JP7540891B2 - Negative-type photosensitive resin composition, and method for producing polyimide and cured relief pattern using the same - Google Patents

Description

The present invention relates to a negative-type photosensitive resin composition, and a method for producing a polyimide and a cured relief pattern using the same.

Conventionally, polyimide resins, polybenzoxazole resins, phenolic resins, and the like, which have excellent heat resistance, electrical properties, and mechanical properties, have been used as insulating materials for electronic components, and passivation films, surface protective films, and interlayer insulating films for semiconductor devices. Among these resins, those provided in the form of a photosensitive resin composition can easily form a heat-resistant relief pattern film by applying the composition, exposing it to light, developing it, and subjecting it to a thermal imidization treatment through curing. Such photosensitive resin compositions have the characteristic of enabling a significant reduction in process times compared to conventional non-photosensitive materials.

There are various methods for packaging semiconductor devices. For example, one semiconductor packaging method is to cover a semiconductor chip with a sealing material (mold resin) to form an element sealing material, and then to form a rewiring layer that electrically connects to the semiconductor chip.

Among semiconductor packaging techniques, the Fan-Out type semiconductor packaging technique has become mainstream in recent years. In the fan-out type semiconductor packaging technique, first, a chip encapsulation body larger than the chip size of the semiconductor chip is formed by covering the semiconductor chip with an encapsulant. Next, a redistribution layer is formed in the area of the semiconductor chip and the encapsulant. In the fan-out type semiconductor packaging technique, the redistribution layer is formed with a thin film thickness. Because the redistribution layer is formed up to the area of the encapsulant, the number of external connection terminals can be increased.

For example, a fan-out type semiconductor device is known, such as that described in Patent Document 1 below.

JP 2011-129767 A

In fan-out type semiconductor devices, there is a trend toward lowering the curing temperature (thermal imidization temperature) from the viewpoint of preventing warping of the wafer during processing. However, lowering the thermal imidization temperature poses the problem of reduced adhesion between the rewiring layer and the sealing material such as molding resin. In addition, since the rewiring layer is composed of two or more layers, there are problems such as the loss of in-plane uniformity and the tendency for cracks to occur in the first layer.

The present invention has been devised in view of such conventional circumstances, and has as one object to provide a negative-type photosensitive resin composition (hereinafter also referred to simply as "photosensitive resin composition" in this specification) that has good adhesion to an encapsulant such as a molding resin, good in-plane uniformity and crack resistance when formed as a multilayer, and excellent elongation after a reliability test. Another object is to provide a method for forming a cured relief pattern using the negative-type photosensitive resin composition of the present invention.

｛式中、Ｘ_１は、４価の有機基であり、Ｙ_１は、２価の有機基であり、ｎ_１は、２～１５０の整数であり、Ｒ_１及びＲ_２は、それぞれ独立に、水素原子又は１価の有機基であり、そしてＲ_１及びＲ_２の少なくとも一方は、下記一般式（２）：

（式中、Ｌ_１、Ｌ_２及びＬ_３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_１は、２～１０の整数である。）
で表される１価の有機基である。｝
で表される構造単位を有するポリイミド前駆体、
（Ｂ）ウレタン結合、及びウレア結合から成る群から選択される少なくとも１種を含む化合物、
（Ｃ）光重合開始剤、並びに
（Ｄ）３－メトキシ―Ｎ，Ｎ－ジメチルプロピオンアミド、及び３－ブトキシ―Ｎ，Ｎ－ジメチルプロピオンアミドから成る群から選択される少なくとも１種の溶媒
を含む、ネガ型感光性樹脂組成物。
［２］
前記（Ｂ）化合物は、ウレア結合を有する化合物である、項目１に記載のネガ型感光性樹脂組成物。
［３］
前記（Ｂ）化合物は、下記一般式（３）又は（４）：

｛式中、Ｒ_７及びＲ_８は、それぞれ独立に、ヘテロ原子を含んでよい炭素数１～２０の１価の有機基であり、そしてＲ_９及びＲ_１０は、それぞれ独立に、水素原子、又はヘテロ原子を含んでよい炭素数１～２０の１価の有機基である。｝

｛式中、Ｒ_１１及びＲ_１２は、それぞれ独立に、ヘテロ原子を含んでよい炭素数１～２０の１価の有機基であり、そしてＲ_１３は、ヘテロ原子を含んでよい炭素数１～２０の２価の有機基である。｝
で表される化合物である、項目１又は２に記載のネガ型感光性樹脂組成物。
［４］
前記（Ｂ）化合物は、（メタ）アクリル基、水酸基、及びアミノ基から成る群から選択される少なくとも１種の官能基を含む、項目１～３のいずれか１項に記載のネガ型感光性樹脂組成物。
［５］
前記（Ａ）ポリイミド前駆体の一般式（１）におけるＹ_１は、下記一般式（５）：

｛式中、Ｒ_１４及びＲ_１５は、それぞれ独立に、水素原子、又はハロゲン原子を含んでよい炭素数１～１０の１価の有機基である。｝
で表される構造である、項目１～４のいずれか１項に記載のネガ型感光性樹脂組成物。
［６］
（Ｅ）防錆剤を更に含む、項目１～５のいずれか１項に記載のネガ型感光性樹脂組成物。
［７］
前記（Ｅ）防錆剤は、含窒素複素環化合物を含む、項目６に記載のネガ型感光性樹脂組成物。
［８］
前記含窒素複素環化合物は、アゾール化合物である、項目７に記載のネガ型感光性樹脂組成物。
［９］
前記含窒素複素環化合物は、プリン、又はプリン誘導体である、項目７に記載のネガ型感光性樹脂組成物。
［１０］
（Ｆ）シランカップリング剤を更に含む、項目１～９のいずれか１項に記載のネガ型感光性樹脂組成物。
［１１］
前記（Ａ）ポリイミド前駆体の一般式（１）におけるＸ_１は、下記一般式（２０ａ）、（２０ｂ）、及び（２０ｃ）：

｛式中、Ｒ_６は、水素原子、フッ素原子、炭素数１～１０の炭化水素基、及び炭素数１～１０の含フッ素炭化水素基から成る群から選択される少なくとも１つであり、そしてｌは、０～２から選択される整数である。｝

｛式中、Ｒ_６は、それぞれ独立に、水素原子、フッ素原子、炭素数１～１０の炭化水素基、及び炭素数１～１０の含フッ素炭化水素基から成る群から選択される少なくとも１つであり、そしてｍは、それぞれ独立に、０～３から選択される整数である。｝

｛式中、Ｒ_６は、それぞれ独立に、水素原子、フッ素原子、炭素数１～１０の炭化水素基、及び炭素数１～１０の含フッ素炭化水素基から成る群から選択される少なくとも１つであり、そしてｍは、それぞれ独立に、０～３から選択される整数である。｝
から成る群から選択される少なくとも１種を含む構造である、項目１～１０のいずれか１項に記載のネガ型感光性樹脂組成物。
［１２］
前記（Ａ）ポリイミド前駆体と、
前記（Ａ）ポリイミド前駆体１００質量部を基準として０．１～３０質量部の前記（Ｂ）化合物と、
前記（Ａ）ポリイミド前駆体１００質量部を基準として０．１～２０質量部の前記（Ｃ）光重合開始剤と、
前記（Ａ）ポリイミド前駆体１００質量部を基準として１０～１０００質量部の前記（Ｄ）溶媒と
を含む、項目１～１１のいずれか１項に記載のネガ型感光性樹脂組成物。
［１３］
項目１～１２のいずれか１項に記載のネガ型感光性樹脂組成物に含まれる前記（Ａ）ポリイミド前駆体をポリイミドに変換する工程を含む、ポリイミドの製造方法。
［１４］
（１）項目１～１２のいずれか１項に記載のネガ型感光性樹脂組成物を基板上に塗布して、感光性樹脂層を前記基板上に形成する工程と、
（２）前記感光性樹脂層を露光する工程と、
（３）露光後の前記感光性樹脂層を現像して、レリーフパターンを形成する工程と、
（４）前記レリーフパターンを加熱処理して、硬化レリーフパターンを形成する工程と
を含む、硬化レリーフパターンの製造方法。 The present inventors have found that the above-mentioned problems can be solved by combining a specific polyimide precursor, a compound containing a specific bond, a photopolymerization initiator, and a specific solvent, and have completed the present invention. Examples of embodiments of the present invention are listed below.
[1]
(A) A compound represented by the following general formula (1):

In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer from 2 to 150, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, and at least one of R ₁ and R ₂ is represented by the following general formula (2):

(In the formula, L ₁ , L ₂ and L ₃ each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ represents an integer of 2 to 10.)
It is a monovalent organic group represented by the following formula:
A polyimide precursor having a structural unit represented by the formula:
(B) a compound containing at least one bond selected from the group consisting of a urethane bond and a urea bond;
(C) a photopolymerization initiator; and (D) at least one solvent selected from the group consisting of 3-methoxy-N,N-dimethylpropionamide and 3-butoxy-N,N-dimethylpropionamide.
[2]
2. The negative type photosensitive resin composition according to item 1, wherein the compound (B) is a compound having a urea bond.
[3]
The compound (B) is represented by the following general formula (3) or (4):

In the formula, R ₇ and R ₈ are each independently a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and R ₉ and R ₁₀ are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom.

In the formula, R ₁₁ and R ₁₂ are each independently a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and R ₁₃ is a divalent organic group having 1 to 20 carbon atoms which may contain a heteroatom.
3. The negative type photosensitive resin composition according to item 1 or 2, wherein the compound is represented by the formula:
[4]
The negative type photosensitive resin composition according to any one of items 1 to 3, wherein the compound (B) contains at least one functional group selected from the group consisting of a (meth)acrylic group, a hydroxyl group, and an amino group.
[5]
Y ₁ in the general formula (1) of the polyimide precursor (A) is represented by the following general formula (5):

In the formula, R ₁₄ and R ₁₅ each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom.
5. The negative type photosensitive resin composition according to any one of items 1 to 4, wherein the structure is represented by:
[6]
(E) The negative type photosensitive resin composition according to any one of items 1 to 5, further comprising a rust inhibitor.
[7]
7. The negative type photosensitive resin composition according to item 6, wherein the (E) rust inhibitor contains a nitrogen-containing heterocyclic compound.
[8]
8. The negative type photosensitive resin composition according to item 7, wherein the nitrogen-containing heterocyclic compound is an azole compound.
[9]
8. The negative type photosensitive resin composition according to item 7, wherein the nitrogen-containing heterocyclic compound is a purine or a purine derivative.
[10]
10. The negative type photosensitive resin composition according to any one of items 1 to 9, further comprising a silane coupling agent (F).
[11]
_X1 in the general formula (1) of the polyimide precursor (A) is represented by the following general formulas (20a), (20b), and (20c):

In the formula, R ₆ is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and l is an integer selected from 0 to 2.

{In the formula, each R ₆ is independently at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and each m is independently an integer selected from 0 to 3.}

{In the formula, each R ₆ is independently at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and each m is independently an integer selected from 0 to 3.}
The negative type photosensitive resin composition according to any one of items 1 to 10, wherein the negative type photosensitive resin composition has a structure comprising at least one selected from the group consisting of:
[12]
The (A) polyimide precursor;
0.1 to 30 parts by mass of the (B) compound based on 100 parts by mass of the (A) polyimide precursor;
0.1 to 20 parts by mass of the photopolymerization initiator (C) based on 100 parts by mass of the polyimide precursor (A);
12. The negative type photosensitive resin composition according to any one of items 1 to 11, comprising 10 to 1000 parts by mass of the (D) solvent based on 100 parts by mass of the (A) polyimide precursor.
[13]
13. A method for producing a polyimide, comprising: a step of converting the polyimide precursor (A) contained in the negative photosensitive resin composition according to any one of items 1 to 12 into a polyimide.
[14]
(1) A step of applying the negative type photosensitive resin composition according to any one of items 1 to 12 onto a substrate to form a photosensitive resin layer on the substrate;
(2) exposing the photosensitive resin layer to light;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising the step of heat-treating the relief pattern to form a cured relief pattern.

According to the present invention, it is possible to provide a negative-type photosensitive resin composition that, when formed as a multilayer, has excellent in-plane uniformity, can suppress the occurrence of cracks, and has excellent elongation in reliability tests, and also provides a method for forming a cured relief pattern using the negative-type photosensitive resin composition. In addition, according to the present invention, it is possible to provide a negative-type photosensitive resin composition that has good adhesion to molding resins used in fan-out type semiconductor packages.

The following describes in detail the form for carrying out the present invention (hereinafter, referred to as the "present embodiment"). Note that the present invention is not limited to the present embodiment described below, and can be carried out in various modifications within the scope of the gist of the invention. Note that throughout this specification, structures represented by the same symbol in a general formula may be the same or different when multiple structures are present in a molecule.

<Negative Photosensitive Resin Composition>
The negative photosensitive resin composition according to the present embodiment contains (A) a specific polyimide precursor, (B) a compound containing at least one selected from the group consisting of a urethane bond and a urea bond, (C) a photopolymerization initiator, and (D) at least one solvent selected from the group consisting of 3-methoxy-N,N-dimethylpropionamide and 3-butoxy-N,N-dimethylpropionamide. In this specification, the term "negative" refers to a photosensitive resin composition in which the unexposed area dissolves and the exposed area remains during development.

From the viewpoint of easily achieving the effects of the present invention and obtaining high chemical resistance, the negative photosensitive resin composition preferably contains (A) a polyimide precursor, 0.1 to 30 parts by mass of (B) a compound based on 100 parts by mass of (A) polyimide precursor, 0.1 to 20 parts by mass of (C) a photopolymerization initiator based on 100 parts by mass of (A) polyimide precursor, and 10 to 1,000 parts by mass of (D) a solvent based on 100 parts by mass of (A) polyimide precursor.

｛式中、Ｘ_１は、４価の有機基であり、Ｙ_１は、２価の有機基であり、ｎ_１は、２～１５０の整数であり、Ｒ_１及びＲ_２は、それぞれ独立に、水素原子又は１価の有機基であり、そしてＲ_１及びＲ_２の少なくとも一方は、下記一般式（２）で表される１価の有機基である。｝ (A) Polyimide Precursor In the present embodiment, the polyimide precursor (A) is a resin component contained in the negative photosensitive resin composition, and is converted to a polyimide by a thermal cyclization treatment. The polyimide precursor is a polyamide having a structural unit represented by the following general formula (1).

In the formula, _X1 is a tetravalent organic group, _Y1 is a divalent organic group, _n1 is an integer from 2 to 150, _R1 and _R2 are each independently a hydrogen atom or a monovalent organic group, and at least one of _R1 and _R2 is a monovalent organic group represented by the following general formula (2).

｛式中、Ｌ_１、Ｌ_２及びＬ_３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_１は、２～１０の整数である。｝ In general formula (1), at least one of R ₁ and R ₂ is a monovalent organic group represented by the following general formula (2).

In the formula, L ₁ , L ₂ and L ₃ each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ represents an integer of 2 to 10.

｛式中、Ｒ_６は、水素原子、フッ素原子、炭素数１～１０の炭化水素基、及び炭素数１～１０の含フッ素炭化水素基から成る群から選択される少なくとも１つであり、ｌは、０～２から選択される整数であり、ｍは０～３から選択される整数であり、そしてｎは、０～４から選択される整数である。｝ In the general formula (1), n ₁ may be an integer of 2 to 150, and from the viewpoint of the photosensitive properties and mechanical properties of the negative photosensitive resin composition, an integer of 3 to 100 is preferable, and an integer of 5 to 70 is more preferable. In the general formula (1), the tetravalent organic group represented by X ₁ is preferably an organic group having 6 to 40 carbon atoms from the viewpoint of achieving both heat resistance and photosensitive properties, and more preferably an aromatic group in which the -COOR ₁ group and the -COOR ₂ group and the -CONH- group are in the ortho position with respect to each other, or an alicyclic aliphatic group. Specific examples of the tetravalent organic group represented by X ₁ include organic groups having 6 to 40 carbon atoms containing an aromatic ring, such as a group having a structure represented by the following general formula (20).

{In the formula, R ₆ is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, l is an integer selected from 0 to 2, m is an integer selected from 0 to 3, and n is an integer selected from 0 to 4.}

｛式中、Ｒ_６は、水素原子、フッ素原子、炭素数１～１０の炭化水素基、及び炭素数１～１０の含フッ素炭化水素基から成る群から選択される少なくとも１つであり、そしてｌは、０～２から選択される整数である。｝

｛式中、Ｒ_６は、それぞれ独立に、水素原子、フッ素原子、炭素数１～１０の炭化水素基、及び炭素数１～１０の含フッ素炭化水素基から成る群から選択される少なくとも１つであり、そしてｍは、それぞれ独立に、０～３から選択される整数である。｝

｛式中、Ｒ_６は、それぞれ独立に、水素原子、フッ素原子、炭素数１～１０の炭化水素基、及び炭素数１～１０の含フッ素炭化水素基から成る群から選択される少なくとも１つであり、そしてｍは、それぞれ独立に、０～３から選択される整数である。｝ The structure of _X1 may be one type or a combination of two or more types. The _X1 group having the structure represented by the above formula (20) is particularly preferred from the viewpoint of achieving both heat resistance and photosensitive properties. As the _X1 group, among the structures represented by the above formula (20), structures represented by at least one of the following formulas (20a), (20b) and (20c) are particularly preferred from the viewpoints of chemical resistance, resolution and void suppression after high-temperature storage test.

In the formula, R ₆ is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and l is an integer selected from 0 to 2.

{In the formula, each R ₆ is independently at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and each m is independently an integer selected from 0 to 3.}

{In the formula, each R ₆ is independently at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and each m is independently an integer selected from 0 to 3.}

｛式中、Ｒ_６は、それぞれ独立に、水素原子、フッ素原子、炭素数１～１０の炭化水素基、及び炭素数１～１０の含フッ素炭化水素基から成る群から選択される少なくとも１つであり、そしてｎは、０～４から選択される整数である。｝ In the above general formula (1), the divalent organic group represented by _Y1 is preferably an aromatic group having 6 to 40 carbon atoms from the viewpoint of achieving both heat resistance and photosensitive properties, and examples thereof include a structure represented by the following formula (21).

In the formula, each R ₆ is independently at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and n is an integer selected from 0 to 4.

｛式中、Ｒ_１４及びＲ_１５は、それぞれ独立に、水素原子、又はハロゲン原子を含んでよい炭素数１～１０の１価の有機基である。｝
これらの中で、硬化膜のガラス転移温度（Ｔｇ）又はヤング率の観点から、Ｒ_１４及びＲ_１５の少なくとも一方又は両方は、メチル基又はトリフルオロメチル基であることが好ましい。 The structure of _Y1 may be one type or a combination of two or more types. The _Y1 group having the structure represented by the above formula (21) is particularly preferred from the viewpoint of achieving both heat resistance and photosensitive properties. As the _Y1 group, the structure represented by the following formula (5) is particularly preferred from the viewpoint of chemical resistance, and in-plane uniformity or crack suppression when formed as a multilayer.

In the formula, R ₁₄ and R ₁₅ each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom.
Among these, from the viewpoint of the glass transition temperature (Tg) or Young's modulus of the cured film, it is preferable that at least one or both of R ₁₄ and R ₁₅ are a methyl group or a trifluoromethyl group.

In the above general formula (2), _L1 is preferably a hydrogen atom or a methyl group, and _L2 and _L3 are preferably hydrogen atoms from the viewpoint of photosensitive properties. In addition, in the general formula (2), _m1 is an integer of 2 to 10, preferably an integer of 2 to 4, from the viewpoint of photosensitive properties.

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は、上記一般式（１）について定義したものである。｝
で表される構造単位を有するポリイミド前駆体であることが好ましい。 In one embodiment, the polyimide precursor (A) is represented by the following general formula (8):

{In the formula, R ₁ , R ₂ , and n ₁ are defined as in the above general formula (1).}
It is preferable that the polyimide precursor has a structural unit represented by the following formula:

In the general formula (8), at least one of R ₁ and R ₂ is more preferably a monovalent organic group represented by the above general formula (2). When the polyimide precursor (A) contains a polyimide precursor having a structural unit represented by the general formula (8), the effect of containing the above formula (5) (for example, improved crack resistance when formed in multiple layers) is obtained, and in addition, the effect of particularly improving the resolution is also improved.

｛式中、Ｒ_１、Ｒ_２、及びｎ_１は、上記一般式（１）に定義したものである。｝
で表される構造単位を有するポリイミド前駆体であることも好ましい。 In one embodiment, in terms of the effect of including the above formula (5) and resolution, the polyimide precursor (A) may be represented by the following general formula (9):

{In the formula, R ₁ , R ₂ , and n ₁ are defined as in the above general formula (1).}
It is also preferable that the polyimide precursor has a structural unit represented by the following formula:

In formula (9), at least one of R ₁ and R ₂ is more preferably a monovalent organic group represented by formula (2) above.

In general formulas (8) and (9), R ₁ , R ₂ , and n ₁ in one formula may be the same as or different from R ₁ , R ₂ , and n ₁ in the other formula, respectively.

(A) Method for Preparing Polyimide Precursor (A) The polyimide precursor can be obtained by first reacting the above-mentioned tetracarboxylic acid dianhydride containing the tetravalent organic group _X1 with an alcohol having a photopolymerizable unsaturated double bond and, optionally, an alcohol having no unsaturated double bond to prepare a partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid/ester body), and then subjecting this to amide polycondensation with a diamine containing the above-mentioned divalent organic group _Y1 .

(Preparation of Acid/Ester Forms)
In the present embodiment, examples of the tetracarboxylic dianhydride containing a tetravalent organic group _X1 that is suitably used for preparing the polyimide precursor (A) include the tetracarboxylic dianhydride represented by the above general formula (20), as well as, for example, pyromellitic anhydride (PMDA), diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride (ODPA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane. Preferred examples include pyromellitic anhydride (PMDA), diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride (ODPA), and 3,3',4,4'-biphenyltetracarboxylic dianhydride. These may be used alone or in combination of two or more.

In this embodiment, examples of alcohols having a photopolymerizable unsaturated double bond that are preferably used to prepare the polyimide precursor (A) include 2-hydroxyethyl methacrylate (HEMA), 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, and 2-hydroxy-3-t-butoxypropyl acrylate. Examples of the methacryloyloxypropyl acrylate include 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

The above-mentioned photopolymerizable alcohols having an unsaturated double bond can also be mixed with alcohols not having an unsaturated double bond, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, and benzyl alcohol.

In addition, a non-photosensitive polyimide precursor prepared only from alcohols not having the above-mentioned unsaturated double bonds may be used as the polyimide precursor by mixing it with the photosensitive polyimide precursor. From the viewpoint of resolution, it is preferable that the non-photosensitive polyimide precursor is 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor.

The above suitable tetracarboxylic dianhydride and the above alcohol are stirred, dissolved, and mixed in a solvent as described below at a temperature of 20 to 50°C for 4 to 10 hours in the presence of a basic catalyst such as pyridine, whereby the esterification reaction of the acid anhydride proceeds and the desired acid/ester can be obtained.

(Preparation of polyimide precursor)
The acid/ester (typically a solution in a solvent described below) is mixed with an appropriate dehydration condensation agent, such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, or N,N'-disuccinimidyl carbonate, under ice cooling to convert the acid/ester into a polyacid anhydride, and then a diamine containing a divalent organic group _Y1 preferably used in the present embodiment, dissolved or dispersed in a separate solvent, is added dropwise to the mixture to carry out amide polycondensation, thereby obtaining a target polyimide precursor. Alternatively, the acid moiety of the acid/ester is converted into an acid chloride using thionyl chloride or the like, and then the mixture is reacted with a diamine compound in the presence of a base such as pyridine to obtain a target polyimide precursor.

Diamines containing a divalent organic group _Y1 that are preferably used in this embodiment include diamines having a structure represented by the above general formula (21), as well as, for example, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether (4,4'-oxydianiline (ODA)), 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'-diaminodiphenyl, Aminobiphenyl, 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-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, and these benzenes. Examples of such an amino group include those in which some of the hydrogen atoms on the Zene ring are substituted with methyl groups, ethyl groups, hydroxymethyl groups, hydroxyethyl groups, halogens, or the like, such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (2,2'-dimethylbiphenyl-4,4'-diamine (m-TB)), 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)-biphenyl, and mixtures thereof.

After the amide polycondensation reaction is completed, the water-absorbing by-product of the dehydrating condensing agent coexisting in the reaction solution is filtered off as necessary, and then a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof is added to the resulting polymer component to precipitate the polymer component. The polymer is purified by repeating redissolution and reprecipitation operations, and then vacuum dried to isolate the desired polyimide precursor. To improve the degree of purification, the polymer solution may be passed through a column packed with anion and/or cation exchange resin swollen with an appropriate organic solvent to remove ionic impurities.

The molecular weight of the polyimide precursor (A) is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, when measured by gel permeation chromatography in terms of polystyrene equivalent weight average molecular weight. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, and when it is 150,000 or less, the dispersibility in the developer is good, and the resolution performance of the relief pattern is good. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as the developing solvent for gel permeation chromatography. The weight average molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended to select the standard monodisperse polystyrene from among the organic solvent-based standard samples STANDARD SM-105 manufactured by Showa Denko KK.

(B) Compound having urethane bond or urea bond The (B) compound used in this embodiment contains at least one selected from the group consisting of a urethane bond and a urea bond in the molecular structure (hereinafter, in this embodiment, it is also referred to as a "urethane/urea compound"). In this embodiment, by containing the (B) compound, it is possible to improve the adhesion to the molding resin and/or the in-plane uniformity when formed as a multilayer. However, such an effect is realized by using the (D) solvent together with the urethane/urea compound.

The (B) compound used in this embodiment may have a urethane bond and/or a urea bond in its molecular structure. Of these, it is preferable that the (B) compound has a urea bond from the viewpoint of suppressing Cu surface voids or chemical resistance.

｛式中、Ｒ_７及びＲ_８は、それぞれ独立に、ヘテロ原子を含んでよい炭素数１～２０の１価の有機基であり、そしてＲ_９及びＲ_１０は、それぞれ独立に、水素原子、又はヘテロ原子を含んでよい炭素数１～２０の１価の有機基である。｝

｛式中、Ｒ_１１及びＲ_１２は、それぞれ独立に、ヘテロ原子を含んでよい炭素数１～２０の１価の有機基であり、そしてＲ_１３は、ヘテロ原子を含んでよい炭素数１～２０の２価の有機基である。｝ Among the compounds having a urea bond, from the viewpoint of developability, the compounds represented by the following formula (3) or (4) are more preferred.

In the formula, R ₇ and R ₈ are each independently a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and R ₉ and R ₁₀ are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom.

In the formula, R ₁₁ and R ₁₂ are each independently a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and R ₁₃ is a divalent organic group having 1 to 20 carbon atoms which may contain a heteroatom.

Examples of the heteroatom according to the present embodiment include an oxygen atom, a nitrogen atom, a phosphorus atom, and a sulfur atom. In formula (3), R ₇ and R ₈ may each independently be a monovalent organic group having 1 to 20 carbon atoms that may contain a heteroatom, and more preferably contain an oxygen atom from the viewpoint of developability. The number of carbon atoms in R ₇ and R ₈ may be 1 to 20, and from the viewpoint of heat resistance, the number of carbon atoms is preferably 1 to 10, and more preferably 3 to 10.

In formula (3), R ₉ and R ₁₀ may each independently be a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and more preferably contains a hydrogen atom or an oxygen atom from the viewpoint of developability. R ₉ and R ₁₀ may each have 1 to 20 carbon atoms, and from the viewpoint of heat resistance, they preferably have 1 to 10 carbon atoms, and more preferably have 3 to 10 carbon atoms.

In addition, in formula (4), R ₁₁ and R ₁₂ may each independently be a monovalent organic group having 1 to 20 carbon atoms, which may contain a heteroatom, and more preferably contain an oxygen atom from the viewpoint of developability. The carbon number of R ₁₁ and R ₁₂ may be 1 to 20, and from the viewpoint of heat resistance, the carbon number is preferably 1 to 10, and more preferably 3 to 10. In formula (4), R ₁₃ may be a divalent organic group having 1 to 20 carbon atoms, which may contain a heteroatom, and from the viewpoint of suppression of crack generation or elongation in a reliability test, it is more preferable to contain at least one oxygen atom. The carbon number of R ₁₃ may be 1 to 20, and from the viewpoint of inclusion of a heteroatom, it is preferably 2 or more, and from the viewpoint of heat resistance, it is preferably 1 to 18.

In this embodiment, it is preferable that the (B) compound further has at least one functional group selected from the group consisting of a (meth)acrylic group, a hydroxyl group, and an amino group, and it is more preferable that the (B) compound has a (meth)acrylic group.

Although the reason why the inclusion of the compound (B) according to this embodiment together with the solvent (D) improves the adhesion to the mold resin or the in-plane uniformity when formed as a multilayer is not clear, the present inventors believe as follows. That is, in one aspect, the negative photosensitive resin composition is heat-cured at a low temperature of 180° C. or less, so that the conversion of the polyimide precursor to polyimide tends to be insufficient. On the other hand, the negative photosensitive resin composition of this embodiment contains the urethane/urea compound (B), and a part of the compound (B) is thermally decomposed to generate amines, etc., which are believed to promote the conversion of the polyimide precursor to polyimide. In addition, in a preferred aspect, the compound (B) further has a (meth)acrylic group, and when the compound is made into a negative photosensitive resin composition, the compound (B) reacts with the side chain portion of the polyimide precursor by light irradiation and crosslinks, so that the compound (B) is more likely to exist in the vicinity of the polyimide precursor, and the conversion efficiency can be dramatically improved.
Therefore, in the production of the polyimide or the production of the cured relief pattern according to this embodiment, despite the fact that heat curing is performed at a low temperature, the conversion to polyimide is almost complete and the cyclization reaction does not proceed any further. As a result, no shrinkage stress is generated and high adhesion can be maintained.
In addition, since the conversion to polyimide is almost complete, when a photosensitive resin composition is coated and prebaked on the first polyimide film to form a second layer, the first layer is considered to have sufficient solvent resistance, resulting in sufficient in-plane uniformity.

In this embodiment, when the (B) compound further has a (meth)acrylic group, the (meth)acrylic equivalent of the (B) compound is preferably 150 to 400 g/mol. When the (meth)acrylic equivalent of the (B) compound is 150 g/mol or more, the chemical resistance of the negative photosensitive resin composition tends to be good, and when it is 400 g/mol or less, the developability tends to be good. The lower limit of the (meth)acrylic equivalent of the (B) compound is more preferably 200 g/mol or more, 210 g/mol or more, 220 g/mol or more, or 230 g/mol or more, more preferably 240 g/mol or more, or 250 g/mol or more, and the lower limit is more preferably 350 g/mol or less, or 330 g/mol or less, and more preferably 300 g/mol or less. The (meth)acrylic equivalent of the (B) compound is even more preferably 210 to 400 g/mol, and particularly preferably 220 to 400 g/mol.

｛式中、Ｒ_３は、水素原子又はメチル基であり、Ａは、－Ｏ－、－ＮＨ－、及び－ＮＬ_４－から成る群から選択される一つの基であり、Ｌ_４は、炭素数１～１２の１価の有機基であり、Ｚ_１は、炭素数２～２４のｍ_２価の有機基であり、Ｚ_２は、炭素数２～８の２価の有機基であり、そしてｍ_２は、１～３の整数である。｝ The urethane/urea compound (B) used in this embodiment is preferably a (meth)acrylic group-containing urethane/urea compound having a structure represented by the following general formula (b3).

{In the formula, R ₃ is a hydrogen atom or a methyl group, A is a group selected from the group consisting of -O-, -NH-, and -NL ₄ -, L ₄ is a monovalent organic group having 1 to 12 carbon atoms, Z ₁ is a _divalent organic group having 2 to 24 carbon atoms, Z ₂ is a divalent organic group having 2 to 8 carbon atoms, and m ₂ is an integer from 1 to 3.}

In formula (b3), R ₃ may be a hydrogen atom or a methyl group, and is preferably a methyl group from the viewpoint of developability. Z ₁ may be a _bivalent organic group having 2 to 24 carbon atoms, and the number of carbon atoms is preferably 2 to 20. Here, Z ₁ may also contain heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and phosphorus atoms. If Z ₁ has 2 or more carbon atoms, the negative photosensitive resin composition tends to have good chemical resistance, and if it has 20 or less carbon atoms, the developability tends to be good. The number of carbon atoms in Z ₁ is more preferably 3 or more, even more preferably 4 or more, and more preferably 18 or less, and even more preferably 16 or less. Z ₂ may be a bivalent organic group having 2 to 8 carbon atoms. Here, Z ₂ may also contain heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and phosphorus atoms. If Z ₂ has 2 or more carbon atoms, the negative photosensitive resin composition tends to have good chemical resistance, and if it has 8 or less carbon atoms, the heat resistance tends to be good. The number of carbon atoms in _Z2 is preferably 6 or less, and more preferably 4 or less. A is a group selected from the group consisting of -O-, -NH-, and -NL ₄ - {wherein L ₄ is a monovalent organic group having 1 to 12 carbon atoms.}. From the viewpoint of chemical resistance, A is preferably -NH- or NL ₄ -.

The (meth)acrylic group-containing urea/urethane compound of the above general formula (b3) can be produced, for example, by reacting an isocyanate compound represented by the following general formula with an amine and/or a hydroxyl group-containing compound.

Among the compounds (B) described above, from the viewpoints of chemical resistance, void suppression, and developability, at least one compound selected from the group consisting of the following formulas (b4) to (b7), and (b11) to (b16) is particularly preferred. The compounds represented by the following formulas (b4) to (b7), and (b11) to (b16) also constitute one embodiment of the present invention.

In another embodiment, tetramethylurea can be used as the compound having a urea bond (B).

In the present embodiment, the (B) compound may be used alone or in a mixture of two or more kinds. The amount of the (B) compound is preferably 0.1 parts by mass or more and 30 parts by mass or less, and more preferably 1 part by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the (A) polyimide precursor. The amount of the (B) compounded is 0.1 parts by mass or more from the viewpoint of photosensitivity or patterning property, and is 30 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative photosensitive resin composition.

(C) Photopolymerization initiator The photopolymerization initiator is preferably a photoradical polymerization initiator. Examples of the photoradical polymerization initiator include benzophenone derivatives such as benzophenone, o-benzoyl methyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzyl derivatives such as benzil, benzil dimethyl ketal, and benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin and benzoin methyl ether; and 1-phenyl-1,2-butanedione-2-(o- methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl) oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl) oxime, and 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl) oxime; N-arylglycines such as N-phenylglycine; peroxides such as benzoyl perchloride; aromatic biimidazoles; titanocenes; and photoacid generators such as α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide. Among the above photopolymerization initiators, oximes are more preferable, particularly from the viewpoint of photosensitivity.

The amount of the photopolymerization initiator (C) is preferably 0.1 parts by mass or more and 20 parts by mass or less, and more preferably 1 part by mass or more and 8 parts by mass or less, relative to 100 parts by mass of the polyimide precursor (A). The amount is 0.1 parts by mass or more from the viewpoint of photosensitivity or patterning property, and 20 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative photosensitive resin composition.

(D) Solvent The solvent according to this embodiment is at least one of 3-methoxy-N,N-dimethylpropionamide and 3-butoxy-N,N-dimethylpropionamide.
By using the above solvent, the effect of the (B) urea/urethane compound is exhibited. Although the reason is not clear, it is presumed that the (B) urea/urethane compound is thermally decomposed and promotes the conversion to polyimide as described above. On the other hand, since the (B) urea/urethane compound has a high cohesive force, it aggregates and the decomposition is difficult to proceed when the solvent evaporates during thermal curing. However, when a solvent specified as 3-methoxy-N,N-dimethylpropionamide or 3-butoxy-N,N-dimethylpropionamide is used, the interaction between the urea/urethane compound and the solvent is large, so condensation is difficult to occur, and the conversion of polyimide is easily promoted, which is considered to improve adhesion. In addition, the elongation after the reliability test tends to improve in order to suppress the aggregation of the (B) compound. Such an effect is as obtained in the examples described later, in the cases where 3-methoxy-N,N-dimethylpropionamide and 3-butoxy-N,N-dimethylpropionamide are used as the (D) solvent, respectively. Based on the mechanism presumed above, it is understood that such an effect can also be obtained when both are used in combination as the solvent (D).

The solvent according to the present embodiment may contain the following solvents (hereinafter, also referred to as "other solvents") to the extent that they do not adversely affect performance. Examples of other solvents include amides, sulfoxides, ureas (excluding the above-mentioned (B) compound containing a urea bond), ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and alcohols. More specifically, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene, and the like can be used.
On the other hand, the content of the other solvent is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less, based on 100 parts by mass of the polyimide precursor (A).
In addition, the content of the other solvent is preferably less than the content of the (D) solvent.

In the negative-type photosensitive resin composition of this embodiment, the amount of the solvent (D) used is preferably 10 to 1000 parts by mass, more preferably 100 to 700 parts by mass, and even more preferably 125 to 500 parts by mass, per 100 parts by mass of the polyimide precursor (A). When 3-methoxy-N,N-dimethylpropionamide and 3-butoxy-N,N-dimethylpropionamide are used in combination, it is preferable that the total amount used is in the above range.

(E) Rust inhibitor The negative photosensitive resin composition of the present embodiment may further contain a rust inhibitor. The rust inhibitor may be any compound capable of preventing metal from rusting, and may be a nitrogen-containing heterocyclic compound. Examples of the nitrogen-containing heterocyclic compound include an azole compound, and a purine or purine derivative.

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

Particularly preferred azole compounds include tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or in combination of two or more.

The (E) rust inhibitor may contain purine or a derivative thereof. Examples of the purine derivatives contained in the (E) rust inhibitor include adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8- These include aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, and 8-azahypoxanthine, as well as derivatives thereof.

When the negative photosensitive resin composition contains an azole compound, or a purine or purine derivative, the amount is preferably 0.05 to 5 parts by mass relative to 100 parts by mass of the polyimide precursor (A), and more preferably 0.1 to 5 parts by mass from the viewpoint of photosensitivity characteristics. When the amount of the azole compound relative to 100 parts by mass of the polyimide precursor (A) is 0.05 parts by mass or more, discoloration of the copper or copper alloy surface is suppressed when the negative photosensitive resin composition of this embodiment is formed on copper or a copper alloy, while when the amount of the azole compound is 5 parts by mass or less, the photosensitivity is excellent.

When the negative photosensitive resin composition of this embodiment contains (D) an anti-rust agent, the formation of voids in the Cu layer is particularly suppressed. The reason for this effect is unclear, but it is thought that the anti-rust agent present on the Cu surface interacts with the (meth)acrylic group, hydroxyl group, alkoxy group, or amino group contained in the preferred embodiment of the urethane/urea compound to form a dense layer near the Cu interface.

(F) Silane Coupling Agent The negative photosensitive resin composition of the present embodiment may further contain a silane coupling agent. Examples of the silane coupling agent 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]propionate ... [propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and 3-(trialkoxysilyl)propylsuccinic anhydride can be mentioned.

More specifically, the silane coupling agent may be 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: product name KBM803, manufactured by Chisso Corporation: product name Sila-Ace S810), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Corporation: product name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: product name LS1375, manufactured by Azmax Corporation: product name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Corporation: product name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Corporation: product name SIM6473.0), 3-mercaptopropyl diethoxy methoxy silane, 3-mercaptopropyl ethoxy dimethoxy silane, 3-mercaptopropyl tripropoxy silane, 3-mercaptopropyl diethoxy propoxy silane, 3-mercaptopropyl ethoxy dipropoxy silane, 3-mercaptopropyl dimethoxy propoxy silane, 3-mercaptopropyl methoxy dipropoxy silane, 2-mercaptoethyl trimethoxy silane, 2-mercaptoethyl diethoxy Examples include dimethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, and 4-mercaptobutyltripropoxysilane.

More specifically, examples of silane coupling agents include N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: product name LS3610, manufactured by Azmax Corporation: product name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Corporation: product name SIU9058.0), N-(3-diethoxymethoxysilylpropyl)urea, N-(3-ethoxydimethoxysilylpropyl)urea, N-(3-tripropoxysilylpropyl)urea, N-(3-diethoxypropoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-dimethoxypropoxysilylpropyl)urea, N-(3-methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea, and N-(3-ethoxydimethoxysilylethyl). Urea, N-(3-tripropoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-tripropoxysilylbutyl)urea, 3-(m-aminophenoxy)propyltrimethoxysilane (trade name: manufactured by Azmax Corporation) Examples include SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: product name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: product name SLA0599.1), and aminophenyltrimethoxysilane (manufactured by Azmax Corporation: product name SLA0599.2).

More specifically, examples of silane coupling agents include 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax Corporation: product name SIT8396.0), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylmethylethyl)pyridine, (3-triethoxysilylpropyl)-t-butylcarbamate, (3-glycidoxypropyl)triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, tetrakis(methoxyethoxysilane), tetrakis(methoxy-n-propoxysilane), ), tetrakis(ethoxyethoxysilane), tetrakis(methoxyethoxyethoxysilane), bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane, bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane, bis(triethoxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide, bis[3-(triethoxysilyl)propyl]tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane silane, phenyl silanetriol, methyl phenyl silanediol, ethyl phenyl silanediol, n-propyl phenyl silanediol, isopropyl phenyl silanediol, n-butyl diphenyl silanediol, isobutyl phenyl silanediol, tert-butyl phenyl silanediol, diphenyl silanediol, dimethoxy diphenyl silane, diethoxy diphenyl silane, dimethoxy di-p-tolyl silane, ethyl methyl phenyl silanol, n-propyl methyl phenyl silanol, isopropyl methyl phenyl silanol, n-butyl methyl phenyl silanol, isopropyl methyl phenyl silanol, Examples of the silane coupling agents include isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, and triphenylsilanol. The silane coupling agents listed above may be used alone or in combination.

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

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

When a silane coupling agent is used, the amount is preferably 0.1 to 20 parts by mass per 100 parts by mass of the polyimide precursor (A). When the negative photosensitive resin composition of this embodiment contains a silane coupling agent (F), void formation in the Cu layer is particularly suppressed. The reason for this effect is unclear, but it is thought that the silane coupling agent unevenly distributed on the Cu surface interacts with the (meth)acrylic group, hydroxyl group, alkoxy group, or amino group contained in the preferred embodiment of the urethane/urea compound to form a dense layer near the Cu interface.

(G) Other Components The negative type photosensitive resin composition of the present embodiment may further contain components other than the above components (A) to (F). Examples of the components other than the components (A) to (F) include a hindered phenol compound, an organic titanium compound, a sensitizer, a photopolymerizable unsaturated monomer, and a thermal polymerization inhibitor.

Hindered Phenol Compounds To inhibit discoloration on copper surfaces, the negative-type photosensitive resin composition may optionally contain a hindered phenol compound. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 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], and the like. 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-hydrocinnamamide), 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, and the like.

Examples of hindered phenol compounds include 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 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-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 lion, 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, and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione. Among the hindered phenol compounds listed above, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione and the like are particularly preferred.

The amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the polyimide precursor (A), and more preferably 0.5 to 10 parts by mass from the viewpoint of photosensitivity characteristics. When the amount of the hindered phenol compound relative to 100 parts by mass of the polyimide precursor (A) is 0.1 part by mass or more, for example, when the photosensitive resin composition of this embodiment is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy is prevented, while when the amount is 20 parts by mass or less, excellent photosensitivity is achieved.

Organic titanium compound The negative photosensitive resin composition of the present embodiment may contain an organic titanium compound. By containing an organic titanium compound, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at a low temperature.

Usable organotitanium compounds include those in which an organic chemical is bonded to a titanium atom via a covalent or ionic bond. Specific examples of organotitanium compounds are shown below in I) to VII):

I) Titanium chelate compounds: Among these, titanium chelates having two or more alkoxy groups are more preferred because they provide good storage stability and patterns for the negative photosensitive resin composition. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate, titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), etc.

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}], etc.

III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc.

IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.

V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.

VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate, etc.

VII) Titanate coupling agents: For example, isopropyl tridodecylbenzenesulfonyl titanate, etc.

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

When an organic titanium compound is added, the amount is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the polyimide precursor (A). When the amount of the organic titanium compound is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited, while when the amount is 10 parts by mass or less, excellent storage stability is exhibited.

Sensitizer The negative photosensitive resin composition of the present embodiment may optionally 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, and p-dimethylaminocinnamylidene indanone. , p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl 7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, and 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, and the like. These may be used alone or in combination of two or more, for example, two to five types.

When the photosensitive resin composition contains a sensitizer, the amount of the sensitizer is preferably 0.1 to 25 parts by mass per 100 parts by mass of the polyimide precursor (A).

Photopolymerizable Unsaturated Monomer The negative photosensitive resin composition may optionally contain a monomer having a photopolymerizable unsaturated bond (photopolymerizable unsaturated monomer) in order to improve the resolution of the relief pattern. As such a monomer, a (meth)acrylic compound that undergoes a radical polymerization reaction by a photopolymerization initiator is preferable, and examples thereof include mono- or diacrylates and methacrylates of ethylene glycol or polyethylene glycol, such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, mono- or diacrylates and methacrylates of propylene glycol or polypropylene glycol, mono-, di- or triacrylates and methacrylates of glycerol, cyclohexane diacrylate and dimethacrylate, diacrylates and dimethacrylates of 1,4-butanediol, and diacrylates and dimethacrylates of 1,6-hexanediol. Examples of such compounds include acrylate and dimethacrylate, diacrylate and dimethacrylate of neopentyl glycol, mono- or diacrylate and methacrylate of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, di- or triacrylate and methacrylate of glycerol, di-, tri-, or tetraacrylate and methacrylate of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds.

When the photosensitive resin composition contains a photopolymerizable unsaturated monomer, the amount of the monomer is preferably 1 to 50 parts by mass per 100 parts by mass of the polyimide precursor (A).

Thermal Polymerization Inhibitor The negative photosensitive resin composition of the present embodiment may optionally contain a thermal polymerization inhibitor in order to improve the stability of the viscosity and photosensitivity of the negative photosensitive resin composition, particularly when stored in a state of a solution containing a solvent. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic 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, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

<Method for Producing Cured Relief Pattern and Semiconductor Device>
The method for producing a cured relief pattern of the present embodiment includes the following steps:
(1) applying the negative type photosensitive resin composition of the present embodiment onto a substrate to form a photosensitive resin layer on the substrate;
(2) a step of exposing the photosensitive resin layer to light;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) heat-treating the relief pattern to form a hardened relief pattern.

(1) Photosensitive resin layer forming step In this step, the negative photosensitive resin composition of the present embodiment is applied onto a substrate, and then dried as necessary to form a photosensitive resin layer. As the application method, a method that has been conventionally used for applying a photosensitive resin composition, such as a method of applying with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, etc., and a method of spray application with a spray coater, etc., can be used.

If necessary, the coating film containing the photosensitive resin composition can be dried. Drying methods that can be used include air drying, heat drying in an oven or on a hot plate, vacuum drying, and the like. Specifically, when air drying or heat drying is performed, drying can be performed under conditions of 20°C to 140°C for 1 minute to 1 hour. In this way, a photosensitive resin layer can be formed on the substrate.

(2) Exposure Step In this step, the photosensitive resin layer formed above is exposed to an ultraviolet light source or the like. As an exposure method, an exposure device such as a contact aligner, a mirror projection, or a stepper can be used. Exposure can be performed directly or through a photomask or reticle having a pattern.

After this, for the purpose of improving the photosensitivity, etc., a post-exposure bake (PEB) and/or a pre-development bake may be performed at any combination of temperature and time, as necessary. As for the range of baking conditions, the temperature is preferably 40°C to 120°C, and the time is preferably 10 seconds to 240 seconds.

(3) Relief Pattern Forming Step In this step, the unexposed portion of the exposed photosensitive resin layer is developed and removed from the substrate, leaving a relief pattern on the substrate. As a developing method for developing the exposed (irradiated) photosensitive resin layer, any method can be selected from conventionally known photoresist developing methods, such as a rotary spray method, a paddle method, and an immersion method accompanied by ultrasonic treatment. After development, post-development baking may be performed at any combination of temperature and time, if necessary, for the purpose of adjusting the shape of the relief pattern.

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

(4) Cured Relief Pattern Formation Step In this step, the relief pattern obtained by the above development is heated to disperse the photosensitive component and imidize the polyimide precursor (A), thereby converting it into a cured relief pattern made of polyimide. As the heat curing method, various methods can be selected, such as using a hot plate, using an oven, or using a temperature-elevating oven that can set a temperature program. Heating can be performed, for example, at 170°C to 400°C, preferably 170°C to 300°C, more preferably 170°C to 250°C, and even more preferably 170°C to 200°C, for example, for 30 minutes to 5 hours. Air may be used as the atmospheric gas during heat curing, and inert gases such as nitrogen and argon may also be used.

｛一般式（１０）中、Ｘ^１及びＹ^１は、それぞれ一般式（１）中のＸ_１及びＹ_１と同じであり、そしてｍは正の整数である。｝ <Polyimide>
The structure of the polyimide contained in the cured relief pattern formed from the polyimide precursor composition is represented by the following general formula (10).

{In the general formula (10), ^X1 and ^Y1 are the same as _X1 and _Y1 in the general formula (1), respectively, and m is a positive integer.}

For the same reason, the preferred _X1 and _Y1 in general formula (1) are also preferred in the polyimide of general formula (10). The number of repeating units m in general formula (10) may be an integer of 2 to 150. In addition, a method for producing a polyimide, which includes a step of converting the polyimide precursor (A) contained in the negative photosensitive resin composition described above into a polyimide, is also an aspect of the present invention.

<Semiconductor Device>
In this embodiment, a semiconductor device having a cured relief pattern obtained by the above-mentioned method for producing a cured relief pattern is also provided. Thus, a semiconductor device can be provided having a substrate that is a semiconductor element and a cured relief pattern of polyimide formed on the substrate by the above-mentioned method for producing a cured relief pattern. This embodiment can also be applied to a method for producing a semiconductor device that uses a semiconductor element as the substrate and includes the above-mentioned method for producing a cured relief pattern as part of the process. The semiconductor device of the present invention can be produced by forming the cured relief pattern formed by the above-mentioned method for producing a cured relief pattern as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a protective film for a semiconductor device having a bump structure, and combining it with a known method for producing a semiconductor device.

<Display device>
In this embodiment, a display device is provided that includes a display element and a cured film provided on the upper portion of the display element, and the cured film is the above-mentioned cured relief pattern. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer sandwiched therebetween. For example, the cured film can be a surface protection film, an insulating film, and a planarizing film for a TFT liquid crystal display element and a color filter element, a protrusion for an MVA type liquid crystal display device, and a partition wall for a cathode of an organic EL element.

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

The present embodiment will be described in detail below with reference to examples, but the present embodiment is not limited thereto. In the 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 methods>
(1) Weight Average Molecular Weight The weight average molecular weight (Mw) of each resin was measured using gel permeation chromatography (standard polystyrene equivalent) under the following conditions.
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40°C
Column: Showa Denko Shodex KD-806M, 2 in series, or
Shodex 805M/806M series manufactured by Showa Denko K.K. Standard monodisperse polystyrene: Shodex STANDARD SM-105 manufactured by Showa Denko K.K.
Mobile phase: 0.1 mol/L LiBr/N-methyl-2-pyrrolidone (NMP)
Flow rate: 1mL/min

(2) Crack evaluation when polyimide film is formed as two layers On a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm), 200 nm thick Ti and 400 nm thick Cu were sputtered in this order using a sputtering device (L-440S-FHL type, manufactured by Canon Anelva Corporation). Next, a negative photosensitive resin composition prepared by the method described below was spin-coated on this wafer using a coater developer (D-Spin 60A type, manufactured by SOKUDO Co., Ltd.), and pre-baked on a hot plate at 110° C. for 180 seconds to form a coating film with a thickness of about 7 μm. This coating film was irradiated with energy of 100 to 500 mJ/cm ² using a test pattern mask by Prisma GHI (manufactured by Ultratech Co., Ltd.). Next, this coating film was spray-developed with a coater developer (D-Spin 60A type, manufactured by SOKUDO Co., Ltd.) using cyclopentanone as a developer, and rinsed with propylene glycol methyl ether acetate to obtain a relief pattern on Cu. The wafer on which the relief pattern was formed on Cu was heat-treated in a temperature-rising programmable curing furnace (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd.) for 2 hours at the curing temperature shown in Table 1 under a nitrogen atmosphere to obtain a cured relief pattern made of resin having a thickness of about 4 to 5 μm on Cu.
Subsequently, the relief pattern after the heat treatment was coated, exposed, and cured again under the same conditions. The cured polyimide film was evaluated as follows: x (bad) if 4 or more cracks occurred per wafer, △ (acceptable) if 1 to 3 cracks occurred per wafer, and ◯ (good) if no cracks occurred.

(3) Adhesion test with sealing material As an epoxy-based sealing material, R4000 series manufactured by Nagase Chemtex Corporation was prepared. The sealing material was spin-coated on an aluminum-sputtered silicon wafer to a thickness of about 150 μm, and the epoxy-based sealing material was cured by thermal curing at 130 ° C. The photosensitive resin composition prepared in each Example and Comparative Example was applied to the above epoxy-based cured film to a final film thickness of 10 μm. The applied photosensitive resin composition was exposed to a ghi ray with an exposure dose of 600 mJ / cm ² using an aligner (PLA-501F, manufactured by Canon Inc.) over the entire surface. Thereafter, the exposed photosensitive resin composition was thermally cured at 180 ° C. for 2 hours to prepare a first layer cured film with a thickness of 10 μm.

The photosensitive resin composition used in forming the first cured film was applied onto the first cured film, and the entire surface was exposed to light under the same conditions as when the first cured film was prepared, and then the film was thermally cured to prepare a second cured film having a thickness of 10 μm. A pin was placed on the sample prepared in the encapsulant deterioration test, and an adhesion test was performed using a pull tester (Quad Group, Sebastian 5 type). That is, the adhesive strength between the epoxy encapsulant and the cured relief pattern prepared from the photosensitive resin composition prepared in each Example and Comparative Example was measured and evaluated according to the following criteria.
Evaluation: Adhesion strength 70 MPa or more...Adhesion strength A
Adhesive strength: 50MPa or more to less than 70MPa...Adhesion strength B
Adhesive strength: 30MPa or more to less than 50MPa...Adhesion C
Adhesive strength less than 30MPa...Adhesion strength D

(4) Elongation after HTS (High Temperature Storage Test: Reliability Test) A negative photosensitive resin composition was coated on a 6-inch silicon wafer that had been previously aluminum-sputtered under the same conditions as in the above (2) crack evaluation, and after curing, an HTS test (150° C., 168 hours, in air) was performed.
After the test, the wafer was cut into a 3 mm wide cut in the polyimide resin film of the wafer using a dicing saw (DAD 3350, manufactured by Disco Corporation), and then immersed in a dilute hydrochloric acid solution overnight to peel off the resin film piece, which was then dried and cut into a length of 50 mm to prepare a sample.
The elongation (%) of the above sample was measured using a TENSILON (UTM-II-20 manufactured by Orientec Co., Ltd.) at a test speed of 40 mm/min and an initial load of 0.5 fs.

Production Example 1: (A) Synthesis of Polymer A-1 as a Polyimide Precursor 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 L separable flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone were added and stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the end of the heat generation due to the reaction, the reaction mixture was allowed to cool to room temperature and left for 16 hours. Next, under ice cooling, a solution obtained by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring, and then a suspension of 93.0 g of 4,4'-oxydianiline (ODA) in 350 mL of γ-butyrolactone was added over 60 minutes while stirring. After further stirring at room temperature for 2 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour, and then 400 mL of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. The reaction solution obtained was added to 3 L of ethyl alcohol to generate a precipitate consisting of a crude polymer. The generated crude polymer was filtered and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 L of water to precipitate the polymer, and the obtained precipitate was filtered and then dried in vacuum to obtain a powdered polymer (polymer A-1). The molecular weight of polymer (A-1) was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 20,000.

Production Example 2: (A) Synthesis of Polymer A-2 as Polyimide Precursor Polymer (A-2) was obtained by carrying out a reaction in the same manner as in the above Production Example 1, except that 98.6 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) was used instead of 93.0 g of 4,4'-oxydianiline (ODA) in Production Example 1. The molecular weight of polymer (A-2) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 21,000.

Production Example 3: Production method of MOI-D (Compound B-1)
55.1 g (0.25 mol) of diethylene glycol bis(3-aminopropyl)ether was placed in a 500 mL separable flask, and 150 mL of tetrahydrofuran was added and stirred at room temperature. Next, under ice cooling, a solution of 77.6 g (0.50 mol) of 2-methacryloyloxyethyl isocyanate (Showa Denko K.K., product name: Karenz MOI) and 150 mL of tetrahydrofuran was added dropwise to the flask over 30 minutes, and the mixture was stirred at room temperature for 5 hours. Thereafter, tetrahydrofuran was distilled off using a rotary evaporator to obtain compound B-1.

Production Example 4: Production method of MOI-AEE (Compound B-7)
Compound B-7 was obtained by the same synthesis method as in Example 1, except that in Production Example 4, 55.1 g of diethylene glycol bis(3-aminopropyl)ether was replaced with 26.3 g (0.25 mol) of 2-(2-aminoethoxy)ethanol and 77.6 g of 2-methacryloyloxyethyl isocyanate (product of Showa Denko K.K., product name: Karenz MOI) was replaced with 38.8 g (0.25 mol).

Production Example 5 Production method of MOI-DOA (Compound B-8)
Compound B-8 was obtained by the same synthesis method as in Example 1, except that in Production Example 4, 55.1 g of diethylene glycol bis(3-aminopropyl)ether was replaced with 60.4 g (0.25 mol) of di-n-octylamine, and 77.6 g of 2-methacryloyloxyethyl isocyanate (product of Showa Denko K.K., product name: Karenz MOI) was replaced with 38.8 g (0.25 mol).

Production example 6 (compound B-11)
2.10 g (0.020 mol) of diethanolamine was placed in a 100 mL three-neck flask, 5.6 g of tetrahydrofuran was added, and the mixture was stirred at room temperature. Next, 2.67 g (0.021 mol) of hexyl isocyanate was added under ice cooling. A solution containing 5.6 g of tetrahydrofuran was added dropwise to the flask over 15 minutes and stirred at room temperature for 4 hours. Then, the tetrahydrofuran was removed using a rotary evaporator to obtain compound B-11. .

Example 1
A negative photosensitive resin composition was prepared using polymer A-1 by the following method, and the prepared composition was evaluated. (A) 100 g of polymer A-1 as a polyimide precursor, (B) 8 g of compound B-1 of Example 1 as a compound, and (C) 3 g of ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) (OXE-02, corresponding to photopolymerization initiator C-1) as a photopolymerization initiator were dissolved in 150 g of 3-methoxy-N,N-dimethylpropionamide. The viscosity of the obtained solution was adjusted to about 30 poise by further adding a small amount of 3-methoxy-N,N-dimethylpropionamide to obtain a negative photosensitive resin composition. The composition was evaluated according to the above-mentioned method. The results are shown in Table 1.

<Examples 2 to 7, Comparative Example 1>
Negative photosensitive resin compositions were prepared in the same manner as in Example 1, except that they were prepared in the blending ratios shown in Table 1, and were evaluated according to the above-mentioned methods. The results are shown in Table 1.

The compounds (B-1, 7, 8, 11), the photopolymerization initiator (C-1), and the solvents (D-1 to D-3) shown in Table 1 are the following compounds.

C-1: Ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) (trade name: IRGACURE OXE-02 (OXE-02))
D-1: 3-Methoxy-N,N-dimethylpropionamide (KJ Chemicals: Trade name KJCMPA-100)
D-2: 3-butoxy-N,N-dimethylpropionamide (KJ Chemicals: Trade name KJCBPA-100)
D-3: N-methyl-2-pyrrolidone (NMP)

The negative photosensitive resin composition of the present invention provides good adhesion to the encapsulant, excellent in-plane uniformity and crack resistance when multi-layered, and excellent elongation after reliability testing. The present invention can be suitably used in the field of photosensitive materials that are useful for manufacturing electrical and electronic materials such as semiconductor devices and multi-layer wiring boards.

Claims (13)

(A) A compound represented by the following general formula (1):
In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer from 2 to 150, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, and at least one of R ₁ and R ₂ is represented by the following general formula (2):
(In the formula, L ₁ , L ₂ and L ₃ each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ represents an integer of 2 to 10.)
It is a monovalent organic group represented by the following formula:
A polyimide precursor having a structural unit represented by the formula:
(B) a compound having a urea bond (excluding 3-ureidopropyltriethoxysilane),
(C) a photopolymerization initiator; and (D) at least one solvent selected from the group consisting of 3-methoxy-N,N-dimethylpropionamide and 3-butoxy-N,N-dimethylpropionamide ;
The compound (B) is represented by the following general formulas (3A), (3B), and (4):
In the formula, R ₇ and R ₈ are each independently a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, R ₉ is a hydrogen atom, and R ₁₀ is a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom.
In the formula, R ₇ is a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, R ₈ is a monovalent organic group having 1 to 20 carbon atoms which contains an oxygen atom, and R ₉ and R ₁₀ are hydrogen atoms.
In the formula, R ₁₁ and R ₁₂ are each independently a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and R ₁₃ is a divalent organic group having 1 to 20 carbon atoms which contains an oxygen atom.
The negative type photosensitive resin composition is any one of compounds represented by the following formula (1) : 2. The negative type photosensitive resin composition according to claim 1 , wherein the compound (B) contains at least one functional group selected from the group consisting of a (meth)acrylic group, a hydroxyl group, and an amino group. The negative type photosensitive resin composition according to claim 1 or 2 , wherein the compound (B) has a (meth)acrylic group or a hydroxyl group. Y ₁ in the general formula (1) of the polyimide precursor (A) is represented by the following general formula (5):
In the formula, R ₁₄ and R ₁₅ each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms which may contain a halogen atom.
The negative type photosensitive resin composition according to any one of claims 1 to 3 , wherein the structure is represented by: The negative type photosensitive resin composition according to any one of claims 1 to 4 , further comprising (E) a rust inhibitor. The negative type photosensitive resin composition according to claim 5 , wherein the (E) rust inhibitor comprises a nitrogen-containing heterocyclic compound. The negative type photosensitive resin composition according to claim 6 , wherein the nitrogen-containing heterocyclic compound is an azole compound. The negative type photosensitive resin composition according to claim 6 , wherein the nitrogen-containing heterocyclic compound is a purine or a purine derivative. The negative type photosensitive resin composition according to any one of claims 1 to 8 , further comprising (F) a silane coupling agent. _X1 in the general formula (1) of the polyimide precursor (A) is represented by the following general formulas (20a), (20b), and (20c):
In the formula, R ₆ is at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and l is an integer selected from 0 to 2.
{In the formula, each R ₆ is independently at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and each m is independently an integer selected from 0 to 3.}
{In the formula, each R ₆ is independently at least one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and each m is independently an integer selected from 0 to 3.}
The negative type photosensitive resin composition according to any one of claims 1 to 9 , which has a structure including at least one selected from the group consisting of: The (A) polyimide precursor;
0.1 to 30 parts by mass of the (B) compound based on 100 parts by mass of the (A) polyimide precursor;
0.1 to 20 parts by mass of the photopolymerization initiator (C) based on 100 parts by mass of the polyimide precursor (A);
The negative type photosensitive resin composition according to any one of claims 1 to 10 , comprising 10 to 1000 parts by mass of the (D) solvent based on 100 parts by mass of the (A) polyimide precursor. A method for producing a polyimide, comprising a step of converting the polyimide precursor (A) contained in the negative photosensitive resin composition according to any one of claims 1 to 11 into a polyimide. (1) A process for forming a photosensitive resin layer on a substrate by applying the negative type photosensitive resin composition according to any one of claims 1 to 11 ;
(2) exposing the photosensitive resin layer to light;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising the step of heat-treating the relief pattern to form a cured relief pattern.