-amino-1H-imidazole, 5-amino-1H-imidazole, 2,5-diamino-1H-pyrrole, 2,4-diamino-1H -pyrrole, 2,3-diamino-1H-pyrrole, 3,4-diamino-1H-pyrrole, 3-amino-1H-pyrrole, 4,6-diaminopyrimidine, 2,6-diaminopyridine, 2,4-diamino Pyrimidine, 2,5-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,4-diamino-6-methyl-1,3,5-triazine, benzoguanamine, 5-aminoindazole, 5- Aminobenzimidazole, 2,6-diamino-1H-benzimidazole, 5-aminopurine, adenine, 6,8-diamino-9H-purine, 4-aminopyrazolo[3,4-d]pyrimidine, 2,6-diaminopurine , 6-amino-7-deazapurine, 8-azaadenine, and mixtures thereof.

After the amide polycondensation reaction is completed, if a dehydration condensation agent is used, water absorption by-products of the dehydration condensation agent coexisting in the reaction solution are filtered off, if necessary. Thereafter, a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is added to the obtained polymer component to precipitate the polymer component. Furthermore, the polymer is purified by repeating redissolution, reprecipitation, etc., and vacuum drying is performed to isolate the desired polyimide precursor. In order to improve the degree of purification, ionic impurities may be removed by passing the polymer solution through a column packed with an anion and/or cation exchange resin swollen with a suitable organic solvent.

The molecular weight of the polyimide precursor is preferably 5,000 to 150,000, more preferably 6,000 to 50,000, when measured as a polystyrene equivalent weight average molecular weight by gel permeation chromatography. When the weight average molecular weight is 6,000 or more, the mechanical properties are good, and when it is 150,000 or less, the dispersibility in a developer is good and the resolution performance of a relief pattern is good. As the developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are preferred. The weight average molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. The standard monodisperse polystyrene is preferably selected from organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko.

One aspect of the present embodiment is a method for producing a polyimide precursor that is a polymer of a tetracarboxylic dianhydride and an amine compound, comprising:
Such a method includes the following (i) and/or (ii):
(i) The number of rings that the amine compound has is one or two. (ii) The ratio of the number of nitrogen atoms to the number of carbon atoms in the amine compound (nitrogen atoms/carbon atoms) is 35% or more and 500%. satisfies the following, and
Including the step of reacting the carboxyl group (-COOH group) contained in the tetracarboxylic dianhydride with the amino group (-NH ₂ ) or the -NH- structure in the heterocycle contained in the amine compound ( A) A method for producing a polyimide precursor.

Regarding the method for producing a polyimide precursor, which is one aspect of the present embodiment, "(i)" and "(ii)" and furthermore, the "reacting step" each adopt the method explained above. Can be done.

《Production method of cured relief pattern》
The method for manufacturing the cured relief pattern of this embodiment is as follows:
(1) A step of applying the above-described negative photosensitive resin composition of this embodiment onto a substrate to form a photosensitive resin layer on the substrate (resin layer forming step);
(2) a step of exposing the photosensitive resin layer (exposure step);
(3) a step of developing the exposed photosensitive resin layer to form a relief pattern (relief pattern forming step);
(4) A step of heat-treating the relief pattern to form a cured relief pattern (cured relief pattern forming step).

(1) Resin layer forming step In this step, the negative photosensitive resin composition of the present embodiment is applied onto a substrate, and if necessary, it is then dried to form a photosensitive resin layer. The coating method includes methods conventionally used for coating photosensitive resin compositions, such as coating with a spin coater, bar coater, blade coater, curtain coater, screen printer, etc., and spray coating with a spray coater. There are several methods.

If necessary, the coating film containing the photosensitive resin composition can be dried. Examples of the drying method include air drying; heating drying using an oven or hot plate; and vacuum drying. Specifically, in the case of air drying or heat drying, drying can be performed at 20° C. to 150° C. for 1 minute to 1 hour. In the manner described above, a photosensitive resin layer can be formed on the substrate.

(2) Exposure process In this process, the photosensitive resin layer formed above is exposed to an ultraviolet light source using an exposure device such as a contact aligner, mirror projection, or stepper, through a patterned photomask or reticle, or directly. etc. to expose to light. By this exposure, the polymerizable groups of the polyimide precursor (A) contained in the negative photosensitive resin composition are crosslinked by the action of the photopolymerization initiator (B). This crosslinking makes the exposed area insoluble in the developer described below, making it possible to form a relief pattern.

Thereafter, for the purpose of improving photosensitivity, etc., a post-exposure bake (PEB) or a pre-development bake, or both may be performed at any combination of temperature and time, if necessary. As for the baking conditions, the temperature is preferably 40°C to 120°C and the time is preferably 10 seconds to 240 seconds, but it is limited to this range as long as it does not impair the properties of the photosensitive resin composition of this embodiment. I can't.

(3) Relief pattern forming step In this step, the unexposed portions of the exposed photosensitive resin layer are developed and removed. The developing method for developing the photosensitive resin layer after exposure (irradiation) may be any of conventionally known photoresist developing methods, such as a rotary spray method, a paddle method, and an immersion method involving ultrasonic treatment. You can select and use the following methods. After development, post-development baking may be performed at any combination of temperature and time, if necessary, for purposes such as adjusting the shape of the relief pattern.

As the developer used for development, for example, a good solvent for the negative photosensitive resin composition of this embodiment, or a combination of the good solvent and a poor solvent is preferable. As a good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. are preferable. . Preferred examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When using a mixture of a good solvent and a poor solvent, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the negative photosensitive resin composition. Two or more kinds of solvents, for example several kinds, can be used in combination.

(4) Cured relief pattern forming step In this step, the relief pattern obtained by the above development is heat-treated to dilute the photosensitive component and to imidize the imide precursor portion of the (A) polyimide precursor. This converts it into a cured relief pattern made of polyimide. Various methods can be selected for the heat treatment, such as a method using a hot plate, a method using an oven, and a method using a heating oven in which a temperature program can be set. The heat treatment can be performed, for example, at 150° C. to 350° C. for 30 minutes to 5 hours. The temperature of the heat treatment is 150°C to 250°C, preferably 150°C to 230°C, more preferably 170°C to 230°C. Air may be used as the atmospheric gas during heat curing, and inert gases such as nitrogen and argon may also be used.

｛式中、Ｘ及びＹ_１は、式（１）におけるＸ及びＹ_１の場合と同様であり、Ｒ_２は、水素原子、又は１価の有機基であり、Ｒ_２は、式（３）で表される１価の有機基、又はそのラジカル重合体であり、ｍは、正の整数である。｝の繰り返し単位、及び／又は、下記一般式（２２）：

｛式中、Ｘ及びＹ_２は、式（１）におけるＸ及びＹ_２の場合と同様であり、Ｒ_２は、水素原子、又は１価の有機基であり、Ｒ_２は、式（３）で表される１価の有機基、又はそのラジカル重合体であり、ｎは、正の整数である。｝の繰り返し単位を含む。 《Polyimide》
Polyimide can be obtained by curing the photosensitive resin composition of this embodiment. The polyimide obtained from the photosensitive resin composition of this embodiment has the following general formula (20):

{In the formula, X and Y ₁ are the same as in the case of X and Y ₁ in formula (1), R ₂ is a hydrogen atom or a monovalent organic group, and R ₂ is the formula (3) It is a monovalent organic group represented by or a radical polymer thereof, and m is a positive integer. } repeating unit and/or the following general formula (22):

{In the formula, X and Y ₂ are the same as in the case of X and Y ₂ in formula (1), R ₂ is a hydrogen atom or a monovalent organic group, and R ₂ is the formula (3) It is a monovalent organic group represented by or a radical polymer thereof, and n is a positive integer. } Contains repeating units.

｛式中、Ｘ及びＹ_１は、式（１）におけるＸ及びＹ_１の場合と同様であり、ｍは、正の整数である。｝の繰り返し単位を含んでよい。 Such polyimide has the following general formula (19):

{In the formula, X and Y ₁ are the same as in the case of X and Y ₁ in Formula (1), and m is a positive integer. } may be included.

Preferred X, Y ₁ and Y ₂ in formulas (1) and (2) are also preferred in formulas (19) to (21) for the same purpose as above. The number of repeating units in formulas (19) to (21) may be an integer from 2 to 150, for example.

《Production method for cured polyimide product》
The method for producing a cured polyimide product of this embodiment is as follows:
Coating the photosensitive resin composition on a substrate to form a photosensitive resin layer on the substrate;
a step of drying the obtained photosensitive resin layer;
a step of exposing the photosensitive resin layer after drying;
a step of developing the photosensitive resin layer after exposure;
A step of heat-treating the photosensitive resin layer after development to form a cured polyimide product of the present embodiment;
has. The examples and preferred embodiments given in the above <<Method for manufacturing a cured relief pattern>> are similarly applicable to the method for manufacturing polyimide.

《Semiconductor device》
According to the present disclosure, there is also provided a semiconductor device having a cured relief pattern obtained by the method for manufacturing a cured relief pattern described above. For example, it is possible to provide a semiconductor device having a base material that is a semiconductor element and a cured polyimide relief pattern formed on the base material by the above-described cured relief pattern manufacturing method. Further, it is also possible to provide a method for manufacturing a semiconductor device that uses a semiconductor element as a base material and includes the above-described method for manufacturing a cured relief pattern of the present disclosure as part of the process. The semiconductor device can be used as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip-chip device, or a semiconductor device having a bump structure, using a hardened relief pattern formed by the method for manufacturing a hardened relief pattern of the present disclosure. It can be manufactured by forming it as a protective film or the like, and combining it with a known semiconductor device manufacturing method.

The polyimide cured product (polyimide cured film) is used, for example, as an insulating layer (also referred to as a "rewiring insulating film" or "interlayer insulating film") in a semiconductor device. In a semiconductor device, the insulating layer is disposed around wiring that electrically connects a semiconductor chip and external connection terminals. In a semiconductor device, one or more insulating layers may be disposed.

FIG. 1 is a schematic cross-sectional view of a semiconductor device according to this embodiment.
As shown in FIG. 1, a semiconductor device (semiconductor IC) 1 includes:
semiconductor chip 2;
a sealing material in contact with the semiconductor chip 2;
A rewiring layer 4 disposed in a region of the semiconductor chip 2 that is not in contact with the sealing material and having a larger area than the semiconductor chip 2 in plan view,
The rewiring layer 4 includes an intermediate layer (eg, wiring 5) and an insulating layer 6. The semiconductor device (semiconductor IC) 1 has a protective layer 8 in which a plurality of holes 8a are formed between the semiconductor chip 2 and the insulating layer 6, and the terminals 2a are connected to the semiconductor chip 2 through the holes 8a. It is connected.

One end of the wiring 5 (semiconductor chip 2 side) is connected to the terminal 2a, and the other end (opposite to the semiconductor chip 2) is connected to the external connection terminal 7. As shown in FIG. 2, the area S2 of the rewiring layer 4 is larger than the area S1 of the semiconductor chip 2 in plan view (view of arrow A in FIG. 1). The semiconductor device 1 shown in FIGS. 1 and 2 is one embodiment of a fan-out type wafer level chip size package (WLCSP) type semiconductor device.

FIG. 3 shows an example of the manufacturing process of the semiconductor device 1. As shown in FIG. In FIG. 3A, a wafer 10 is prepared. Thereafter, a photosensitive resin composition is applied, exposed and developed to form a relief pattern. In FIG. 3B, the wafer is diced to obtain a plurality of semiconductor chips 2. The semiconductor chips 2 are pasted on the support 11 at predetermined intervals, as shown in FIGS. 3C and 3D. Then, molding resin 12 is applied from the top of the semiconductor chip 2 to the top of the support 11. The support 11 is peeled off, the mold resin 12 is turned over (see FIG. 3E), and then, as shown in FIG. 3F, a photosensitive resin composition 13 is applied onto the semiconductor chip 2 and the mold resin 12. The applied photosensitive resin composition 13 is exposed and developed to form a relief pattern. The relief pattern is heated to form a cured relief pattern, and then wiring is formed in locations where the cured relief pattern is not formed. Pattern formation may be repeated so that the redistribution layer has multiple insulating layers.
In FIG. 3G, a plurality of external connection terminals 7 corresponding to each semiconductor chip 2 are formed, and the semiconductor chips 2 are diced. Thereby, the semiconductor device 1 can be obtained as shown in FIG. 3H. However, the configuration of the semiconductor device 1 and the manufacturing process thereof are merely examples, and are not limited to the contents of this embodiment.

《Display device》
The present disclosure provides a display device including a display element and a cured film provided on the top of the display element, the cured film being the above-mentioned cured relief pattern. . Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer in between. Examples of the cured film include surface protective films, insulating films, and planarizing films for TFT liquid crystal display elements and color filter elements, protrusions for MVA type liquid crystal display devices, and partition walls for organic EL element cathodes.

In addition to being applied to semiconductor devices as described above, the negative photosensitive resin composition of this embodiment can be used for interlayer insulation of multilayer circuits, cover coats for flexible copper clad boards, solder resist films, liquid crystal alignment films, etc. is also useful.

[Second aspect]
The second aspect will be explained below.
The second aspect is the following formula:
Thermogravimetric reduction rate (%) = (Weight after heating to 230°C/Weight at 23°C) x 100
It is a polyimide precursor having a thermogravimetric reduction rate expressed by 5% or more and less than 25%.
According to this, it is possible to suppress volatilization of side chain components in the polymer during the curing process while maintaining good chemical resistance, and therefore, shrinkage of the film during the curing process can be suppressed.

The second aspect can be achieved, for example, by using an amine compound having a 5- to 6-membered heterocycle containing a nitrogen atom as the amine compound forming the polyimide precursor. The second aspect is
(i) The number of rings that the amine compound has is one or two. (ii) The ratio of the number of nitrogen atoms to the number of carbon atoms in the amine compound (nitrogen atoms/carbon atoms) is 35% or more. 500% or less, preferably both. Thereby, based on the same purpose as the first aspect, it is possible to realize low curing shrinkage, and also form a cured relief pattern that can achieve both low curing shrinkage and high adhesion, and also has a high glass transition temperature. Can be done.

When a secondary amino group in a 5- to 6-membered heterocycle containing a nitrogen atom reacts with an acid component to form an amide bond, the amide moiety does not cause imide cyclization, so the polymer side chain component in the curing process is Weight loss due to desorption and volatilization is less likely to occur. Furthermore, even when a substituted amino group in an amine compound having a 5- to 6-membered heterocycle containing a nitrogen atom reacts with an acid component to form an amide bond, due to the electron-withdrawing property of the nitrogen-containing heterocycle, The nucleophilicity of the amide moiety is reduced, and imide cyclization in the curing process and accompanying volatilization of side chain components are suppressed. From this viewpoint, the thermogravimetric reduction rate when the polyimide precursor is heated to 230° C. is preferably 7% or more and less than 20%, more preferably 10% or more and less than 18%.

Basically, the configuration that can be adopted in the first aspect can also be adopted in the second aspect. The configuration preferred in the first aspect is basically also preferred in the second aspect.

Hereinafter, this embodiment will be specifically described with reference to Examples.

《Measurement and evaluation method》
The physical properties of the polyimide precursor or negative photosensitive resin composition were measured and evaluated according to the following methods.

<Weight average molecular weight>
The weight average molecular weight (Mw) of each resin was measured using a gel permeation chromatography method (standard polystyrene conversion) under the following conditions.
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40℃
Column: Showa Denko K.K. Shodex KD-805/KD-804/KD-803 series Standard monodisperse polystyrene: Showa Denko K.K. Shodex STANDARD SM-105
Mobile phase: 0.1 mol/L LiBr/N-methyl-2-pyrrolidone (NMP)
Flow rate: 1mL/min

<Thermogravimetric reduction rate>
The thermogravimetric loss rate of each resin was measured using a differential thermal/thermogravimetric (TG/DTA) simultaneous measuring device (DTG-60A, Shimadzu Corporation) under the following conditions.
Measurement atmosphere: Nitrogen Gas flow rate: 50 (ml/min)
Temperature profile:
The starting temperature was 23°C, the temperature was raised to 230°C at a rate of 5°C/min, and then held at 230°C for 2 hours.
The thermogravimetric reduction rate at 230°C is calculated by the following formula:
Thermogravimetric reduction rate (%) = (sample mass after measurement / sample mass before measurement) x 100
defined according to.

<Copper adhesion of cured film>
Titanium (Ti) with a thickness of 200 nm and copper with a thickness of 400 nm were deposited on a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625 ± 25 μm) using a sputtering device (Model L-440S-FHL, manufactured by Canon Anelva). (Cu) was sputtered in this order. Subsequently, the photosensitive resin composition prepared by the method described below was spin-coated using a coater developer (D-Spin 60A type, manufactured by SOKUDO), prebaked on a hot plate at 110°C for 180 seconds, and then coated for about 10 minutes. A coating film with a thickness of .0 μm was formed. This coating film was entirely exposed to light at an exposure dose of 800 mJ/cm ² using a same-magnification projection exposure device PrismaGHI S/N5503 (manufactured by Ultratech) equipped with a gh-ray cut filter. The resulting exposed film was heat-treated at 230°C for 2 hours in a nitrogen atmosphere using a temperature-programmed curing furnace (Model VF-2000, manufactured by Koyo Lindberg Co., Ltd.) to form a cured film (polyimide film). I got it. In accordance with the cross-cut method of the JIS K 5600-5-6 standard, the adhesive properties between the copper substrate and the cured film were evaluated based on the following criteria.

<Evaluation criteria>
E (◎): The number of lattices in the cured film adhered to the substrate is 100. G (〇): The number of lattices in the cured film adhered to the substrate is 80 or more and 99 or less. A (△): Adhered to the substrate. The number of lattices in the cured film is 40 or more and less than 80. F(×): The number of lattices in the cured film is 1 or more and less than 40. FF(XX): It is adhered to the substrate. The number of lattices in the cured film is 0.

<Change in film thickness before and after heat treatment>
On a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625 ± 25 μm), 200 nm thick Ti and 400 nm thick Cu were deposited in this order using a sputtering device (Model L-440S-FHL, manufactured by Canon Anelva). It spattered. Subsequently, a photosensitive resin composition prepared by the method described below was spin-coated onto this wafer using a coater developer (D-Spin 60A type, manufactured by SOKUDO), and prebaked on a hot plate at 110° C. for 180 seconds. A coating film with a thickness of about 7.5 μm was formed. The entire surface of this coating film was exposed to light at an exposure dose of 800 mJ/cm ² using a same-magnification projection exposure device PrismaGHI S/N5503 (manufactured by Ultratech) equipped with a gh-ray cut filter. Thereafter, the coating film formed on the wafer was spray developed using cyclopentanone using a developing machine (Model D-SPIN 636, manufactured by Dainippon Screen Mfg. Co., Ltd., Japan). After rinsing with propylene glycol methyl ether acetate, drying was performed by spin drying. The film thickness after this development and drying was measured, and the obtained film thickness was defined as film thickness 1. After this development and drying, the film was further heat-treated at 230°C for 2 hours in a nitrogen atmosphere using a temperature-programmed curing furnace (VF-2000, manufactured by Koyo Lindbergh Co., Ltd.) to form a cured film (polyimide film). I got it. The film thickness after the heat treatment was measured, and the obtained film thickness was defined as film thickness 2. Using these film thicknesses, the following formula:
Film thickness change rate (%) before and after heat treatment = (film thickness 2/film thickness 1) x 100
The film thickness change rate before and after the heat treatment was calculated and evaluated.

<Evaluation criteria>
E (〇): Film thickness change rate before and after heat treatment is 90% or more and less than 95% A (△): Film thickness change rate before and after heat treatment is 85% or more and less than 90% F (x): Film before and after heat treatment Thickness change rate less than 85%

<Glass transition temperature>
A photosensitive resin composition prepared by the method described below was spin-coated onto a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625 ± 25 μm) using a coater developer (Model D-Spin 60A, manufactured by SOKUDO). did. Thereafter, prebaking was performed on a hot plate at 110° C. for 180 seconds to form a coating film with a thickness of about 10.0 μm. The entire surface of this coating film was exposed to light at an exposure dose of 800 mJ/cm ² using a same-magnification projection exposure device PrismaGHI S/N5503 (manufactured by Ultratech) equipped with a gh-ray cut filter. The resulting exposed film was heat-treated at 230°C for 2 hours in a nitrogen atmosphere using a temperature-programmed curing furnace (VF-2000, manufactured by Koyo Lindberg Co., Ltd.) to form a cured film (polyimide film). I got it. The obtained cured film was cut into strips with a width of 3 mm using a dicing saw (model DAD3350, manufactured by DISCO), and then peeled off from the silicon wafer using 46% hydrofluoric acid to obtain a polyimide tape. After leaving the obtained polyimide tape in an atmosphere with a temperature of 23°C and a humidity of 50% for 24 hours or more, it was analyzed using a thermomechanical analyzer (TMA, manufactured by Shimadzu Corporation) at a temperature of 50 to 450°C under the following conditions. The elongation of the test piece was measured, and the inflection point was determined as the glass transition temperature.
Load: 5g
Measurement atmosphere: Nitrogen (flow rate 20ml/min)
Temperature increase rate: 10℃/min
Temperature: 50-450℃

<Evaluation criteria>
E (◎): The glass transition temperature of polyimide is 270°C or higher. G (○): The glass transition temperature of polyimide is 250°C or higher and lower than 270°C. A (△): The glass transition temperature of polyimide is 230°C or higher and lower than 250°C. F( ×): Glass transition temperature of polyimide is less than 230°C

《(A) Polyimide precursor》
<Synthesis example 1>
In a 3 L separable flask, 31.02 g (0.1 mol) of 4,4'-oxydiphthalic dianhydride (ODPA), 27.33 g (0.21 mmol) of 2-hydroxyethyl methacrylate (HEMA), and 0.0 g of hydroquinone were added. 1 g and a catalytic amount of DBU (diazabicycloundecene) was dissolved in 100 mL of γ-butyrolactone and stirred at room temperature for 24 hours. As a result, an ester (ODPA-HEMA ester) solution was obtained. Subsequently, 26.17 g (0.22 mmol) of thionyl chloride was added dropwise to the ester (ODPA-HEMA ester) solution over 60 minutes with stirring under ice cooling to obtain an acid chloride solution.

Next, under ice cooling, a solution of 8.49 g (0.086 mmol) of 3,5-diamino-1,2,4-triazole dissolved in 25 mL of γ-butyrolactone was added over 30 minutes with stirring. Subsequently, under ice-cooling, a solution of 17.40 g (0.22 mol) of pyridine dissolved in 50 mL of γ-butyrolactone was added dropwise over 30 minutes while stirring. After the reaction mixture was further stirred for 5 hours under ice cooling, 100 mL of γ-butyrolactone was added.

The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 L of water to precipitate the polymer, and the obtained precipitate was filtered and dried under vacuum to obtain polyimide precursor A-1, which is a powdered polyamic acid ester. Obtained. The weight average molecular weight (Mw) of Precursor A-1 was 14,000 as measured by gel permeation chromatography (standard polystyrene standard).

<Synthesis example 2>
The procedure was carried out in the same manner as in Synthesis Example 1, except that 29.42 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used in place of 31.02 g of ODPA in Synthesis Example 1. Thus, precursor A-2 was obtained. Mw of polyimide precursor A-2 was 16,000.

<Synthesis example 3>
Instead of 31.02 g of ODPA in Synthesis Example 1, 52.05 g of 5,5'-[1-methyl-1,1-ethanediylbis(1,4-phenylene)bisoxy]]bis(isobenzofuran-1,3-dione) Polyimide precursor A-3 was obtained in the same manner as in Synthesis Example 1 except that . The Mw of precursor A-3 was 17,000.

<Synthesis example 4>
The same procedure as described in Synthesis Example 1 except that 7.21 g of 3-amino-1,2,4-triazole was used in place of 8.49 g of 3,5-diamino-1,2,4-triazole in Synthesis Example 1. Polyimide precursor A-4 was obtained in the same manner as in the method. The Mw of precursor A-4 was 10,500.

<Synthesis example 5>
The method described in Synthesis Example 1 except that 8.41 g of 1H-pyrazole-3,5-diamine was used in place of 8.49 g of 3,5-diamino-1,2,4-triazole in Synthesis Example 1. In the same manner, polyimide precursor A-5 was obtained. The Mw of precursor A-5 was 14,000.

<Synthesis example 6>
Polyimide was prepared in the same manner as in Synthesis Example 1, except that 7.12 g of 4-aminopyrazole was used in place of 8.49 g of 3,5-diamino-1,2,4-triazole in Synthesis Example 1. Precursor A-6 was obtained. The Mw of precursor A-6 was 10,500.

<Synthesis example 7>
The method described in Synthesis Example 1 except that 8.41 g of 2,5-diamino-1H-imidazole was used in place of 8.49 g of 3,5-diamino-1,2,4-triazole in Synthesis Example 1. In the same manner, polyimide precursor A-7 was obtained. The Mw of precursor A-7 was 12,500.

<Synthesis example 8>
The method described in Synthesis Example 1 except that 8.32 g of 2,5-diamino-1H-pyrrole was used in place of 8.49 g of 3,5-diamino-1,2,4-triazole in Synthesis Example 1. In the same manner, polyimide precursor A-8 was obtained. The Mw of precursor A-8 was 14,000.

<Synthesis example 9>
Polyimide was prepared in the same manner as in Synthesis Example 1, except that 12.87 g of 8-aminoadenine was used in place of 8.49 g of 3,5-diamino-1,2,4-triazole in Synthesis Example 1. Precursor A-9 was obtained. The Mw of precursor A-9 was 16,000.

<Synthesis example 10>
Polyimide precursor A was prepared in the same manner as in Synthesis Example 1, except that 11.58 g of adenine was used in place of 8.49 g of 3,5-diamino-1,2,4-triazole in Synthesis Example 1. I got -10. The Mw of precursor A-10 was 10,500.

<Synthesis example 11>
The method described in Synthesis Example 1, except that 12.70 g of 2,6-diamino-1H-benzimidazole was used in place of 8.49 g of 3,5-diamino-1,2,4-triazole in Synthesis Example 1. In the same manner as above, polyimide precursor A-11 was obtained. The Mw of precursor A-11 was 14,000.

<Synthesis example 12>
Proceed in the same manner as in Synthesis Example 1, except that 9.35 g of 2,4-diaminopyrimidine was used in place of 8.49 g of 3,5-diamino-1,2,4-triazole in Synthesis Example 1. , polyimide precursor A-12 was obtained. The Mw of precursor A-12 was 12,000.

<Synthesis example 13>
In the same manner as in Synthesis Example 1, except that 9.35 g of 2,6-diaminopyridine was used in place of 8.49 g of 3,5-diamino-1,2,4-triazole in Synthesis Example 1. , polyimide precursor A-13 was obtained. The Mw of precursor A-13 was 11,000.

<Synthesis example 14>
Synthesis Example 1 except that 9.52 g of 2,4-diamino-1,3,5-triazine was used instead of 8.49 g of 3,5-diamino-1,2,4-triazole in Synthesis Example 1. Polyimide precursor A-14 was obtained in the same manner as described above. The Mw of precursor A-14 was 10,500.

<Synthesis example 15>
In a three-neck flask with a capacity of 100 mL, 8.49 g (0.086 mol) of 3,5-diamino-1,2,4-triazole was dissolved in 30 g of γ-butyrolactone, and after cooling the solution to 10°C, γ-butyrolactone was added in advance. 18.7 g (0.086 mol) of di-tert-butyl dicarbonate mixed with 20 g were added. After reacting the reaction mixture at room temperature for 4 hours, the precipitate was filtered and dried under vacuum to obtain powdered 3,5-diamino-1-tBoc-1,2,4-triazole.

In place of 8.49 g of 3,5-diamino-1,2,4-triazole in Synthesis Example 1, 17.08 g of the obtained 3,5-diamino-1-tBoc-1,2,4-triazole was used. Polyimide precursor A-15 was obtained in the same manner as in Synthesis Example 1 except for this. The Mw of precursor A-15 was 11,000.

<Synthesis example 16>
In a three-necked flask with a capacity of 100 mL, 8.49 g (0.086 mol) of 3,5-diamino-1,2,4-triazole was dissolved in 30 g of γ-butyrolactone, and after cooling the solution to 0°C, γ-butyrolactone was added in advance. 13.3 g (0.086 mol) of 2-methacryloyloxyethyl isocyanate mixed with 20 g was added. The reaction mixture was reacted at room temperature for 4 hours to obtain a solution of 3,5-diamino-1-MOI-1,2,4-triazole in γ-butyrolactone.

Instead of 8.49 g of 3,5-diamino-1,2,4-triazole in Synthesis Example 1, the total amount of the obtained γ-butyrolactone solution of 3,5-diamino-1-MOI-1,2,4-triazole Polyimide precursor A-16 was obtained in the same manner as in Synthesis Example 1 except that . The Mw of precursor A-16 was 10,500.

<Synthesis example 17>
Polyimide precursor A-17 was obtained in the same manner as in Synthesis Example 1, except that 15.51 g of ODPA and 14.71 g of BPDA were used in place of 31.02 g of ODPA in Synthesis Example 1. The Mw of precursor A-17 was 14,500.

<Synthesis example 18>
The procedure was carried out in the same manner as in Synthesis Example 1, except that 17.16 g of 4,4'-diaminodiphenyl ether was used instead of 8.49 g of 3,5-diamino-1,2,4-triazole in Synthesis Example 1. Thus, polyimide precursor A'-1 was obtained. The Mw of precursor A'-1 was 18,000.

<Synthesis example 19>
Synthesis Example 1 except that 18.37 g of 2,2'-dimethylbiphenyl-4,4'-diamine was used in place of 8.49 g of 3,5-diamino-1,2,4-triazole in Synthesis Example 1. Polyimide precursor A'-2 was obtained in the same manner as described in . The Mw of precursor A'-2 was 21,000.

<Synthesis example 20>
Polyimide precursor A'-3 was obtained in the same manner as in Synthesis Example 18, except that 29.42 g of BPDA was used in place of 31.02 g of ODPA in Synthesis Example 18. The Mw of precursor A'-3 was 16,000.

<Synthesis example 21>
Polyimide was prepared in the same manner as in Synthesis Example 1, except that 9.27 g of p-phenylenediamine was used in place of 8.49 g of 3,5-diamino-1,2,4-triazole in Synthesis Example 1. Precursor A'-4 was obtained. The Mw of precursor A'-4 was 15,000.

<Synthesis example 22>
Synthesis Example except that 19.22 g of 5-amino-2-(p-aminophenyl)-benzimidazole was used in place of 8.49 g of 3,5-diamino-1,2,4-triazole in Synthesis Example 1. Polyimide precursor A'-5 was obtained in the same manner as described in 1. The Mw of precursor A'-5 was 17,000.

<Synthesis example 23>
Synthesis except that 29.18 g of 2,2'-p-phenylenebis(5-aminobenzimidazole) was used in place of 8.49 g of 3,5-diamino-1,2,4-triazole in Synthesis Example 1. Polyimide precursor A'-6 was obtained in the same manner as described in Example 1. The Mw of precursor A'-6 was 19,000.

Synthesis Examples 1 to 24 are summarized in the table below.

《Preparation of resin composition》
<Examples 1 to 21 and Comparative Examples 1 to 7>
(A) precursor, (B) photopolymerization initiator, (C) solvent, (D) radically polymerizable compound, (E) thermal crosslinking agent, and (F) hindered phenol compound in the amounts shown in the table below. They were mixed to prepare a resin composition solution. The blending amounts in the table below are parts by mass of each component when component (A) is 100 parts by mass. The resulting solution was filtered through a polyethylene filter with pores of 0.2 μm to obtain resin compositions of Examples 1 to 17 and Comparative Examples 1 to 6. The symbols in the table mean the following components, respectively. The composition was evaluated according to the method described above, and the evaluation results are shown in the table below.

(A) As the polyimide precursor, the above precursors (A-1) to (A-17) and (A'-1) to (A'-6) were used.

(B) The following (B-1) was used as a photopolymerization initiator.
(B-1): 1-[4-(phenylthio)phenyl]-3-propane-1,2-dione-2-(O-acetyloxime) (Product name: PBG-3057, manufactured by Changzhou Powerful Electronics Co., Ltd.)

(C) The following (C-1) and (C-2) were used as the radically polymerizable compound.
(C-1): γ-Butyrolactone (C-2): Dimethyl sulfoxide

(D) The following (D-1) and (D-2) were used as the radically polymerizable compound.
(D-1): NK ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)
(D-2): Tetraethylene glycol dimethacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

(E) The following (E-1) and (E-2) were used as the thermal crosslinking agent.
(E-1): Nikalac MW-390 (manufactured by Sanwa Chemical Co., Ltd.)
(E-2): SBB-70P (manufactured by Asahi Kasei Corporation)

(F) The following components were used as the hindered phenol compound.
(F-1): 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H ,5H)-trione

As shown in the table above, according to Examples 1 to 21, it was possible to achieve low curing shrinkage, achieve both low curing shrinkage and high adhesion, and form a cured relief pattern that also had a high glass transition temperature. It has been confirmed that a negative photosensitive resin composition can be provided. Furthermore, high glass transition temperatures were confirmed in Examples 1 to 3, 5, 7 to 9, and 15 to 21. Among them, high glass transition temperatures were confirmed in Examples 20 and 21 containing a thermal crosslinking agent.

By using the present invention, cured relief patterns with high flatness, high adhesion, and high glass transition temperature can be obtained. The present invention can be suitably used, for example, in the field of photosensitive materials useful for manufacturing electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

1 Semiconductor device 2 Semiconductor chip 2a Terminal 3 Sealing material 4 Rewiring layer 5 Wiring 6 Insulating layer 7 External connection terminal 8 Protective layer 8a Hole 10 Wafer 11 Support 12 Mold resin 13 Photosensitive resin composition

Claims (17)

(A) The following general formula (1) and/or (2):

{During the ceremony,
X is each independently a tetravalent organic group,
Y ₁ and Y ₂ are groups derived from an amine compound having a 5- to 6-membered heterocycle containing a nitrogen atom, and the ratio of the number of nitrogen atoms to the number of carbon atoms in the amine compound (nitrogen atom/carbon atom) is 35% or more and 500% or less,
R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms,
At least one of R ₁ and R ₂ is a group having an ethylenically unsaturated bond, and
At least one of m and n is an integer of 1 or more. }
A polyimide precursor containing a structural unit represented by
A negative photosensitive resin composition containing (B) a photopolymerization initiator and (C) a solvent. The group having an ethylenically unsaturated bond has the following general formula (3):

(In the formula,
R ₃ , R ₄ , and R ₅ are hydrogen atoms or monovalent organic groups having 1 to 3 carbon atoms, and
l is an integer selected from 2 to 10. )
The negative photosensitive resin composition according to claim 1, which is a group represented by: The above Y ₁ and Y ₂ are represented by the following general formula (4) or (5):

(In the formula,
He ₁ is a tetrazole ring, triazole ring, imidazole ring, pyrazole ring, pyrrole ring, pyrimidine ring, pyridine ring, or triazine ring, which may be substituted with a monovalent organic group,
_He2 is an imidazole ring, pyrazole ring, or pyrrole ring, which may be substituted with a monovalent organic group,
Ar is a 5- to 6-membered aromatic ring or a 5- to 6-membered heterocycle, which may be substituted with a monovalent organic group, and
Ar and He ₂ form a condensed ring structure. )
The negative photosensitive resin composition according to claim 1, which is a group derived from an amine compound represented by: The negative photosensitive resin composition according to claim 3, wherein the He ₁ is a tetrazole ring, a triazole ring, an imidazole ring, a pyrazole ring, or a pyrrole ring, which may be substituted with a monovalent organic group. The above Y ₁ and Y ₂ are represented by the following general formula (6) or (7):

(In the formula,
He ₃ is a triazole ring, imidazole ring, or pyrazole ring that may be substituted with a monovalent organic group,
He ₄ is an imidazole ring or a pyrrole ring, which may be substituted with a monovalent organic group,
Ar is a 6-membered aromatic ring or a 6-membered heterocycle which may be substituted with a monovalent organic group, and
Ar and He ₄ form a condensed ring structure. )
The negative photosensitive resin composition according to claim 1, which has a structure derived from an amine compound represented by: The above X represents the following general formulas (8) to (11):

The negative photosensitive resin composition according to claim 1, which is at least one member selected from the group consisting of: The photopolymerization initiator (B) has the following general formula (12):

(In the formula,
R ₆ , R ₇ and R ₈ are monovalent organic groups, and
R ₆ and R ₇ may be linked to each other to form a ring structure. )
The negative photosensitive resin composition according to claim 1, having an oxime ester structure represented by: The photopolymerization initiator (B) has the following general formulas (13) to (15):

(In the formula,
R _a is a monovalent organic group having 1 to 10 carbon atoms,
R _b is an organic group having 1 to 20 carbon atoms,
R _c is an organic group having 1 to 10 carbon atoms,
R _d is an organic group having 1 to 10 carbon atoms,
a is an integer from 0 to 2,
R _e is an organic group having 1 to 4 carbon atoms,
When there is a plurality of R _e , the plurality of R _e may form a ring,
R _g is a monovalent organic group having 1 to 20 carbon atoms,
R _h is an organic group having 1 to 10 carbon atoms,
R _f is a hydrogen atom or an organic group having 1 to 10 carbon atoms, and
R _i and R _j are monovalent organic groups having 1 to 10 carbon atoms. )
The negative photosensitive resin composition according to claim 1, which is at least one selected from the group consisting of: (D) The negative photosensitive resin composition according to claim 1, further comprising a radically polymerizable compound. (E) The negative photosensitive resin composition according to claim 1, further comprising a thermal crosslinking agent. A method for producing polyimide, comprising the step of curing the negative photosensitive resin composition according to any one of claims 1 to 10 to form polyimide. The following steps:
(1) applying the negative photosensitive resin composition according to any one of claims 1 to 10 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) A method for producing a cured relief pattern, including the step of heat-treating the relief pattern to form a cured relief pattern. (A) The following general formula (1) and/or (2):

{In the formula, each X is independently a tetravalent organic group,
Y ₁ and Y ₂ are groups derived from an amine compound having a 5- to 6-membered heterocycle containing a nitrogen atom,
R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms,
At least one of R ₁ and R ₂ is a group having an ethylenically unsaturated bond, and
At least one of m and n is an integer of 1 or more. }
Contains the structural unit represented by
A structural unit M represented by the general formula (1),
The structural unit N represented by the general formula (2) is 0/100≦(number of moles of structural unit M/number of moles of structural unit N)<100/0
a polyimide precursor containing in a proportion of
A negative photosensitive resin composition containing (B) a photopolymerization initiator and (C) a solvent. The following formula:
Thermogravimetric reduction rate (%) = (Weight after heating to 230°C/Weight at 23°C) x 100
A polyimide precursor having a thermogravimetric reduction rate expressed by 5% or more and less than 25%. A negative photosensitive resin composition comprising (A) a polyimide precursor that is a polymer of tetracarboxylic dianhydride and an amine compound,
The polyimide precursor (A) has an ethylenically unsaturated bond in its side chain,
The number of rings that the amine compound has is one or two, and
At least one of the rings includes a 5- to 6-membered heterocycle containing a nitrogen atom,
Negative photosensitive resin composition. A method for producing a negative photosensitive resin composition comprising a polyimide precursor that is a polymer of tetracarboxylic dianhydride and an amine compound having a 5- to 6-membered heterocycle containing a nitrogen atom, the method comprising:
The method includes the following (i) and/or (ii):
(i) The number of rings that the amine compound has is one or two. (ii) The ratio of the number of nitrogen atoms to the number of carbon atoms in the amine compound (nitrogen atoms/carbon atoms) is 35% or more. 500% or less, and
A carboxyl group (-COOH group) contained in tetracarboxylic dianhydride,
A method for producing a negative photosensitive resin composition, comprising a step of reacting an amino group (-NH ₂ ) or -NH- in a heterocycle contained in the amine compound to obtain (A) a polyimide precursor. . A method for producing a polyimide precursor that is a polymer of tetracarboxylic dianhydride and an amine compound having a 5- to 6-membered heterocycle containing a nitrogen atom, comprising:
The method includes the following (i) and/or (ii):
(i) The number of rings that the amine compound has is one or two. (ii) The ratio of the number of nitrogen atoms to the number of carbon atoms in the amine compound (nitrogen atoms/carbon atoms) is 35% or more. 500% or less, and
A step of reacting the carboxyl group (-COOH group) contained in the tetracarboxylic dianhydride with the amino group (-NH ₂ ) or the -NH- structure in the heterocycle contained in the amine compound, (A) Method for producing polyimide precursor.

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