JP2023086715A - Photosensitive resin composition, method for manufacturing cured relief pattern, and semiconductor device - Google Patents

Abstract

To provide: a photosensitive resin composition which has high adhesion even onto copper or copper alloys and can form a cured film reduced in migration; and a method for manufacturing a cured relief pattern and a semiconductor device which employ the composition.SOLUTION: A negative photosensitive resin composition comprises (A) a resin containing a polyimide precursor, a polyimide, or both, (B) a photoinitiator, and (C) a nitrogen-containing heterocyclic compound. The (C) nitrogen-containing heterocyclic compound is at least one selected from compounds of general formulas (4) and (5).SELECTED DRAWING: None

Description

The present disclosure relates to a photosensitive resin composition, a method for producing a cured relief pattern, and a semiconductor device.

BACKGROUND ART Conventionally, polyimide resins, which have excellent heat resistance, electrical properties and mechanical properties, have been used as insulating materials for electronic parts, passivation films, surface protective films, interlayer insulating films, etc. for semiconductor devices. Among these polyimide resins, those provided in the form of photosensitive polyimide precursors easily form a heat-resistant relief pattern film by thermal imidization treatment by applying, exposing, developing, and curing the precursor. be able to. Such a photosensitive polyimide precursor has the feature of enabling a significant reduction in the process compared to conventional non-photosensitive polyimides.

On the other hand, in recent years, the method of mounting semiconductor devices on printed wiring boards has also changed from the viewpoint of improvements in integration and functions, and miniaturization of chip sizes. The polyimide film directly contacts the solder bumps, such as BGA (Ball Gripped Array), CSP (Chip Size Packaging), etc. where higher density mounting is possible from the conventional mounting method using metal pins and lead-tin eutectic solder. Structures that do When forming such a bump structure, the film is required to have high heat resistance and chemical resistance. Patent Document 1 discloses a method for improving the heat resistance of a polyimide film or a polybenzoxazole film by adding a thermal crosslinking agent to a composition containing a polyimide precursor or a polybenzoxazole precursor.

As the miniaturization of semiconductor devices advances, the wiring resistance of semiconductor devices cannot be ignored. Therefore, the gold or aluminum wiring that has been used hitherto is being replaced with copper or copper alloy wiring, which has a lower resistance. However, conventional photosensitive resin compositions have a problem of poor adhesion to copper, resulting in peeling of the resin from the copper wiring.

Such a metal rewiring layer is required to exhibit insulating properties even after a reliability test. The reliability test performed here includes, for example, a high-temperature storage test in which the device is stored for 168 hours at 150° C. in air with a humidity of 5%. However, in conventional photosensitive resin compositions, copper migration occurs during this reliability test, increasing the possibility of short-circuiting and disconnection occurring in the rewiring layer.

Patent Documents 2 and 3 disclose a method for improving adhesion to copper or a copper alloy and preventing corrosion by adding tetrazole or a derivative thereof to a composition containing a polyimide precursor.

JP 2003-287889 A Japanese Patent Application Laid-Open No. 2020-2281 Japanese Patent No. 3170174

However, the compositions described in Patent Documents 2 and 3 do not have a sufficient effect of suppressing migration or an effect of improving adhesion, and it has been difficult to achieve both of these properties. Therefore, the present disclosure provides a photosensitive resin composition that provides a cured film with high adhesion even on copper or a copper alloy and with suppressed migration, a method for producing a cured relief pattern using the same, and a semiconductor device. intended to provide

｛式中、Ｘ_１は、炭素数６～４０の４価の有機基であり、Ｙ_１は、炭素数６～４０の２価の有機基であり、ｎは、２～５０の整数であり、そしてＲ_１及びＲ_２は、それぞれ独立に、水素原子、又は下記一般式（２ａ）若しくは（２ｂ）：

（式中、Ｒ_３は、水素原子又は炭素数１～３の有機基であり、Ｒ_４及びＲ_５は、それぞれ独立に、水素原子又は炭素数１～３の有機基であり、そして、ｍは、２～１０の整数である。）で表される１価の有機基、又は炭素数１～４の飽和脂肪族基である。但し、Ｒ_１及びＲ_２の両者は同時に水素原子であることはない。｝
で表されるポリアミド酸エステル又はポリアミド酸塩であり、
上記（Ａ）ポリイミドが、下記一般式（３）：

｛式中、Ｘ_２は、炭素数６～４０の４価の有機基であり、Ｙ_２は、炭素数６～４０の２価の有機基であり、ｎは、２～５０の整数である。｝
で表されるポリイミド樹脂であり、
上記（Ｃ）含窒素複素環化合物が、下記一般式（４）：

｛式中、Ｒ_６は、水素原子、ハロゲン原子、アルコキシ基、（メタ）アクリロイルオキシ基、ケイ素原子含有基、水酸基、アミノ基、炭素数１～２５のアルキル基、アルコキシアルキル基、芳香族基若しくは含窒素複素環を有する基、及びこれらの組み合わせからなる群から選択される１価の有機基であり、Ｒ_７～Ｒ_１０は、それぞれ独立に、水素原子、ハロゲン原子、水酸基、炭素数１～１０のアルキル基、アルコキシアルキル基若しくは芳香族基、及びこれらの組み合わせからなる群から選択される１価の有機基である。｝で表される化合物、及び
下記一般式（５）：

｛式中、Ｒ_３１～Ｒ_３３は、それぞれ独立に、水素原子、水酸基、カルボキシ基、アミノ基、アゾ結合含有基、脂肪族炭化水素基、アルコキシ基、ヒドロキシアルキル基、芳香族基、含窒素複素環を有する基、及びこれらの組み合わせからなる群から選択される１価の有機基であり、ただし、Ｒ_３１～Ｒ_３３の少なくとも一つが含窒素複素環を有する基である。｝
で表される化合物からなる群から選択される少なくとも一つである、感光性樹脂組成物。
［２］
上記（Ｃ）含窒素複素環化合物が、下記一般式（４ａ）：

｛式中、Ｒ_１１は水素原子、ハロゲン原子、ケイ素原子含有基、水酸基、アミノ基、及び炭素数１～１０のアルキル基若しくは芳香族基からなる群から選択される１価の有機基である。｝
で表される化合物を含む、項目１に記載の感光性樹脂組成物。
［３］
上記（Ｃ）含窒素複素環化合物が、下記一般式（４ｂ）：

｛式中、Ｒ_１２は水素原子、ハロゲン原子、（メタ）アクリロイルオキシ基、ケイ素原子含有基、水酸基、アミノ基、炭素数１～１５のアルキル基、芳香族基若しくは含窒素複素環を有する基、及びこれらの組み合わせからなる群から選択される１価の有機基であり、そして、ｍは１～１０の整数である。｝
で表される化合物を含む、項目１又は２に記載の感光性樹脂組成物。
［４］
上記一般式（４ｂ）において、Ｒ_１２が、上記含窒素複素環を有する基、または上記ケイ素原子含有基である、項目３に記載の感光性樹脂組成物。
［５］
上記一般式（４ｂ）において、Ｒ_１２がイミダゾール骨格を有する基である、項目３又は４に記載の感光性樹脂組成物。
［６］
上記一般式（４ｂ）において、Ｒ_１２がアルコキシシリル基を有する基である、項目３～５のいずれか一項に記載の感光性樹脂組成物。
［７］
上記一般式（５）で表される含窒素複素環化合物において、Ｒ_３１～Ｒ_３３の少なくとも二つが含窒素複素環を有する基である、項目１～６のいずれか一項に記載の感光性樹脂組成物。
［８］
（Ｄ）テトラゾール化合物をさらに含む、項目１～７のいずれか一項に記載の感光性樹脂組成物。
［９］
上記（Ｄ）テトラゾール化合物が、５－アミノ－１Ｈ－テトラゾールである、項目８に記載の感光性樹脂組成物。
［１０］
上記（Ｃ）含窒素複素環化合物が、下記一般式（５ａ）及び（５ｂ）：

｛式（５ａ）及び（５ｂ）中、Ｒ_３４は水素原子、ハロゲン原子、ケイ素原子含有基、リン原子含有基、水酸基、カルボキシ基、アミノ基、炭素数１～２０のアルキル基、芳香族基若しくは含窒素複素環を有する基からなる群から選択される１価の有機基であり、式（５ａ）中、２つのＲ_３５は、それぞれ独立に、ＣＨ又は窒素原子である。｝
で表される化合物から選択される少なくとも一つを含む、項目１～９のいずれか一項に記載の感光性樹脂組成物。
［１１］
上記一般式（１）のＸ_１及び／又は上記一般式（３）のＸ_２が、下記一般式（６）～（８）：

｛一般式（８）中、Ｒ_１３は酸素原子、硫黄原子、または２価の有機基である。｝
からなる群から選択される少なくとも１種以上の有機基である、項目１～１０のいずれか一項に記載の感光性樹脂組成物。
［１２］
上記一般式（１）のＹ_１及び／又は上記一般式（３）のＹ_２が、下記一般式（９）～（１２）：

｛Ｒ_１４、Ｒ_１５、Ｒ_１６及びＲ_１７は、それぞれ独立に、水素原子、炭素数が１～５の１価の脂肪族基、又は水酸基であり、互いに同一であっても異なっていてもよい。｝

｛Ｒ_２６は２価の基であり、Ｒ_１８～Ｒ_２５は、それぞれ独立に、水素原子、ハロゲン原子、炭素数が１～５の１価の脂肪族基、又は水酸基であり、互いに同一であっても異なっていてもよい。｝

｛Ｒ_２７及びＲ_２８は２価の基であり、Ｒ_２９及びＲ_３０は、それぞれ独立に、水素原子、ハロゲン原子、炭素数が１～５の１価の脂肪族基、又は水酸基であり、互いに同一であっても異なっていてもよい。｝
からなる群から選択される少なくとも１種以上の有機基である、項目１～１１のいずれか一項に記載の感光性樹脂組成物。
［１３］
上記一般式（１）で表される（Ａ）ポリイミド前駆体を少なくとも２種類以上含む、及び／又は、上記一般式（３）で表される（Ａ）ポリイミドを少なくとも２種類以上含む、項目１～１２のいずれか一項に記載の感光性樹脂組成物。
［１４］
上記一般式（１）において、Ｘ_１を少なくとも２種類以上有する、及び／又は、上記一般式（３）において、Ｘ_２を少なくとも２種類以上有する、項目１～１３のいずれか一項に記載の感光性樹脂組成物。
［１５］
（１）項目１～１４のいずれか一項に記載の感光性樹脂組成物を基板上に塗布することによって感光性樹脂層を上記基板上に形成する工程と、
（２）上記感光性樹脂層を露光する工程と、
（３）上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）上記レリーフパターンを加熱処理することによっ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。
［１６］
上記基板が、銅又は銅合金から形成されている、項目１５に記載の硬化レリーフパターンの製造方法。
［１７］
項目１５又は１６に記載の硬化レリーフパターンの製造方法により得られる硬化レリーフパターンを含む、半導体装置。 Examples of embodiments in the present disclosure are listed in items [1] to [17] below.
[1]
Ingredients for:
(A) a resin comprising a polyimide precursor, a polyimide, or both;
(B) a photopolymerization initiator, and (C) a negative photosensitive resin composition containing a nitrogen-containing heterocyclic compound,
The (A) polyimide precursor has the following general formula (1):

{wherein X ₁ is a tetravalent organic group having 6 to 40 carbon atoms, Y ₁ is a divalent organic group having 6 to 40 carbon atoms, and n is an integer of 2 to 50; , and R ₁ and R ₂ are each independently a hydrogen atom, or the following general formula (2a) or (2b):

(wherein R ₃ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10) or a saturated aliphatic group having 1 to 4 carbon atoms. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. }
A polyamic acid ester or polyamic acid salt represented by
The (A) polyimide has the following general formula (3):

{Wherein, X ₂ is a tetravalent organic group having 6 to 40 carbon atoms, Y ₂ is a divalent organic group having 6 to 40 carbon atoms, and n is an integer of 2 to 50 . }
is a polyimide resin represented by
The nitrogen-containing heterocyclic compound (C) has the following general formula (4):

{Wherein, R ₆ is a hydrogen atom, a halogen atom, an alkoxy group, a (meth)acryloyloxy group, a silicon atom-containing group, a hydroxyl group, an amino group, an alkyl group having 1 to 25 carbon atoms, an alkoxyalkyl group, an aromatic group or a group having a nitrogen-containing heterocyclic ring, and a monovalent organic group selected from the group consisting of combinations thereof, and R ₇ to R ₁₀ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or a carbon number of 1 1 to 10 alkyl groups, alkoxyalkyl groups or aromatic groups, and monovalent organic groups selected from the group consisting of combinations thereof. } and the following general formula (5):

{wherein R ₃₁ to R ₃₃ each independently represent a hydrogen atom, a hydroxyl group, a carboxy group, an amino group, an azo bond-containing group, an aliphatic hydrocarbon group, an alkoxy group, a hydroxyalkyl group, an aromatic group, a nitrogen-containing a heterocyclic ring-containing group and a monovalent organic group selected from the group consisting of combinations thereof, provided that at least one of R ₃₁ to R ₃₃ is a nitrogen-containing heterocyclic ring-containing group; }
A photosensitive resin composition which is at least one selected from the group consisting of the compounds represented by:
[2]
The nitrogen-containing heterocyclic compound (C) has the following general formula (4a):

{In the formula, R ₁₁ is a monovalent organic group selected from the group consisting of a hydrogen atom, a halogen atom, a silicon atom-containing group, a hydroxyl group, an amino group, and an alkyl group having 1 to 10 carbon atoms or an aromatic group. . }
The photosensitive resin composition according to item 1, comprising a compound represented by:
[3]
The nitrogen-containing heterocyclic compound (C) has the following general formula (4b):

{Wherein, R ₁₂ is a hydrogen atom, a halogen atom, a (meth)acryloyloxy group, a silicon atom-containing group, a hydroxyl group, an amino group, an alkyl group having 1 to 15 carbon atoms, an aromatic group, or a group having a nitrogen-containing heterocyclic ring , and combinations thereof, and m is an integer of 1-10. }
3. The photosensitive resin composition according to item 1 or 2, comprising a compound represented by:
[4]
The photosensitive resin composition according to item 3, wherein in the general formula (4b), R ₁₂ is the nitrogen-containing heterocyclic ring-containing group or the silicon atom-containing group.
[5]
5. The photosensitive resin composition according to item 3 or 4, wherein in the general formula (4b), R ₁₂ is a group having an imidazole skeleton.
[6]
The photosensitive resin composition according to any one of items 3 to 5, wherein in the general formula (4b), R ₁₂ is a group having an alkoxysilyl group.
[7]
Photosensitivity according to any one of items 1 to 6, wherein in the nitrogen-containing heterocyclic compound represented by the general formula (5), at least two of R ₃₁ to R ₃₃ are groups having a nitrogen-containing heterocyclic ring. Resin composition.
[8]
(D) The photosensitive resin composition according to any one of Items 1 to 7, further comprising a tetrazole compound.
[9]
9. The photosensitive resin composition according to item 8, wherein (D) the tetrazole compound is 5-amino-1H-tetrazole.
[10]
The nitrogen-containing heterocyclic compound (C) is represented by the following general formulas (5a) and (5b):

{In formulas (5a) and (5b), R ₃₄ is a hydrogen atom, a halogen atom, a silicon atom-containing group, a phosphorus atom-containing group, a hydroxyl group, a carboxyl group, an amino group, an alkyl group having 1 to 20 carbon atoms, an aromatic group or a monovalent organic group selected from the group consisting of groups having a nitrogen-containing heterocyclic ring, and in formula (5a), two R ₃₅ are each independently CH or a nitrogen atom. }
The photosensitive resin composition according to any one of items 1 to 9, comprising at least one selected from the compounds represented by
[11]
X ₁ in the general formula (1) and/or X ₂ in the general formula (3) are represented by the following general formulas (6) to (8):

{In general formula (8), R ₁₃ is an oxygen atom, a sulfur atom, or a divalent organic group. }
The photosensitive resin composition according to any one of items 1 to 10, which is at least one organic group selected from the group consisting of
[12]
Y ₁ of the general formula (1) and/or Y ₂ of the general formula (3) are represented by the following general formulas (9) to (12):

{R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and may be the same or different good. }

{R ₂₆ is a divalent group, R ₁₈ to R ₂₅ are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and are the same There may be or may be different. }

{R ₂₇ and R ₂₈ are divalent groups, R ₂₉ and R ₃₀ are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, They may be the same or different. }
The photosensitive resin composition according to any one of items 1 to 11, which is at least one organic group selected from the group consisting of
[13]
Item 1, containing at least two (A) polyimide precursors represented by the general formula (1) and/or containing at least two (A) polyimides represented by the general formula (3) 13. The photosensitive resin composition according to any one of items 1 to 12.
[14]
According to any one of items 1 to 13, having at least two types of X ₁ in the general formula (1) and/or having at least two types of X ₂ in the general formula (3) A photosensitive resin composition.
[15]
(1) forming a photosensitive resin layer on the substrate by applying the photosensitive resin composition according to any one of items 1 to 14 onto the substrate;
(2) exposing the photosensitive resin layer;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) forming a cured relief pattern by heat-treating the relief pattern;
A method of manufacturing a cured relief pattern, comprising:
[16]
16. A method for manufacturing a hardened relief pattern according to item 15, wherein the substrate is made of copper or a copper alloy.
[17]
A semiconductor device comprising a cured relief pattern obtained by the method for producing a cured relief pattern according to item 15 or 16.

According to the present disclosure, it is intended to provide a photosensitive resin composition that has excellent adhesion even on copper or a copper alloy and is capable of suppressing migration, a method for forming a cured relief pattern using the same, and a semiconductor device. can be done.

<Photosensitive resin composition>
The photosensitive resin composition of the present disclosure contains, as the (A) resin component, a polyimide precursor, a polyimide, or both of these (in the present disclosure, these are collectively referred to simply as "(A) resin"). . The photosensitive resin composition further contains (B) a photopolymerization initiator and (C) a nitrogen-containing heterocyclic compound. (A) The polyimide precursor is a polyamic acid ester or polyamic acid salt represented by the general formula (1) described later, and (A) the polyimide is a polyimide resin represented by the general formula (3) described later. . And (C) the nitrogen-containing heterocyclic compound is at least one selected from compounds represented by general formulas (4) and (5) described below. The photosensitive resin composition of the present disclosure can provide a photosensitive resin composition that has excellent adhesion even on copper or a copper alloy and that can suppress migration by having the above configuration.

Each component will be described in detail below. Throughout the present specification, structures represented by the same reference numerals in general formulas may be the same or different when a plurality of structures are present in a molecule.

｛式（１）中、Ｘ_１は、炭素数６～４０の４価の有機基であり、Ｙ_１は、炭素数６～４０の２価の有機基であり、ｎは、２～５０の整数であり、そしてＲ_１及びＲ_２は、それぞれ独立に、水素原子、後述する一般式（２ａ）若しくは（２ｂ）で表される１価の有機基、又は炭素数１～４の飽和脂肪族基である。但し、Ｒ_１及びＲ_２の両者は同時に水素原子であることはない。｝ (A) Polyimide Precursor (A) The polyimide precursor is a polyamic acid ester or polyamic acid salt having a structural unit represented by the following general formula (1). (A) A polyimide precursor is converted into a polyimide by subjecting it to a heating (for example, 200° C. or higher) cyclization treatment.

{In formula (1), X ₁ is a tetravalent organic group having 6 to 40 carbon atoms, Y ₁ is a divalent organic group having 6 to 40 carbon atoms, and n is 2 to 50 is an integer, and R ₁ and R ₂ are each independently a hydrogen atom, a monovalent organic group represented by general formula (2a) or (2b) described later, or a saturated aliphatic group having 1 to 4 carbon atoms is the base. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. }

｛式（２ａ）及び（２ｂ）中、Ｒ_３は、水素原子又は炭素数１～３の有機基であり、Ｒ_４及びＲ_５は、それぞれ独立に、水素原子又は炭素数１～３の有機基であり、そして、ｍは、２～１０の整数である。｝Ｒ_１及び／又はＲ_２が一般式（２ｂ）である場合、一般式（１）の対応する部分がカルボン酸イオン（－ＣＯＯ^－）の形態をとり対イオンとなる。Ｒ_３としては、より具体的には、水素原子、メチル基、エチル基、及びプロピル基が挙げられ、好ましくはメチル基である。Ｒ_４及びＲ_５としては、より具体的には、水素原子、メチル基、エチル基、及びプロピル基が挙げられ、好ましくは水素原子である。ｍは、より好ましくは２～５の整数、更に好ましくは２又は３である。式（２ａ）及び（２ｂ）に共通するＲ_３～Ｒ_５及びｍは、互いに同一であってもよく、異なってもよい。 R ₁ and R ₂ in formula (1) may each independently be a monovalent organic group represented by the following general formula (2a) or (2b).

{In formulas (2a) and (2b), R ₃ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms. and m is an integer from 2-10. } When R ₁ and/or R ₂ have the general formula (2b), the corresponding portion of the general formula (1) takes the form of a carboxylate ion (—COO ⁻ ) and becomes a counterion. More specific examples of R ₃ include a hydrogen atom, a methyl group, an ethyl group, and a propyl group, preferably a methyl group. More specific examples of R ₄ and R ₅ include a hydrogen atom, a methyl group, an ethyl group, and a propyl group, preferably a hydrogen atom. m is more preferably an integer of 2-5, more preferably 2 or 3. R ₃ to R ₅ and m common to formulas (2a) and (2b) may be the same or different.

In the above general formula (1), the tetravalent organic group represented by X ₁ preferably has 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, and still more preferably an organic group having 6 to 20 carbon atoms. is. The tetravalent organic represented by X ₁ is more preferably an aromatic group or an alicyclic aliphatic group in which the -COOR ₁ or -COOR ₂ group and the -CONH- group are ortho-positioned to each other. .

｛一般式（８）中、Ｒ_１３は酸素原子、硫黄原子、または２価の有機基である。｝
から選ばれる少なくとも１種以上の有機基であることが好ましい。 In general formula (1), X ₁ is represented by the following general formulas (6) to (8):

{In general formula (8), R ₁₃ is an oxygen atom, a sulfur atom, or a divalent organic group. }
It is preferably at least one or more organic groups selected from

で表される構造であることが、さらに好ましい。また、Ｘ_１の構造は１種でも２種以上の組み合わせでもよい。 X ₁ is, more specifically, the following formula (13):

A structure represented by is more preferable. Moreover, the structure of _X1 may be one or a combination of two or more.

In the above general formula (1), examples of the tetravalent organic group represented by X ₁ include 4,4'-oxydiphthalic anhydride (ODPA), pyromellitic dianhydride (PMDA), and biphenyltetracarboxylic dianhydride. It is particularly preferable to select from at least one of the compounds (BPDA) from the viewpoint of achieving both heat resistance and photosensitive properties.

The structure of _X1 may be of one type or a combination of two or more types, but a combination of two or more types is more preferable from the viewpoint of improving the resolution.

In general formula (1) above, the divalent organic group represented by Y ₁ preferably has 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, in terms of achieving both heat resistance and photosensitive properties. and more preferably an aromatic group having 6 to 20 carbon atoms.

｛Ｒ_１４、Ｒ_１５、Ｒ_１６及びＲ_１７は、それぞれ独立に、水素原子、炭素数が１～５の１価の脂肪族基又は水酸基であり、互いに同一であっても異なっていてもよい。｝

｛Ｒ_２６は２価の基であり、Ｒ_１８～Ｒ_２５は、それぞれ独立に、水素原子、ハロゲン原子、炭素数が１～５の１価の脂肪族基又は水酸基であり、互いに同一であっても異なっていてもよい。｝

｛Ｒ_２７及びＲ_２８は２価の基であり、Ｒ_２９及びＲ_３０は、それぞれ独立に、水素原子、ハロゲン原子、炭素数が１～５の１価の脂肪族基又は水酸基であり、互いに同一であっても異なっていてもよい。｝ In general formula (1), Y ₁ is preferably at least one organic group selected from general formulas (9) to (12) below.

{R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms or a hydroxyl group, and may be the same or different . }

{R ₂₆ is a divalent group, R ₁₈ to R ₂₅ are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms or a hydroxyl group, and are the same as each other. may be different. }

{R ₂₇ and R ₂₈ are divalent groups; R ₂₉ and R ₃₀ are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms or a hydroxyl group; They may be the same or different. }

で表される構造が挙げられるが、これらに限定されるものではない。また、Ｙ_１の構造は１種でも２種以上の組み合わせでもよい。 More specifically, the divalent organic group represented by Y ₁ has the following formula (14):

Examples include, but are not limited to, structures represented by: Moreover, the structure of _Y1 may be one type or a combination of two or more types.

In the above general formula (1), the divalent organic group represented by Y ₁ includes diaminodiphenyl ether (DADPE), p-phenylenediamine (pPD), 2,2-bis[4-(4-aminophenoxy)phenyl ] Propane (BAPP) and 4,4′-diamino-2,2′-dimethylbiphenyl (mTB) are particularly preferable in terms of achieving both heat resistance and photosensitive characteristics.

(A) It is preferable that at least one of R ₁ and R ₂ in the general formula (1) has a group represented by the general formula (2a) or (2b) in the polyimide precursor. In addition, it is more preferable to include precursors having double bonds at the ends of R ₁ and R ₂ containing groups represented by general formula (2a) or (2b).

(A) A polyimide precursor is converted into a polyimide by subjecting it to a heating (for example, 200° C. or higher) cyclization treatment.

｛式中、Ｘ_２は、炭素数６～４０の４価の有機基であり、Ｙ_２は、炭素数６～４０の２価の有機基であり、ｎは、２～５０の整数である。｝感光性樹脂組成物が一般式（３）で表される樹脂を含有することは、熱処理の工程で化学変化を要さずに十分な膜特性を発現することができるので、より低温での熱処理に好適である点で特に好ましい。 (A) Polyimide Polyimide is a polyimide resin having a structural unit represented by the following general formula (3).

{Wherein, X ₂ is a tetravalent organic group having 6 to 40 carbon atoms, Y ₂ is a divalent organic group having 6 to 40 carbon atoms, and n is an integer of 2 to 50 . } When the photosensitive resin composition contains the resin represented by the general formula (3), it is possible to express sufficient film properties without requiring chemical changes in the heat treatment process, so that it can be used at a lower temperature. It is particularly preferable in that it is suitable for heat treatment.

From the viewpoint of heat resistance, the divalent organic group of X ₂ and/or the tetravalent organic group of Y ₂ preferably contains an aromatic ring structure, more preferably a benzene ring structure. From the viewpoint of solubility in organic solvents, at least one of X ₂ and Y ₂ is preferably a fluorine atom-containing group, and both X ₂ and Y ₂ are preferably fluorine atom-containing groups. The tetravalent organic group for X ₂ and/or the divalent organic group for Y ₂ preferably has a structure in which 2 to 6 benzene rings are bonded via a single bond or a divalent linking group. Examples of the divalent linking group here include an alkylene group, a fluorinated alkylene group, an ether group, and the like. Alkylene groups and fluorinated alkylene groups may be linear or branched.

_X2 may be the same as or different from the structure of _X1 described above in the description of the general formula (1) of the polyimide precursor. X ₂ is an organic group preferably having 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, still more preferably 6 to 20 carbon atoms. X ₂ is more preferably an aromatic group or an alicyclic aliphatic group in which the -COOR ₁ or -COOR ₂ group and the -CONH- group are ortho-positioned to each other. X ₂ is preferably at least one organic group selected from the general formulas (6) to (8) described above in the description of the general formula (1) of the polyimide precursor, specifically the above-described formula (13) The structure represented by is more preferable.

Y ₂ may have the same structure as or different from Y ₁ described above in the description of general formula (1) of the polyimide precursor. Y ₂ is preferably an aromatic group having 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, still more preferably 6 to 20 carbon atoms. Y ₂ is preferably at least one organic group selected from the general formulas (9) to (12) described above in the description of the general formula (1) of the polyimide precursor, specifically the above-described formula (14) The structure represented by is more preferable.

(A) The resin is preferably at least one resin selected from the group consisting of polyimide precursors and polyimides. (A) As the resin, only a polyimide precursor may be used, or only polyimide may be used. (A) When the resin is a mixture of a polyimide precursor and a polyimide, the total mass of these is 100 parts by mass, for example, the polyimide precursor is 50 parts by mass to 90 parts by mass, and the polyimide is 10 parts by mass to 50 parts by mass. can be a department. (A) It is preferable that the resin contains a polyimide precursor from the viewpoint of higher photosensitivity.

(A) Preparation method of polyimide precursor The polyimide precursor represented by the general formula (1) is, for example, the above-mentioned tetracarboxylic dianhydride containing a tetravalent organic group X ₁ having 6 to 40 carbon atoms and (a) partially esterified tetracarboxylic acid (hereinafter referred to as acid/ester body ), followed by polycondensation with a diamine compound containing a divalent organic group _Y1 .

(Preparation of acid/ester form)
Examples of the tetracarboxylic dianhydride containing a tetravalent organic group X ₁ having 6 to 40 carbon atoms include pyromellitic anhydride, diphenyl ether-3,3′,4,4′-tetracarboxylic dianhydride, Benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenylsulfone-3,3',4,4' -tetracarboxylic dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 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 and the like can be mentioned. . Moreover, these can be used individually by 1 type or in mixture of 2 or more types.

(a) Aliphatic alcohols having 5 to 30 carbon atoms or aromatic alcohols having 6 to 30 carbon atoms, which are formed by bonding a monovalent organic group represented by the general formula (2a) and a hydroxyl group, for example, 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, benzyl alcohol and the like.

The content of the component (a) in the negative photosensitive resin composition is preferably more than 80 mol% of the total content of _R1 and _R2 . When the content of component (a) exceeds 80 mol %, desired photosensitive properties can be obtained, which is preferable. The content of the component (a) in the negative photosensitive resin composition is more preferably 85 mol% or more, more preferably 90 mol% or more, based on the total content of _R1 and _R2 . is more preferable, and 95 mol % or more is particularly preferable.

The tetracarboxylic dianhydride and the alcohol are stirred, dissolved and mixed in a reaction solvent at a reaction temperature of 20 to 50° C. for 4 to 10 hours in the presence of a basic catalyst such as pyridine. Thereby, the half-esterification reaction of the acid dianhydride proceeds to obtain the desired acid/ester form.

The reaction solvent preferably dissolves the acid/ester and the polyimide precursor which is a polycondensation product of the acid/ester and the diamine compound. Examples of reaction solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, gamma-butyrolactone, ketones, esters, lactones, and ethers. , halogenated hydrocarbons, hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane , 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene and the like. These may be used alone or in combination of two or more as needed.

(Preparation of polyimide precursor)
A known dehydration-condensing agent can be added to and mixed with the acid/ester compound (typically, the solution in the reaction solvent) under ice-cooling to convert the acid/ester compound into a polyacid anhydride. After that, a diamine compound containing a divalent organic group _Y1 is separately dissolved or dispersed in a solvent, and then added dropwise thereto for polycondensation to obtain a polyimide precursor. Dehydration condensation agents include, for example, dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N' - includes disuccinimidyl carbonate and the like.

Diamines containing a divalent organic group Y ₁ suitably used in the present disclosure include, for example, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3, 3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone , 3,3′-diaminodiphenyl sulfone, 4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 4,4′-diaminobenzophenone, 3,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis (4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4 ,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl ] ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4- aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl)propane, 2,2-bis[4-(4-amino phenoxy)phenyl)hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolysine sulfone, and 9,9-bis(4-aminophenyl)fluorene, etc., and on their benzene rings part of the hydrogen atoms are substituted with a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a halogen, etc., such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl,3,3'-dimethyl-4,4'-diaminodiphenylmethane,2,2'-dimethyl-4,4'-diaminodiphenylmethane,3,3'-dimethoxy-4,4'-diaminobiphenyl and 3,3'-dichloro-4,4'-diaminobiphenyl, mixtures thereof, and the like can be used. Among these, 4,4'-diaminodiphenyl ether, p-phenylenediamine, 4,4-dimethyl-2,2'-diaminobiphenyl, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane are used. More preferably, 4,4'-diaminodiphenyl ether, p-phenylenediamine, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane are used.

Diaminosiloxanes such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane are commonly used for the purpose of improving adhesion to various substrates. It can also be polymerized.

After completion of the reaction, the water absorption by-product of the dehydration condensation agent coexisting in the reaction solution was filtered off as necessary, and a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof was obtained. It can be added to the polymer component to precipitate the polymer component. Then, by repeating redissolution, reprecipitation, and the like, the polymer is purified and vacuum-dried to isolate the desired polyimide precursor. In order to improve the degree of purification, the polymer solution may be passed through a column packed with an anion exchange resin swollen with a suitable organic solvent to remove ionic impurities.

(A) The molecular weight of the polyimide precursor is preferably 8,000 to 150,000, preferably 9,000 to 50,000, when measured by polystyrene equivalent weight average molecular weight by gel permeation chromatography. is more preferred, and 20,000 to 40,000 is particularly preferred. When the weight-average molecular weight is 8,000 or more, the mechanical properties are favorable. It is preferable because it is good. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. Also, the molecular weight is obtained from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select STANDARD SM-105, an organic solvent-based standard sample manufactured by Showa Denko. The photosensitive resin composition may contain at least two types of (A) polyimide precursors represented by general formula (1).

(A) Preparation method of polyimide (A) Polyimide is obtained by reacting tetracarboxylic acid, corresponding tetracarboxylic acid dianhydride, tetracarboxylic acid diester dichloride, etc. with diamine, corresponding diisocyanate compound, trimethylsilylated diamine. be able to. Polyimide is generally obtained by dehydrating and ring-closing polyamic acid, which is one of the polyimide precursors obtained by reacting tetracarboxylic dianhydride and diamine, by heating or chemical treatment with an acid or base.

Suitable tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'- Benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1- Bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis (2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5, 6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluoric dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride aromatic tetracarboxylic dianhydrides such as anhydrides, diphenylmethane-3,3′,4,4′-tetracarboxylic dianhydrides and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydrides; anhydrides, or aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,3′,4,4′- Compounds represented by diphenylsulfonetetracarboxylic acid dianhydride and the like can be mentioned.

Among them, pyromellitic anhydride (PMDA), diphenyl ether-3,3′,4,4′-tetracarboxylic dianhydride (ODPA), benzophenone-3,3′,4,4′-tetracarboxylic dianhydride (BTDA), biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA), 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), 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 (6FDA) is preferably used. These are used alone or in combination of two or more.

Suitable diamines include 3,4′-diaminodiphenyl ether (3,4′-ODA), 4,4′-diamino-2,2′-bis(trifluoromethyl)biphenyl (TFMB), 3,3′, 5,5′-tetramethylbenzidine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3′-diaminodiphenylsulfone, 3,3′dimethylbenzidine, 3,3′-bis( trifluoromethyl)benzidine, 2,2′-bis(p-aminophenyl)hexafluoropropane, bis(trifluoromethoxy)benzidine (TFMOB), 2,2′-bis(pentafluoroethoxy)benzidine (TFEOB), 2 ,2′-trifluoromethyl-4,4′-oxydianiline (OBABTF), 2-phenyl-2-trifluoromethyl-bis(p-aminophenyl)methane, 2-phenyl-2-trifluoromethyl-bis (m-aminophenyl)methane, 2,2′-bis(2-heptafluoroisopropoxy-tetrafluoroethoxy)benzidine (DFPOB), 2,2-bis(m-aminophenyl)hexafluoropropane (6-FmDA) , 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 3,6-bis(trifluoromethyl)-1,4-diaminobenzene (2TFMPDA), 1-(3,5-diaminophenyl )-2,2-bis(trifluoromethyl)-3,3,4,4,5,5,5-heptafluoropentane, 3,5-diaminobenzotrifluoride (3,5-DABTF), 3,5 -diamino-5-(pentafluoroethyl)benzene, 3,5-diamino-5-(heptafluoropropyl)benzene, 2,2′-dimethylbenzidine (DMBZ), 2,2′,6,6′-tetramethyl Benzidine (TMBZ), 3,6-diamino-9,9-bis(trifluoromethyl)xanthene (6FCDAM), 3,6-diamino-9-trifluoromethyl-9-phenylxanthene (3FCDAM), 3,6- compounds represented by diamino-9,9-diphenylxanthene;

The ratio of diamine to acid dianhydride used may basically be 1:1 in terms of molar ratio. However, one may be used in excess to obtain the desired terminal structure. Specifically, by using an excessive amount of diamine, the ends (both ends) of polyimide (A) tend to become amino groups. On the other hand, when the acid dianhydride is used excessively, the ends (both ends) of the polyimide (A) tend to become acid anhydride groups. As described above, in the present disclosure, polyimide (A) preferably has an acid anhydride group at its terminal. Therefore, in the present disclosure, it is preferable to use an excess amount of acid dianhydride when synthesizing the polyimide (A).

The terminal amino groups and/or acid anhydride groups of the polyimide obtained by condensation polymerization may be reacted with some reagent so that the polyimide terminals have desired functional groups.

(A) The molecular weight of the polyimide is preferably 5,000 to 150,000, more preferably 7,000 to 100,000, when measured by a polystyrene equivalent weight average molecular weight by gel permeation chromatography. Preferably, 10,000 to 50,000 is particularly preferred. When the weight-average molecular weight is 5,000 or more, the mechanical properties are favorable. It is preferable because it is good. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. Also, the molecular weight is obtained from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select STANDARD SM-105, an organic solvent-based standard sample manufactured by Showa Denko.

(B) Photopolymerization Initiator As the photopolymerization initiator (B), any compound conventionally used as a photopolymerization initiator for UV curing can be selected. (B) Photopolymerization initiators include, for example, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenylketone, dibenzylketone, benzophenone derivatives such as fluorenone, 2,2′-diethoxy Acetophenone and acetophenone derivatives such as 2-hydroxy-2-methylpropiophenone, thioxanthone derivatives such as 1-hydroxycyclohexylphenyl ketone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and diethylthioxanthone, benzyl, benzyl dimethyl ketal and benzyl derivatives such as benzyl-β-methoxyethyl acetal, benzoin derivatives such as benzoin methyl ether, 2,6-di(4'-diazidobenzal)-4-methylcyclohexanone, and 2,6'-di(4'- diazidobenzal) azides such as cyclohexanone, 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione- 2-(O-ethoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxy oximes such as propanetrione-2-(O-benzoyl)oxime, N-arylglycines such as N-phenylglycine, peroxides such as benzoyl peroxide, aromatic biimidazoles, and titanocenes are used. be done. Among these, the above oximes are preferable from the viewpoint of photosensitivity.

The amount of the photopolymerization initiator (B) is preferably 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of the resin (A), and more preferably 2 parts by mass to 15 parts by mass from the viewpoint of photosensitivity characteristics. Department. The photosensitive resin composition has excellent photosensitivity by containing 0.1 parts by mass or more of the photopolymerization initiator (B) with respect to 100 parts by mass of the (A) resin, while containing 20 parts by mass or less of the photopolymerization initiator. Excellent thick film curability.

(C) Nitrogen-Containing Heterocyclic Compound The nitrogen-containing heterocyclic compound includes a 2,4,6-substituted-1,3,5-triazine derivative represented by the general formula (4) described below, and a ) is at least one selected from the group consisting of 2,4,6-substituted pyridine derivatives represented by By using these (C) nitrogen-containing heterocyclic compounds, it is possible to provide a photosensitive resin composition which is excellent in adhesion on copper or a copper alloy and in the effect of inhibiting migration. The chemical mechanism of the excellent adhesion and migration control effect on copper or copper alloy is not clear, but by using a specific nitrogen-containing heterocyclic compound, the surface free energy is relatively high compared to resins and additives. It is presumed that the copper can be closer to the copper and can exist more stably near the copper interface than the surrounding resin and additives. Since the π-conjugated heterocyclic ring interacts with d-orbital electrons of copper, it is speculated that it exhibits copper adhesion and prevents the diffusion of copper ions, thereby suppressing copper migration.

｛式中、Ｒ_６は、水素原子、ハロゲン原子、アルコキシ基、（メタ）アクリロイルオキシ基、ケイ素原子含有基、水酸基、アミノ基、炭素数１～２５のアルキル基、アルコキシアルキル基、芳香族基若しくは含窒素複素環を有する基、及びこれらの組み合わせからなる群から選択される１価の有機基であり、Ｒ_７～Ｒ_１０は、それぞれ独立に、水素原子、ハロゲン原子、水酸基、炭素数１～１０のアルキル基、アルコキシアルキル基若しくは芳香族基、及びこれらの組み合わせからなる群から選択される１価の有機基である。｝ The 2,4,6-substituted-1,3,5-triazine derivative can be represented by the following general formula (4).

{Wherein, R ₆ is a hydrogen atom, a halogen atom, an alkoxy group, a (meth)acryloyloxy group, a silicon atom-containing group, a hydroxyl group, an amino group, an alkyl group having 1 to 25 carbon atoms, an alkoxyalkyl group, an aromatic group or a group having a nitrogen-containing heterocyclic ring, and a monovalent organic group selected from the group consisting of combinations thereof, and R ₇ to R ₁₀ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or a carbon number of 1 1 to 10 alkyl groups, alkoxyalkyl groups or aromatic groups, and monovalent organic groups selected from the group consisting of combinations thereof. }

In the general formula (4), the number of carbon atoms in the group having an alkyl group, alkoxyalkyl group, aromatic group or nitrogen-containing heterocyclic ring for R ₆ is 1 to 25, for example 1 to 20, 1 to 15 or 1 to 10. can be R ₆ in general formula (4) is more preferably a group having a nitrogen-containing heterocyclic ring having a total of 1 to 25 carbon atoms; an alkyl group having a silyl group; an alkyl group having a total carbon number of 5 to 25, 5 to 20, 5 to 15 or 5 to 10 and having a (meth)acryloyloxy group; and a total carbon number of 4 to 25, 4 to 20 , 4 to 15 or 4 to 10 amino groups having one or two alkoxyalkyl groups. Groups having a nitrogen-containing heterocyclic ring include substituted or unsubstituted pyrrolyl, imidazolyl, triazole, pyridinyl, triazinyl, thiazolyl, pyrazinyl groups, and combinations thereof. Examples of the substituent which the nitrogen-containing heterocyclic ring may have include an alkyl group having 1 to 12 carbon atoms, a halogen atom, an alkoxy group, an alkoxysilyl group, a hydroxyl group, an amino group, and the like. Examples of alkoxyalkyl groups include alkoxyalkyl groups having a total of 2 to 10 carbon atoms, such as methoxymethyl, ethoxymethyl and ethoxyethyl groups.

R ₇ to R ₁₀ in general formula (4) are more preferably hydrogen atoms and alkoxyalkyl groups. Examples of alkoxyalkyl groups include alkoxyalkyl groups having a total of 2 to 10 carbon atoms, such as methoxymethyl, ethoxymethyl and ethoxyethyl groups.

Specific examples of 2,4,6-substituted-1,3,5-triazine derivatives represented by general formula (4) include 2,4-diamino-1,3,5-triazine, 2,4-diamino -6-methyl-1,3,5-triazine, 2,4,6-triamino-1,3,5-triazine, 2,4-diamino-6-hydroxy-1,3,5-triazine, 2-vinyl -4,6-diamino-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-chloro-1,3,5-triazine , 2,4-diamino-6-dimethylamino-1,3,5-triazine, 2,4-diamino-6-(cyclopropylamino)-1,3,5-triazine, 2,4-diamino-6- isopropoxy-1,3,5-triazine, 2,4-diamino-6-butylamino-1,3,5-triazine, 2,4-diamino-6-diethylamino-1,3,5-triazine, 2, 4-diamino-6-phenyl-1,3,5-triazine, 2,4-diamino-6-diallylamino-1,3,5-triazine, 2-chloro-4-ethylamino-6-isopropylamino-1 ,3,5-triazine, 2,4-diamino-6-[2-(2-undecyl-1-imidazolyl)ethyl]-1,3,5-triazine, 2,4-diamino-6-[2-( 2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine, 2,4-diamino-6-[2-(2-ethyl-4-methyl-1-imidazolyl)ethyl]-1,3, 5-triazine, 2,4-diamino-6-(triethoxysilyl)ethyl-1,3,5-triazine, 2,4-diamino-6-methacryloyloxyethyl-1,3,5-triazine, 2,4 ,6-tris(chloroamino)-1,3,5-triazine, N,N′-diisopropyl-6-(methylthio)-1,3,5-triazine-2,4-diamine, 2-(tert-butyl amino)-4-(cyclopropylamino)-6-(methylthio)-1,3,5-triazine, 4-(4,6-dimorpholino-1,3,5-triazin-2-yl)aniline, 2, 4,6-tris[bis(methoxymethyl)amino]-1,3,5-triazine, N,N′,N″-tri(m-tolyl)-1,3,5-triazine-2,4, 6-triamine, 3,9-bis[2-(3,5-diamino-2,4,6-triazaphenyl)ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 2,4,6-tri(9H-carbazol-9-yl)-1,3,5-triazine, 4,4′,4″-(1,3,5-triazine-2,4,6-triy tris(2-ethylhexyl) trisbenzoate and the like.

｛式中、Ｒ_１１は水素原子、ハロゲン原子、ケイ素原子含有基、水酸基、アミノ基、及び炭素数１～１０のアルキル基若しくは芳香族基からなる群から選択される１価の有機基である。｝で表される化合物、または下記一般式（５）：

｛式中、Ｒ_１２は水素原子、ハロゲン原子、（メタ）アクリロイルオキシ基、ケイ素原子含有基、水酸基、アミノ基、炭素数１～１５のアルキル基、芳香族基若しくは含窒素複素環を有する基、及びこれらの組み合わせからなる群から選択される１価の有機基であり、そして、ｍは１～１０の整数である。｝
で表される化合物からなる群より選ばれる少なくとも１種のトリアジン誘導体であることが、銅又は銅合金の上での密着性の観点から好ましい。 The 2,4,6-substituted-1,3,5-triazine derivative has the following general formula (4a):

{In the formula, R ₁₁ is a monovalent organic group selected from the group consisting of a hydrogen atom, a halogen atom, a silicon atom-containing group, a hydroxyl group, an amino group, and an alkyl group having 1 to 10 carbon atoms or an aromatic group. . }, or the following general formula (5):

{Wherein, R ₁₂ is a hydrogen atom, a halogen atom, a (meth)acryloyloxy group, a silicon atom-containing group, a hydroxyl group, an amino group, an alkyl group having 1 to 15 carbon atoms, an aromatic group, or a group having a nitrogen-containing heterocyclic ring , and combinations thereof, and m is an integer of 1-10. }
At least one triazine derivative selected from the group consisting of compounds represented by is preferable from the viewpoint of adhesion on copper or copper alloy.

In the general formula (4b), the alkyl group, aromatic group or nitrogen-containing heterocyclic ring-containing group for R ₁₂ has 1 to 15 carbon atoms, and may be 1 to 10 carbon atoms, for example. R ₁₂ in general formula (4b) is more preferably a group having a nitrogen-containing heterocyclic ring having 1 to 15 or 1 to 10 carbon atoms in total; an alkoxysilyl group having 3 to 15 or 3 to 10 carbon atoms in total; and a (meth)acryloyloxy group. Groups having a nitrogen-containing heterocyclic ring include substituted or unsubstituted pyrrolyl, imidazolyl, triazole, pyridinyl, triazinyl, thiazolyl, pyrazinyl groups, and combinations thereof. Examples of these substituents include alkyl groups having 1 to 12 carbon atoms, halogen atoms, alkoxy groups, alkoxysilyl groups, hydroxyl groups, and amino groups.

In general formula (4b), R ₁₂ is more preferably a group having a nitrogen-containing heterocyclic ring or a group having a silicon atom-containing group. By having a nitrogen-containing heterocyclic structure or a silicon atom-containing group in R ₁₂ , stronger adhesion to copper can be exhibited, and good breaking elongation can be maintained even after a wet heat durability test.

In general formula (4b), R ₁₂ is more preferably a group having an imidazole skeleton. Since R ₁₂ has an imidazole skeleton, the number of nitrogen atoms increases and the coordinating force with copper increases, so stronger copper adhesion is exhibited. In addition, due to the basicity of the imidazole group, the imidization reaction proceeds efficiently at high temperatures, forming a stronger film, so that a good breaking elongation can be maintained even after the wet heat durability test. The group having an imidazole skeleton is, for example, a substituted or unsubstituted imidazolyl group, and the substituent is preferably an alkyl group having 1 to 12 carbon atoms.

In general formula (4b), R ₁₂ is more preferably a group having an alkoxysilyl group. Since R ₁₂ has an alkoxysilyl group, the alkoxysilyl group forms a covalent bond with other components such as a polymer through a polymerization reaction, so that a stronger adhesion to the copper substrate is exhibited, and a wet heat durability test is performed. Good breaking elongation can be maintained even after.

Specific examples of the compound represented by the general formula (4a) or (4b) include 2,4-diamino-6-[2-(2-undecyl-1-imidazolyl)ethyl]-1,3, 5-triazine, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine, 2,4-diamino-6-[2-(2-ethyl -4-methyl-1-imidazolyl)ethyl]-1,3,5-triazine, 2,4-diamino-6-(triethoxysilyl)ethyl-1,3,5-triazine, 2,4-diamino-6 -methacryloyloxyethyl-1,3,5-triazine and the like.

｛式中、Ｒ_３１～Ｒ_３３は、それぞれ独立に、水素原子、水酸基、カルボキシ基、アミノ基、アゾ結合含有基、脂肪族炭化水素基、アルコキシ基、ヒドロキシアルキル基、芳香族基、含窒素複素環を有する基、及びこれらの組み合わせからなる群から選択される１価の有機基であり、ただし、Ｒ_３１～Ｒ_３３の少なくとも一つが含窒素複素環を有する基である。｝ The 2,4,6-substituted-pyridine derivative can be represented by the following general formula (5).

{wherein R ₃₁ to R ₃₃ each independently represent a hydrogen atom, a hydroxyl group, a carboxy group, an amino group, an azo bond-containing group, an aliphatic hydrocarbon group, an alkoxy group, a hydroxyalkyl group, an aromatic group, a nitrogen-containing a heterocyclic ring-containing group and a monovalent organic group selected from the group consisting of combinations thereof, provided that at least one of R ₃₁ to R ₃₃ is a nitrogen-containing heterocyclic ring-containing group; }

In general formula (5), at least one of R ₃₁ to R ₃₃ is preferably a group having a total carbon number of 1 to 25, for example 1 to 20, and having a nitrogen-containing heterocyclic ring. Groups having a nitrogen-containing heterocyclic ring include substituted or unsubstituted pyrrolyl, imidazolyl, triazole, pyridinyl, triazinyl, thiazolyl, pyrazinyl groups, and combinations thereof. Combinations of nitrogen-containing heterocycles include, for example, a pyrazinyl group having a pyridinyl group and a triazinyl group having one or two pyridinyl groups. Examples of substituents that the nitrogen-containing heterocyclic ring may have include an alkyl group, a halogen atom, an alkoxy group, an alkoxysilyl group, a hydroxyl group, an amino group, and the like.

In general formula (5), at least two of R ₃₁ to R ₃₃ are more preferably groups having a nitrogen-containing heterocyclic ring. As described above, the nitrogen-containing heterocyclic ring is preferably a group having a nitrogen-containing heterocyclic ring having a total carbon number of preferably 1 to 25, for example 1 to 20. Groups having a nitrogen-containing heterocyclic ring include substituted or unsubstituted pyrrolyl, imidazolyl, triazole, pyridinyl, triazinyl, thiazolyl, pyrazinyl groups, and combinations thereof. Examples of substituents that the nitrogen-containing heterocyclic ring may have include an alkyl group, a halogen atom, an alkoxy group, an alkoxysilyl group, a hydroxyl group, an amino group, and the like.

｛式（５ａ）及び（５ｂ）中、Ｒ_３４は水素原子、ハロゲン原子、ケイ素原子含有基、リン原子含有基、水酸基、カルボキシ基、アミノ基、炭素数１～２０のアルキル基、芳香族基若しくは含窒素複素環を有する基からなる群から選択される１価の有機基であり、式（５ａ）中、２つのＲ_３５は、それぞれ独立に、ＣＨ又は窒素原子である。｝ As the 2,4,6-substituted-pyridine derivative, compounds represented by the following general formulas (5a) and (5b) are more preferable because of their high migration-suppressing effect.

{In formulas (5a) and (5b), R ₃₄ is a hydrogen atom, a halogen atom, a silicon atom-containing group, a phosphorus atom-containing group, a hydroxyl group, a carboxyl group, an amino group, an alkyl group having 1 to 20 carbon atoms, an aromatic group or a monovalent organic group selected from the group consisting of groups having a nitrogen-containing heterocyclic ring, and in formula (5a), two R ₃₅ are each independently CH or a nitrogen atom. }

R ₃₄ in formulas (5a) and (5b) is more preferably a hydrogen atom or a group having a nitrogen-containing heterocyclic ring having 1 to 20 carbon atoms. Groups having a nitrogen heterocycle include substituted or unsubstituted pyrrolyl, imidazolyl, triazole, pyridinyl, triazinyl, thiazolyl, pyrazinyl groups, and combinations thereof. More preferably, both R ₃₅ in formula (5a) are nitrogen atoms.

Examples of 2,4,6-substituted-pyridine derivatives represented by general formula (5) include the following compounds.

The amount of the nitrogen-containing heterocyclic compound (C) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 3 parts by mass, per 100 parts by mass of the resin (A). When the amount is 0.01 parts by mass or more, the adhesiveness on copper or copper alloy is excellent, and when it is 10 parts by mass or less, the storage stability is excellent.

(D) Tetrazole compound The photosensitive resin composition may optionally contain (D) a tetrazole compound. In the present disclosure, the "tetrazole compound" has a structure not included in (C) the nitrogen-containing heterocyclic compound described above.

Tetrazole compounds include 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, 5,5′-bis-1H- tetrazole, 1-methyl-5-ethyl-tetrazole, 1-methyl-5-mercapto-tetrazole, 1-carboxymethyl-5-mercapto-tetrazole and the like. From the viewpoint of improving copper adhesion, 5-amino-1H-1 tetrazole is particularly preferred.

The amount of (D) the tetrazole compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) resin, and more preferably 0.5 to 10 parts by mass from the viewpoint of photosensitivity characteristics. preferable. When the amount of the tetrazole compound per 100 parts by mass of the resin (A) is 0.1 parts by mass or more, even if the photosensitive resin composition is formed on copper or a copper alloy and exposed to a high temperature environment, copper or copper Adhesion to the alloy is excellent, and on the other hand, storage stability is excellent when the content is 20 parts by mass or less.

(other ingredients)
The negative photosensitive resin composition may further contain components other than the above components (A) to (D). Other components include, for example, (A) a resin component other than the resin, a sensitizer, a monomer having a photopolymerizable unsaturated bond, an adhesion aid, a thermal polymerization inhibitor, a hindered phenol compound, an organic titanium compound, Examples include solvents.

The negative photosensitive resin composition may further contain resin components other than the (A) resin. Examples of resin components that can be contained in the negative photosensitive resin composition include polyimides, polyoxazoles, polyoxazole precursors, phenol resins, polyamides, epoxy resins, siloxane resins, and acrylic resins.

The blending amount of these resin components is preferably in the range of 0.01 to 20 parts by mass per 100 parts by mass of resin (A).

The negative photosensitive resin composition may further contain a sensitizer to improve photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal). ) cyclohexanone, 2,6-bis(4′-diethylaminobenzal)-4-methylcyclohexanone, 4,4′-bis(dimethylamino)chalcone, 4,4′-bis(diethylamino)chalcone, p-dimethylamino thinner mylideneindanone, 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, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2- Mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylamino) styryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene and the like. These can be used singly or in combination of a plurality (for example, 2 to 5 types).

The blending amount of the sensitizer is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the resin (A).

The negative photosensitive resin composition may further contain a monomer having a photopolymerizable unsaturated bond in order to improve the resolution of the relief pattern. Such a monomer is preferably a (meth)acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator, and is not particularly limited to the following, but includes ethylene glycol such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate. or mono- or di-acrylates and methacrylates of polyethylene glycol, mono- or di-acrylates and methacrylates of propylene glycol or polypropylene glycol, mono-, di- or triacrylates and methacrylates of glycerol, cyclohexane diacrylates and dimethacrylates, diacrylates of 1,4-butanediol. Acrylates and dimethacrylates, diacrylates and dimethacrylates of 1,6-hexanediol, diacrylates and dimethacrylates of neopentyl glycol, mono- or diacrylates and methacrylates of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and derivatives thereof, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, di- or tri-acrylates and methacrylates of glycerol, di-, tri-, or tetra-acrylates and methacrylates of pentaerythritol, and ethylene oxide or propylene oxide additions of these compounds compounds such as substances.

The amount of the monomer having a photopolymerizable unsaturated bond is preferably 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the resin (A).

The negative photosensitive resin composition may further contain an adhesion aid in order to improve the adhesion between the film formed using the same and the substrate. Examples of adhesion promoters include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl ) succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3′-bis(N-[3-triethoxysilyl]propylamide)-4,4′-dicarboxylic acid, benzene- Silanes such as 1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, and N-phenylaminopropyltrimethoxysilane Coupling agents, and aluminum-based adhesion aids such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like. Among these adhesion aids, silane coupling agents are more preferable from the viewpoint of adhesive strength.

The amount of the adhesion promoter compounded is preferably in the range of 0.5 parts by mass to 25 parts by mass with respect to 100 parts by mass of the resin (A).

The negative photosensitive resin composition may further contain a thermal polymerization inhibitor in order to improve the stability of viscosity and photosensitivity, especially when stored in a solvent-containing solution. Examples of thermal polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, ptert-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- sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt and the like are used.

The content of the thermal polymerization inhibitor is preferably in the range of 0.005 parts by mass to 12 parts by mass with respect to 100 parts by mass of the resin (A).

The negative photosensitive resin composition may further contain a hindered phenol compound to suppress discoloration on copper.
Hindered phenol compounds include, for example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl -4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4′-methylenebis(2,6-di-t-butylphenol), 4,4′-thio-bis(3-methyl-6-t-butylphenol), 4,4′-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3 -t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2 -thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydro cinnamamide), 2,2′-methylene-bis(4-methyl-6-t-butylphenol), 2,2′-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5 -trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl )-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl )-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl )-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6 -dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6- 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, but are limited thereto. not to be Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H )-trione is particularly preferred.

The amount of the hindered phenol compound compounded is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin (A), and from the viewpoint of photosensitivity characteristics, it is 0.5 to 10 parts by mass. It is more preferable to have When the amount of the hindered phenol compound per 100 parts by mass of the resin (A) is 0.1 parts by mass or more, for example, when a negative photosensitive resin composition is formed on copper or a copper alloy, copper or copper Discoloration and corrosion of the alloy are prevented, and on the other hand, when the amount is 20 parts by mass or less, the photosensitivity is excellent, which is preferable.

The negative photosensitive resin composition may further contain an organic titanium compound for the purpose of improving the elongation after the wet heat durability test. The organic titanium compound that can be used is not particularly limited as long as it has an organic chemical substance bonded to the titanium atom via a covalent bond or an ionic bond.

Specific examples of organotitanium compounds are shown below in I) to VII).
I) Titanium chelate compound: Among them, a titanium chelate having two or more alkoxy groups is more preferable because the storage stability of the negative photosensitive resin composition and a good pattern can be obtained. (Triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis (tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and the like.

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

III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium 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) Monoalkoxy titanium compounds: for example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide and the like.

V) Titanium oxide compounds: for example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide and the like.

VI) Titanium tetraacetylacetonate compounds: such as titanium tetraacetylacetonate.

VII) Titanate coupling agent: For example, isopropyltridodecylbenzenesulfonyl titanate and the like.

Among the above I) to VII), the organotitanium compound is more preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds. It is preferable from the viewpoint of exhibiting good chemical resistance. 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.

The amount of these organic titanium compounds added is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the polyamic acid ester used as component (A). 2 parts by mass. When the amount added is 0.01 parts by mass or more, the adhesion is excellent, and when the amount is 10 parts by mass or less, the storage stability is excellent.

The photosensitive resin composition of the present disclosure is typically used as a varnish-like photosensitive resin composition by dissolving each of the above components and optionally further optional components in a solvent. A component can include a solvent. As the solvent, it is preferable to use a polar organic solvent from the viewpoint of solubility in the (A) resin.
Specifically, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α -Acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone and the like, and these can be used alone or in combination of two or more.

The solvent is in the range of, for example, 30 to 1500 parts by weight, preferably 100 to 1000 parts by weight, with respect to 100 parts by weight of the resin (A), depending on the desired coating thickness and viscosity of the photosensitive resin composition. can be used.

Furthermore, solvents containing alcohols are preferable from the viewpoint of improving the storage stability of the photosensitive resin composition. Alcohols that can be suitably used are typically alcohols having an alcoholic hydroxyl group in the molecule and no olefinic double bond. Specific examples include methyl alcohol, ethyl alcohol, n- Alkyl alcohols such as propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol and tert-butyl alcohol, lactic acid esters such as ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol Propylene glycol monoalkyl ethers such as 1-ethyl ether, propylene glycol-2-ethyl ether, propylene glycol-1-(n-propyl) ether, propylene glycol-2-(n-propyl) ether, ethylene glycol methyl ether , ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, and other monoalcohols, 2-hydroxyisobutyric acid esters, ethylene glycol, and propylene glycol, and other dialcohols. Among these, lactic acid esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyric acid esters, and ethyl alcohol are preferred, and ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, and propylene glycol-1-(n-propyl) ether are more preferred.

When the solvent contains an alcohol having no olefinic double bond, the content of the alcohol having no olefinic double bond in the total solvent is preferably 5 to 50% by mass, more preferably It is preferably 10 to 30% by mass. When the content of the alcohol having no olefinic double bond is 5% by mass or more, the storage stability of the photosensitive resin composition is improved, and when it is 50% by mass or less, the solubility of the (A) resin is get better.

<Method for manufacturing cured relief pattern>
The method for producing a cured relief pattern comprises the following steps (1) to (4):
(1) a step of applying the negative photosensitive resin composition described above onto a substrate to form a photosensitive resin layer on the substrate;
(2) exposing the photosensitive resin layer;
(3) developing the exposed photosensitive resin layer to form a relief pattern; and (4) heating the relief pattern to form a cured relief pattern. A manufacturing method can be provided.

Each step will be described below.
(1) A step of applying a negative photosensitive resin composition onto a substrate to form a photosensitive resin layer on the substrate. , then drying to form a photosensitive resin layer. As the substrate, at least the surface (the surface on which the photosensitive resin layer is formed) can be made of copper or a copper alloy. In particular, by using the photosensitive resin composition of the present disclosure, it is possible to provide a cured film and a cured relief pattern that have high adhesiveness even on copper or a copper alloy and have suppressed migration.

As a method for applying the photosensitive resin composition onto the substrate, a method conventionally used for applying the photosensitive resin composition, such as a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, or the like, can be used. A coating method, a spray coating method using a spray coater, or the like can be used.

If necessary, the coating film made of the negative photosensitive resin composition can be dried. As a drying method, for example, methods such as air drying, heat drying using an oven or a hot plate, and vacuum drying are used. Moreover, it is desirable to dry the coating film under conditions that do not cause imidization of the (A) polyimide precursor in the negative photosensitive resin composition. Specifically, when air drying or heat drying is performed, drying can be performed at 20° C. to 140° C. for 1 minute to 1 hour. As described above, a photosensitive resin layer can be formed on the substrate.

(2) Step of exposing the photosensitive resin layer In this step, the photosensitive resin layer formed in the above step (1) is exposed using an exposure device such as a contact aligner, mirror projection, stepper, or the like to form a photomask having a pattern. Alternatively, it is exposed to an ultraviolet light source or the like through a reticle or directly.

After that, for the purpose of improving photosensitivity, if necessary, post-exposure baking (PEB) and/or pre-development baking may be performed at any combination of temperature and time. The range of baking conditions is preferably 40° C. to 120° C. and a time of 10 seconds to 240 seconds. It is not limited to this range.

(3) Step of developing the exposed photosensitive resin layer to form a relief pattern In this step, an unexposed portion of the exposed photosensitive resin layer is removed by development. As a developing method for developing the photosensitive resin layer after exposure (irradiation), any of conventionally known photoresist developing methods such as a rotary spray method, a paddle method, an immersion method accompanied by ultrasonic treatment, and the like can be used. method can be selected and used. Further, after development, for the purpose of adjusting the shape of the relief pattern, etc., post-development baking may be performed at any combination of temperature and time, if necessary. A developer used for development is preferably, for example, a good solvent for the negative photosensitive resin composition, or a combination of the good solvent and a poor solvent. Examples of good solvents include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, and the like. . Preferred examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate and water. When a good solvent and a poor solvent are mixed and used, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the negative photosensitive resin composition. Moreover, two or more kinds of each solvent can be used, for example, several kinds can be used in combination.

(4) Step of heat-treating the relief pattern to form a cured relief pattern In this step, the relief pattern obtained by the development is heated to dilute the photosensitive component, and (A) the polyimide precursor The imidization transforms it into a cured relief pattern made of polyimide. As the heat-curing method, various methods can be selected, for example, using a hot plate, using an oven, or using a heating oven capable of setting a temperature program. Heating can be performed, for example, at 200° C. to 400° C. for 30 minutes to 5 hours. Air may be used as the atmospheric gas during heat curing, or an inert gas such as nitrogen or argon may be used.

<Semiconductor device>
Also provided is a semiconductor device comprising a hardened relief pattern obtainable by the method for producing a hardened relief pattern described above. Therefore, it is possible to provide a semiconductor device having a base material which is a semiconductor element and a cured relief pattern of polyimide formed on the base material by the above-described cured relief pattern manufacturing method. The present disclosure can also be applied to a semiconductor device manufacturing method that uses a semiconductor element as a base material and includes the above-described cured relief pattern manufacturing method as part of the process. The semiconductor device of the present disclosure is a semiconductor device having a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a bump structure in which the cured relief pattern formed by the cured relief pattern manufacturing method described above is used. It can be manufactured by forming it as a protective film or the like and combining it with a known method for manufacturing a semiconductor device.

<Display device>
Provided is a display device comprising a display element and a cured film provided on top of the display element, wherein the cured film is the cured relief pattern described above. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer interposed therebetween. Examples of the cured film include surface protective films, insulating films, and flattening films for TFT liquid crystal display elements and color filter elements, projections for MVA type liquid crystal display devices, and barrier ribs for cathodes of organic EL devices. .

The negative photosensitive resin composition of the present disclosure, in addition to the application to the semiconductor device as described above, for applications such as interlayer insulation of multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, and liquid crystal alignment films is also useful.

Examples of the present disclosure will be specifically described below, but the present disclosure is not limited thereto. In Examples, Comparative Examples, and Production Examples, the physical properties of the polymer or negative photosensitive resin composition were measured and evaluated according to the following methods.

《Measurement and evaluation method》
(1) Evaluation of copper migration On a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625 ± 25 μm), a sputtering device (L-440S-FHL type, manufactured by Canon Anelva) was used to obtain Ti with a thickness of 200 nm, 400 nm thick copper was sputtered in this order. Subsequently, on this wafer, a photosensitive polyamic acid ester composition prepared by the method described later is spin-coated using a coater developer (D-Spin 60A type, manufactured by SOKUDO) and dried to a thickness of 10 μm. A film was formed. Using a mask with a test pattern, this coating film was irradiated with energy of 300 mJ/cm 2 by a parallel light mask aligner (PLA-501FA type, manufactured by Canon Inc.). Next, this coating film was developed by spraying with a coater developer (D-Spin 60A type, manufactured by SOKUDO) using cyclopentanone as a developer. A relief pattern on copper was then obtained by rinsing with propylene glycol methyl ether acetate.

The wafer having the relief pattern formed on the copper was heat-treated at 200° C. for 2 hours in a nitrogen atmosphere using a temperature-rising programmable curing furnace (Model VF-2000, manufactured by Koyo Lindbergh Co., Ltd.). In this way, a hardened relief pattern of about 6-7 μm thick polyimide resin on copper was obtained. Occurrence of copper migration was confirmed in the obtained cured relief pattern by the following high-temperature storage test. First, a wafer having the cured relief pattern formed on copper is heated at 150° C. for 168 hours in air with a humidity of 5% using a temperature-rising programmable curing furnace (Model VF-2000, manufactured by Koyo Lindbergh Co., Ltd.). bottom. Subsequently, using a focused ion beam processing observation device JIB4000 (manufactured by JEOL Ltd.), the polyimide resin layer on the copper was cut to obtain a cross section of the polyimide resin-copper interface. A cross section of the obtained polyimide resin layer and copper interface was observed by FE-SEM (S-4800 type, manufactured by Hitachi High-Technologies Corporation). Using a length measurement program on the FE-SEM, the thickness of the migration layer occurring at the interface was measured.
"A": The thickness of copper migration is 0 nm or more and less than 25 nm "B": The thickness of copper migration is 25 nm or more and less than 50 nm "C": The thickness of copper migration is 50 nm or more and less than 75 nm "D": The thickness of copper migration is 75 nm or more

(2) Evaluation of copper adhesion The photosensitive resin composition prepared by the method described later is coated on a 6-inch silicon wafer on which Ti and Cu have been sputtered in advance in the same manner as in the preparation of the cured relief pattern described above, and prebaked. After that, using a temperature-rising programmable curing furnace (Model VF-2000, manufactured by Koyo Lindbergh Co., Ltd.), heat treatment is performed at 200 ° C. for 2 hours in a nitrogen atmosphere to cure a resin with a thickness of about 10 μm on Cu. A relief pattern was obtained. The film after the heat treatment was evaluated for adhesion properties between the copper substrate and the cured resin coating film according to the cross-cut method of JIS K 5600-5-6 standards, based on the following criteria.
"A": The lattice number of the cured resin coating adhered to the substrate is 100
"B": The lattice number of the cured resin coating adhered to the substrate is 70 to less than 100 "C": The lattice number of the cured resin coating adhered to the substrate is 40 to less than 70 "D": to the substrate The lattice number of the adhesive cured resin coating is less than 40

(3) Breaking elongation measurement after wet heat test On a 6-inch silicon wafer, the photosensitive resin composition was spin coated and dried so that the film thickness after curing was about 7 μm, then the entire surface was exposed and a temperature rising program was applied. Using a curing furnace (Model VF-2000, manufactured by Koyo Lindbergh Co., Ltd., Japan), the substrate was heated at 200° C. for 2 hours in a nitrogen atmosphere to obtain a cured relief pattern (thermally cured polyimide coating film). The resulting polyimide coating film was subjected to a high temperature accelerated test (PC-442R8D manufactured by Hirayama Seisakusho, 130 ° C., 85% RH, 168 hours), and then a dicing saw (DAD3350 type, manufactured by DISCO) to a width of 3 mm. After being cut into strips, it was peeled off from the silicon wafer using 46% hydrofluoric acid to obtain a polyimide tape. The elongation of the obtained polyimide tape was measured according to ASTM D882-09 using a tensile tester (UTM-II-20 type, manufactured by Orientec).
"A": Breaking elongation is 25% or more "B": Breaking elongation is 20% or more and less than 25% "C": Breaking elongation is 15% or more and less than 20% "D": Breaking elongation is less than 15%

<<(A) Production example of resin>>
<Production Example 1> (Synthesis of polymer A-1 as (A) resin)
155 g (0.5 mol) of 4,4′-oxydiphthalic dianhydride (ODPA) was placed in a 2-liter separable flask, followed by 135 g (1.04 mol) of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone. I put The mixture was stirred at room temperature, 79.1 g of pyridine was added while stirring, and the mixture was stirred for 16 hours.

Next, under ice-cooling, a solution of 203 g of dicyclohexylcarbodiimide (DCC) dissolved in 200 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Subsequently, a suspension of 89 g (0.44 mol) of diaminodiphenyl ether (DADPE) in 280 ml of γ-butyrolactone was added with stirring over 60 minutes. After further stirring at room temperature for 4 hours, 40 ml of ethyl alcohol was added and stirred for 1 hour, then 1 liter of γ-butyrolactone was added. A precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

The resulting reaction solution was added to 4 liters of ethyl alcohol to form a precipitate consisting of crude polymer. The resulting crude polymer was separated by filtration and dissolved in 2.5 liters of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was dropped into 30 liters of water to precipitate the polymer, and the obtained precipitate was separated by filtration and vacuum dried to obtain a powdery polymer (polymer A-1). When the molecular weight of polymer A-1 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 24,000.

<Production Example 2> (Synthesis of polymer A-2 as (A) resin)
The method described in Production Example 1 above, except that 147 g (0.5 mol) of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 155 g of ODPA in Production Example 1. A reaction was carried out in the same manner to obtain a polymer A-2. When the molecular weight of polymer A-2 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 20,000.

<Production Example 3> (Synthesis of polymer A-3 as (A) resin)
Reaction was carried out in the same manner as in Production Example 1 above, except that 94 g (0.44 mol) of 2,2′-dimethyl-4,4-diaminobiphenyl (mTB) was used instead of 89 g of DADPE in Production Example 1. was performed to obtain a polymer A-3. When the molecular weight of polymer A-3 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 26,000.

<Production Example 4> (Synthesis of polymer A-4 as (A) resin)
Except for using 46 g (0.44 mol) of p-phenylenediamine (pPD) instead of 89 g of DADPE in Production Example 1, the reaction was carried out in the same manner as in Production Example 1 to obtain polymer A-4. rice field. When the molecular weight of polymer A-4 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 19,000.

<Production Example 5> (Synthesis of polymer A-5 as (A) resin)
The method described in Production Example 1 above, except that 176 g (0.44 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) was used instead of 89 g of DADPE in Production Example 1. A reaction was carried out in the same manner to obtain Polymer A-5. When the molecular weight of polymer A-5 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 25,000.

<Production Example 6> (Synthesis of polymer A-6 as (A) resin)
Except that 124 g (0.4 mol) of ODPA and 29 g (0.1 mol) of BPDA were used in place of 155 g of ODPA in Production Example 1, the reaction was carried out in the same manner as in Production Example 1 to obtain Polymer A-6. rice field. When the molecular weight of polymer A-6 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 20,000.

<Production Example 7> (Synthesis of polymer A-7 as (A) resin)
The method described in Production Example 1 above, except that 62 g (0.2 mol) of ODPA and 65 g (0.3 mol) of PMDA were used instead of 155 g of ODPA in Production Example 1, and 94 g (0.44 mol) of mTB was used instead of 89 g of DADPE. A reaction was carried out in the same manner to obtain a polymer A-7. When the molecular weight of polymer A-7 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 20,000.

<Production Example 8> (Synthesis of polymer A-8 as (A) resin)
64.1 g (.20 mol) of 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB), 4, 97.7 g (0.22 mol) of 4′-(hexafluoroisopropylidene)diphthalic dianhydride (6FDA) and 500 g of dimethylacetamide (DMAc) were added and stirred to dissolve TFMB and 6FDA in DMAc. Furthermore, under a nitrogen stream, a polymerization reaction was carried out by continuing stirring at room temperature for 12 hours to obtain a polyamic acid solution.

After adding 16 g of pyridine to the resulting polyamic acid solution, 82 g of acetic anhydride was added dropwise at room temperature. After that, the liquid temperature was kept at 20 to 100° C. and stirring was continued for 24 hours for imidization reaction to obtain a polyimide solution.

The obtained polyimide solution was poured into 1,000 g of methanol while stirring in a 5 L container to precipitate the polyimide resin. After that, the solid polyimide resin was separated by filtration using a suction filtration device, and further washed with 1,000 g of methanol. Then, using a vacuum dryer, drying was performed at 100° C. for 24 hours, and further drying was performed at 200° C. for 3 hours. As a result, a polyimide powder polymer (A-8) having an acid anhydride group at the end was obtained. When the molecular weight of polymer A-8 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 25,000.

Table 1 summarizes the compounds used in synthesizing Polymer A-1 to Polymer A-8.

<<Production example of photosensitive resin composition>>
<Example 1>
Using the polymer A, a negative photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. Polymer A 100 g ((A) polyimide precursor), TR-PBG-3057 2.0 g ((B) photoinitiator), 2,4-diamino-6-[2-(2-undecyl-1-imidazolyl)ethyl ]-1,3,5-triazine ((C) 2,4-substituted-1,3,5-triazine derivative, manufactured by Shikoku Kasei Co., Ltd.), tetraethylene glycol dimethacrylate 8.0 g (NK Ester 4G, Shin Nakamura Chemical Kogyosha) was dissolved in 150 g of γ-butyrolactone (hereinafter referred to as GBL) and 40 g of dimethylsulfoxide (hereinafter referred to as DMSO). The viscosity of the resulting solution was adjusted to about 40 poise by further adding a small amount of the solvent to prepare a negative photosensitive resin composition. The compositions were evaluated according to the methods described above.

<Examples 2 to 29 and Comparative Example 1>
A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that the composition was blended at the compounding ratio shown in Table 2, and the same evaluation as in Example 1 was performed. Table 2 shows the evaluation results. In addition, in Table 2, compounds indicated by abbreviations are shown in Tables 3 and 4.

As is clear from Table 2, in Examples 1 to 29 containing (C) a nitrogen-containing heterocyclic compound represented by general formula (4) or (5), all of them after copper adhesion, copper migration, and wet heat tests Good results were obtained in the breaking elongation of However, in the comparative examples containing no (C) nitrogen-containing heterocyclic compound, sufficient results were not obtained in terms of copper adhesion, copper migration, and breaking elongation after the wet heat test.

Although examples of embodiments of the present disclosure have been described above, the present disclosure is not limited to these, and can be modified as appropriate without departing from the spirit of the invention.

By using the photosensitive resin composition according to the present disclosure, the adhesiveness is excellent even on copper or copper alloy, and migration can be suppressed. It can be widely used as a method of forming a relief pattern and a semiconductor device having a cured relief pattern.

Claims (17)

Ingredients for:
(A) a resin comprising a polyimide precursor, a polyimide, or both;
(B) a photopolymerization initiator, and (C) a negative photosensitive resin composition containing a nitrogen-containing heterocyclic compound,
The (A) polyimide precursor has the following general formula (1):

{wherein X ₁ is a tetravalent organic group having 6 to 40 carbon atoms, Y ₁ is a divalent organic group having 6 to 40 carbon atoms, and n is an integer of 2 to 50; , and R ₁ and R ₂ are each independently a hydrogen atom, or the following general formula (2a) or (2b):

(wherein R ₃ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10) or a saturated aliphatic group having 1 to 4 carbon atoms. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. }
A polyamic acid ester or polyamic acid salt represented by
The (A) polyimide has the following general formula (3):

{Wherein, X ₂ is a tetravalent organic group having 6 to 40 carbon atoms, Y ₂ is a divalent organic group having 6 to 40 carbon atoms, and n is an integer of 2 to 50 . }
is a polyimide resin represented by
The (C) nitrogen-containing heterocyclic compound has the following general formula (4):

{Wherein, R ₆ is a hydrogen atom, a halogen atom, an alkoxy group, a (meth)acryloyloxy group, a silicon atom-containing group, a hydroxyl group, an amino group, an alkyl group having 1 to 25 carbon atoms, an alkoxyalkyl group, an aromatic group or a group having a nitrogen-containing heterocyclic ring, and a monovalent organic group selected from the group consisting of combinations thereof, and R ₇ to R ₁₀ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or a carbon number of 1 1 to 10 alkyl groups, alkoxyalkyl groups or aromatic groups, and monovalent organic groups selected from the group consisting of combinations thereof. } and the following general formula (5):

{wherein R ₃₁ to R ₃₃ each independently represent a hydrogen atom, a hydroxyl group, a carboxy group, an amino group, an azo bond-containing group, an aliphatic hydrocarbon group, an alkoxy group, a hydroxyalkyl group, an aromatic group, a nitrogen-containing a heterocyclic ring-containing group and a monovalent organic group selected from the group consisting of combinations thereof, provided that at least one of R ₃₁ to R ₃₃ is a nitrogen-containing heterocyclic ring-containing group; }
A photosensitive resin composition which is at least one selected from the group consisting of the compounds represented by: The (C) nitrogen-containing heterocyclic compound has the following general formula (4a):

{In the formula, R ₁₁ is a monovalent organic group selected from the group consisting of a hydrogen atom, a halogen atom, a silicon atom-containing group, a hydroxyl group, an amino group, and an alkyl group having 1 to 10 carbon atoms or an aromatic group. . }
The photosensitive resin composition according to claim 1, comprising a compound represented by. The (C) nitrogen-containing heterocyclic compound has the following general formula (4b):

{Wherein, R ₁₂ is a hydrogen atom, a halogen atom, a (meth)acryloyloxy group, a silicon atom-containing group, a hydroxyl group, an amino group, an alkyl group having 1 to 15 carbon atoms, an aromatic group, or a group having a nitrogen-containing heterocyclic ring , and combinations thereof, and m is an integer of 1-10. }
The photosensitive resin composition according to claim 1 or 2, comprising a compound represented by. 4. The photosensitive resin composition according to claim 3, wherein in the general formula (4b), _R12 is the nitrogen-containing heterocyclic ring-containing group or the silicon atom-containing group. The photosensitive resin composition according to claim 3 or 4, wherein in the general formula (4b), _R12 is a group having an imidazole skeleton. The photosensitive resin composition according to claim 3 or 4, wherein in the general formula (4b), _R12 is a group having an alkoxysilyl group. 2. The photosensitive resin composition according to claim 1, wherein in the nitrogen-containing heterocyclic compound represented by the general formula (5), at least two of R ₃₁ to R ₃₃ are groups having a nitrogen-containing heterocyclic ring. 6. The photosensitive resin composition according to claim 5, further comprising (D) a tetrazole compound. 9. The photosensitive resin composition according to claim 8, wherein (D) the tetrazole compound is 5-amino-1H-tetrazole. The nitrogen-containing heterocyclic compound (C) has the following general formulas (5a) and (5b):

{In formulas (5a) and (5b), R ₃₄ is a hydrogen atom, a halogen atom, a silicon atom-containing group, a phosphorus atom-containing group, a hydroxyl group, a carboxyl group, an amino group, an alkyl group having 1 to 20 carbon atoms, an aromatic group or a monovalent organic group selected from the group consisting of groups having a nitrogen-containing heterocyclic ring, and in formula (5a), two R ₃₅ are each independently CH or a nitrogen atom. }
The photosensitive resin composition according to claim 1 or 2, comprising at least one selected from compounds represented by. X ₁ in the general formula (1) and/or X ₂ in the general formula (3) are represented by the following general formulas (6) to (8):

{In general formula (8), R ₁₃ is an oxygen atom, a sulfur atom, or a divalent organic group. }
3. The photosensitive resin composition according to claim 1, which is at least one or more organic groups selected from the group consisting of: Y ₁ of the general formula (1) and/or Y ₂ of the general formula (3) are represented by the following general formulas (9) to (12):

{R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and may be the same or different good. }

{R ₂₆ is a divalent group, R ₁₈ to R ₂₅ are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and are the same There may be or may be different. }

{R ₂₇ and R ₂₈ are divalent groups, R ₂₉ and R ₃₀ are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, They may be the same or different. }
3. The photosensitive resin composition according to claim 1, which is at least one or more organic groups selected from the group consisting of: (A) containing at least two types of polyimide precursors represented by the general formula (1), and/or containing at least two types of (A) polyimides represented by the general formula (3). 3. The photosensitive resin composition according to 1 or 2. The photosensitive resin composition according to claim 1 or 2, having at least two kinds of X ₁ in the general formula (1) and/or having at least two kinds of X ₂ in the general formula (3). thing. (1) forming a photosensitive resin layer on a substrate by coating the photosensitive resin composition according to claim 1 or 2 on the substrate;
(2) exposing the photosensitive resin layer;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) forming a cured relief pattern by heat-treating the relief pattern;
A method of manufacturing a cured relief pattern, comprising: 16. The method of manufacturing a hardened relief pattern according to claim 15, wherein said substrate is made of copper or a copper alloy. A semiconductor device comprising a cured relief pattern obtained by the method for producing a cured relief pattern according to claim 15 or 16.