JP7156786B2 - Negative photosensitive resin composition, method for producing cured relief pattern, and semiconductor device - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photosensitive resin composition, and a semiconductor device, a display device, and the like having a cured relief pattern obtained by curing the photosensitive resin composition.

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 a photosensitive polyimide precursor 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 process reduction compared to conventional non-photosensitive polyimide resins.

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 the degree of integration and arithmetic functions, as well as miniaturization of chip sizes. Polyimide coating directly contacts solder bumps, such as BGA (Ball Grid 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 are coming into use. When forming such a bump structure, the film is required to have high heat resistance and chemical resistance.

Furthermore, the problem of wiring delay has become apparent as the miniaturization of semiconductor devices progresses. As a means of improving the wiring resistance of a semiconductor device, the gold or aluminum wiring that has been used so far is being changed to a copper or copper alloy wiring having a lower resistance. Furthermore, a method of preventing wiring delay by increasing insulation between wirings is also adopted. In recent years, semiconductor devices are often made of low-dielectric-constant materials as materials with high insulating properties. A problem exists in that shrinkage due to temperature changes destroys the low dielectric constant material portion when mounted in a low dielectric constant material.

As a means for solving this problem, for example, Patent Document 1 discloses a photosensitive polyimide precursor in which a part of a photosensitive group having 4 or more carbon atoms having a terminal ethylene bond is substituted with a hydrocarbon group having 1 to 3 carbon atoms. is disclosed.

JP-A-6-80776

However, although the photosensitive resin composition composed of the polyimide precursor described in Patent Document 1 is improved in resolution or elongation, there is still room for improvement in chemical resistance.
In order to improve chemical resistance, it is necessary to increase the imidization rate. Conventionally, a large amount of an imidization accelerator (for example, a compound exhibiting basicity) has been added. However, if the amount of the imidization accelerator is large, there is a problem that the imidization progresses even during storage, resulting in poor storage stability.

Therefore, the present invention provides a photosensitive resin composition that can achieve a high imidization rate while maintaining storage stability and has high chemical resistance, and to produce a cured relief pattern using the photosensitive resin composition. It is an object of the present invention to provide a method and a semiconductor device or a display device comprising the cured relief pattern.

｛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_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、Ｒ_１及びＲ_２の少なくともいずれかは下記一般式（２）：
－Ｒ_３ （２）
（式（２）中、Ｒ_３は、アルキレンオキシド基を有する１価の有機基である。）で表される基である｝で表される前駆体を含み、そして、
前記（Ａ）ポリイミド前駆体中に含まれる前記一般式（１）で表される前駆体のＲ_１、及びＲ_２の全てに対する、上記一般式（２）で表される１価の有機基の割合が８０％を超える、ことを特徴とするネガ型感光性樹脂組成物。
［２］
前記（Ｃ）酸、塩基、またはラジカルの作用により重合可能な基を含む化合物は、アルキレンオキシド基を有する、［１］に記載のネガ型感光性樹脂組成物。
［３］
前記（Ｃ）酸、塩基、またはラジカルの作用により重合可能な基を含む化合物が、
下記一般式（３）：

（式（３）中、Ｒ_４及びＲ_５はそれぞれ独立に炭素数１～６の１価の有機基であり、Ｚ_１及びＺ_２はそれぞれ独立に１価の基であり、複数のＺ_１及びＺ_２はそれぞれ同一でも異なっていてもよく、ｍ_１は２～２００の整数である。）で表される化合物を含む［１］又は［２］に記載のネガ型感光性樹脂組成物。
［４］
（Ｃ）酸、塩基、またはラジカルの作用により重合可能な基を含む化合物が、下記一般式（４）：

（式（４）中、Ｚ_１及びＺ_２はそれぞれ独立に１価の基であり、複数のＺ_１及びＺ_２はそれぞれ同一でも異なっていてもよく、ｍ_１は２～２００の整数である。）で表される化合物を含む［３］に記載のネガ型感光性樹脂組成物。
［５］
前記ｍ１が６～２５である、［３］又は［４］に記載のネガ型感光性樹脂組成物。
［６］
前記感光性樹脂組成物中において、前記一般式（３）又は前記一般式（４）で表される化合物全てのｍ_１の平均値の値が６～２５である、［３］～［５］に記載のネガ型感光性樹脂組成物。
［７］
前記（Ｃ）酸、塩基、またはラジカルの作用により重合可能な基を含む化合物は、少なくとも一方の末端に二重結合を有する、［２］～［６］のいずれかに記載のネガ型感光性樹脂組成物。
［８］
前記（Ａ）ポリイミド前駆体は、下記一般式（５）：

｛式（５）中、ｎ_２は、２～１５０の整数であり、Ｒ_４及びＲ_５は、それぞれ独立に、水素原子、又は１価の有機基であり、Ｒ_４及びＲ_５の少なくともいずれかは酸、塩基、またはラジカルの作用により重合可能な基、又は、前記一般式（２）で表される基を含む。｝
で表される前駆体を含む、［１］～［７］のいずれかに記載のネガ型感光性樹脂組成物。
［９］
前記（Ａ）ポリイミド前駆体は、下記一般式（６）：

｛式（６）中、ｎ_１は、２～１５０の整数であり、Ｒ_６及びＲ_７は、それぞれ独立に、水素原子、又は１価の有機基であり、Ｒ_６及びＲ_７の少なくともいずれかは酸、塩基、またはラジカルの作用により重合可能な基、又は、前記一般式（２）で表される基を含む。｝
で表される前駆体を含む、［８］に記載のネガ型感光性樹脂組成物。
［１０］
前記（Ａ）ポリイミド前駆体は、
下記一般式（７）：

｛式（７）中、ｎ_２は、２～１５０の整数であり、Ｒ_８及びＲ_９は、それぞれ独立に、水素原子、又は１価の有機基であり、Ｒ_８及びＲ_９の少なくともいずれかは酸、塩基、またはラジカルの作用により重合可能な基、又は、前記一般式（２）で表される基を含む。｝
で表される前駆体を含む、［８］又は［９］に記載のネガ型感光性樹脂組成物。
［１１］
前記（Ａ）ポリイミド前駆体は、
前記一般式（１）で表され、且つ、前記Ｒ_１及びＲ_２の少なくともいずれかが前記一般式（２）で表される基を含み、且つ、
前記一般式（２）で表される基を含む前記Ｒ_１及びＲ_２の末端に二重結合を有する前駆体を含む、［１］～［１０］のいずれかに記載のネガ型感光性樹脂組成物。
［１２］
前記ネガ型感光性樹脂組成物中に含まれる全固形分を１００質量部としたときに、前記ネガ型感光性樹脂組成物中に含まれる塩基性を示す化合物の量が１０質量部以下である、［１］～［１１］のいずれかに記載のネガ型感光性樹脂組成物。
［１３］
前記ネガ型感光性樹脂組成物中に含まれる前記塩基性を示す化合物の量が５質量部以下である、［１２］に記載のネガ型感光性樹脂組成物。
［１４］
ポリイミド前駆体、光重合開始剤、及び溶剤を含むネガ型感光性樹脂組成物であって、
該樹脂組成物を温度２３℃、湿度５０％Ｒｈで４週間保存した際の樹脂組成物の粘度変化率が初期と比較して５％以内であり、かつ、
該樹脂組成物を１８０℃で２時間加熱して硬化塗膜を得た際に、該硬化塗膜のイミド化率が７０％以上である、ネガ型感光性樹脂組成物。
［１５］
前記樹脂組成物を１８０℃で２時間加熱して硬化塗膜を得た際に、該硬化塗膜のイミド化率が８５％以上である、［１４］に記載のネガ型感光性樹脂組成物。
［１６］
前記ネガ型感光性樹脂組成物中に含まれる全固形分を１００質量部としたときに、塩基性を示す化合物の量が１０質量部以下である、［１４］又は［１５］に記載のネガ型感光性樹脂組成物。
［１７］
前記塩基性を示す化合物の量が５質量部以下である、［１６］に記載のネガ型感光性樹脂組成物。
［１８］
以下の工程：
（１）［１］～［１７］のいずれかに記載の感光性樹脂組成物を基板上に塗布して、感光性樹脂層を該基板上に形成する工程と、
（２）該感光性樹脂層を露光する工程と、
（３）該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）該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。
［１９］
［１８］に記載の方法により製造された硬化レリーフパターン。
［２０］
半導体素子と、該半導体素子の上部に設けられた硬化膜とを備える半導体装置であって、該硬化膜は、［１９］に記載の硬化レリーフパターンである、半導体装置。
［２１］
表示体素子と、該表示体素子の上部に設けられた硬化膜とを備える表示体装置であって、該硬化膜は、［１９］に記載の硬化レリーフパターンである、表示体装置。 In view of the above-described problems of the prior art, the present inventors have made intensive studies and repeated experiments. The inventors have found that it is possible to achieve both of the contradictory properties of stability and obtain a photosensitive resin composition having high chemical resistance, and have completed the present invention. That is, the present invention is as follows.
[1]
(A) a polyimide precursor;
(B) a photoinitiator;
(C) a compound containing a group polymerizable by the action of an acid, base, or radical;
A negative photosensitive resin composition comprising
The (A) polyimide precursor has the following general formula (1):

{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, n ₁ is 2 to 150 and 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 has the following general formula (2):
-R ₃ (2)
(In formula (2), R ₃ is a monovalent organic group having an alkylene oxide group.) is a group represented by}, and
of the monovalent organic group represented by the general formula (2) for all of R ₁ and R ₂ of the precursor represented by the general formula (1) contained in the polyimide precursor (A) A negative photosensitive resin composition characterized by having a proportion exceeding 80%.
[2]
The negative photosensitive resin composition according to [1], wherein (C) the compound containing a group polymerizable by the action of an acid, a base, or a radical has an alkylene oxide group.
[3]
(C) a compound containing a group polymerizable by the action of an acid, a base, or a radical,
The following general formula (3):

(In formula (3), R ₄ and R ₅ are each independently a monovalent organic group having 1 to 6 carbon atoms, Z ₁ and Z ₂ are each independently a monovalent group, and a plurality of Z ₁ and Z ₂ may be the same or different, and m ₁ is an integer of 2 to 200.).
[4]
(C) a compound containing a group polymerizable by the action of an acid, a base, or a radical, represented by the following general formula (4):

(In formula (4), Z ₁ and Z ₂ are each independently a monovalent group, a plurality of Z ₁ and Z ₂ may be the same or different, and m ₁ is an integer of 2 to 200. .) The negative photosensitive resin composition according to [3], which contains a compound represented by:
[5]
The negative photosensitive resin composition according to [3] or [4], wherein m1 is 6 to 25.
[6]
In the photosensitive resin composition, the _average value of m1 of all the compounds represented by the general formula (3) or the general formula (4) is 6 to 25, [3] to [5] The negative photosensitive resin composition according to .
[7]
The negative photosensitive material according to any one of [2] to [6], wherein (C) the compound containing a group polymerizable by the action of an acid, a base, or a radical has a double bond on at least one end. Resin composition.
[8]
The (A) polyimide precursor has the following general formula (5):

{In formula (5), n ₂ is an integer of 2 to 150, R ₄ and R ₅ are each independently a hydrogen atom or a monovalent organic group, and at least one of R ₄ and R ₅ or includes a group polymerizable by the action of an acid, a base, or a radical, or a group represented by the general formula (2). }
The negative photosensitive resin composition according to any one of [1] to [7], comprising a precursor represented by
[9]
The (A) polyimide precursor has the following general formula (6):

{In formula (6), n ₁ is an integer of 2 to 150, R ₆ and R ₇ are each independently a hydrogen atom or a monovalent organic group, and at least one of R ₆ and R ₇ or includes a group polymerizable by the action of an acid, a base, or a radical, or a group represented by the general formula (2). }
The negative photosensitive resin composition according to [8], comprising a precursor represented by:
[10]
The (A) polyimide precursor is
The following general formula (7):

{In formula (7), n ₂ is an integer of 2 to 150, R ₈ and R ₉ are each independently a hydrogen atom or a monovalent organic group, and at least one of R ₈ and R ₉ or includes a group polymerizable by the action of an acid, a base, or a radical, or a group represented by the general formula (2). }
The negative photosensitive resin composition according to [8] or [9], comprising a precursor represented by.
[11]
The (A) polyimide precursor is
represented by the general formula (1), and at least one of the R ₁ and R ₂ contains a group represented by the general formula (2), and
The negative photosensitive resin according to any one of [1] to [10], which contains a precursor having double bonds at the ends of R ₁ and R ₂ containing the group represented by the general formula (2). Composition.
[12]
When the total solid content contained in the negative photosensitive resin composition is 100 parts by mass, the amount of the compound exhibiting basicity contained in the negative photosensitive resin composition is 10 parts by mass or less. , the negative photosensitive resin composition according to any one of [1] to [11].
[13]
The negative photosensitive resin composition according to [12], wherein the amount of the compound exhibiting basicity contained in the negative photosensitive resin composition is 5 parts by mass or less.
[14]
A negative photosensitive resin composition containing a polyimide precursor, a photopolymerization initiator, and a solvent,
When the resin composition is stored at a temperature of 23° C. and a humidity of 50% Rh for 4 weeks, the viscosity change rate of the resin composition is within 5% compared to the initial period, and
A negative photosensitive resin composition, wherein the cured coating film has an imidization rate of 70% or more when the resin composition is heated at 180° C. for 2 hours to obtain a cured coating film.
[15]
The negative photosensitive resin composition according to [14], wherein when the resin composition is heated at 180° C. for 2 hours to obtain a cured coating film, the imidization rate of the cured coating film is 85% or more. .
[16]
The negative according to [14] or [15], wherein the amount of the compound exhibiting basicity is 10 parts by mass or less when the total solid content contained in the negative photosensitive resin composition is 100 parts by mass. type photosensitive resin composition.
[17]
The negative photosensitive resin composition according to [16], wherein the amount of the compound exhibiting basicity is 5 parts by mass or less.
[18]
The following steps:
(1) a step of applying the photosensitive resin composition according to any one of [1] to [17] onto a substrate to form a photosensitive resin layer on the substrate;
(2) exposing the photosensitive resin layer;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a hardened relief pattern, comprising the step of heat-treating the relief pattern to form a hardened relief pattern.
[19]
A cured relief pattern produced by the method described in [18].
[20]
A semiconductor device comprising a semiconductor element and a cured film provided on the semiconductor element, wherein the cured film is the cured relief pattern according to [19].
[21]
A display device comprising a display element and a cured film provided on the display element, wherein the cured film is the cured relief pattern according to [19].

According to the present invention, a photosensitive resin composition that can achieve a high imidization rate while maintaining storage stability and has high chemical resistance, and a cured relief pattern is produced using the photosensitive resin composition. and a semiconductor device or display device comprising said cured relief pattern.

EMBODIMENT OF THE INVENTION Hereinafter, the form (it abbreviates as "embodiment" hereafter) for implementing this invention is demonstrated in detail. It should be noted that the present invention is not limited to the following embodiments, and can be modified in various ways within the scope of the gist of the present invention.

In the present embodiment, the photosensitive resin composition includes (A) a polyimide precursor, (B) a photopolymerization initiator, and (C) an acid, a base, or a compound containing a group polymerizable by the action of a radical. is a negative photosensitive resin composition comprising If desired, other ingredients are included. Each component is described in turn 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_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、Ｒ_１及びＲ_２の少なくともいずれかは下記一般式（２）：
－Ｒ_３ （２）
（式（２）中、Ｒ_３は、アルキレンオキシド基を有する１価の有機基である。）で表される基である。｝で表される前駆体を含む。
そして、（Ａ）ポリイミド前駆体中に含まれる一般式（１）で表される前駆体のＲ_１、及びＲ_２の全てに対する、上記一般式（２）で表される１価の有機基の割合が８０％を超える。
（Ａ）ポリイミド前駆体において、Ｒ_１及びＲ_２の少なくともいずれかは一般式（２）で表される１価の有機基を含み、その割合が８０％を超えることで、反応性が向上し、本実施形態の感光性樹脂組成物は、高いイミド化率と保存安定性という、相反する特性の両立を達成することができ、ひいては耐薬品性の高いものとなる。 (A) Polyimide precursor In the present embodiment, (A) polyimide precursor is a resin component contained in a negative photosensitive resin composition, and is a polyamide having a structure represented by the following general formula (1) .

{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, n ₁ is 2 to 150 and 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 has the following general formula (2):
-R ₃ (2)
(In formula (2), R ₃ is a monovalent organic group having an alkylene oxide group.). } contains precursors represented by
Then, (A) the monovalent organic group represented by the general formula (2) for all of R ₁ and R ₂ of the precursor represented by the general formula (1) contained in the polyimide precursor The percentage exceeds 80%.
(A) In the polyimide precursor, at least one of R ₁ and R ₂ contains a monovalent organic group represented by the general formula (2), and if the proportion exceeds 80%, the reactivity is improved. , the photosensitive resin composition of the present embodiment can achieve both contradictory properties of a high imidization rate and storage stability, and as a result, has high chemical resistance.

In the above general formula (1), X ₁ is not limited as long as it is a tetravalent organic group having 6 to 40 carbon atoms, but from the viewpoint of achieving both heat resistance and photosensitive properties, preferably -COOR ₁ group and --COOR ₂ group and --CONH-- group are aromatic groups or alicyclic-aliphatic groups in the ortho position to each other. Further, the tetravalent organic group represented by X ₁ is more preferably an aromatic ring-containing organic group having 6 to 40 carbon atoms.

More preferably, X ₁ is a tetravalent organic group represented by the following general formula (8).

Moreover, the structure of X ₁ may be one or a combination of two or more.

（式中、Ａは、それぞれ独立に、メチル基（－ＣＨ_３）、エチル基（－Ｃ_２Ｈ_５）、プロピル基（－Ｃ_３Ｈ_７）又はブチル基（－Ｃ_４Ｈ_９）を表す。｝ In general formula (1) above, Y ₁ is not limited as long as it is a divalent organic group having 6 to 40 carbon atoms. It is preferably a cyclic organic group having 1 to 4 aliphatic rings or aliphatic rings, or an aliphatic group or siloxane group having no cyclic structure. More preferably, Y ₁ has a structure represented by the following general formula (9) or (10).

(In the formula, each A independently represents a methyl group (--CH ₃ ), an ethyl group (--C ₂ H ₅ ), a propyl group (--C ₃ H ₇ ) or a butyl group (--C ₄ H ₉ ). .}

Also, the structure of Y ₁ may be one or a combination of two or more.

R ₁ and R ₂ in general formula (1) 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):
-R ₃ (2)
(In formula (2), R ₃ is a monovalent organic group having an alkylene oxide group.).

n in the general formula (1) is not limited as long as it is an integer of 2 to 150, but from the viewpoint of the photosensitive properties and mechanical properties of the photosensitive resin composition, an integer of 3 to 100 is preferable, and an integer of 5 to 70 is more preferred.

｛式（５）中、ｎ_２は、２～１５０の整数であり、Ｒ_４及びＲ_５は、それぞれ独立に、水素原子、又は１価の有機基であり、Ｒ_４及びＲ_５の少なくともいずれかは酸、塩基、またはラジカルの作用により重合可能な基、又は、前記一般式（２）で表される基を含む。｝
で表される前駆体を含むことが好ましい。
（Ａ）ポリイミド前駆体が、一般式（５）で表される前駆体を含むことにより、特に保存安定性とイミド化率（耐薬品性）の効果が高くなる。 Specifically, (A) the polyimide precursor has the following general formula (5):

{In formula (5), n ₂ is an integer of 2 to 150, R ₄ and R ₅ are each independently a hydrogen atom or a monovalent organic group, and at least one of R ₄ and R ₅ or includes a group polymerizable by the action of an acid, a base, or a radical, or a group represented by the general formula (2). }
It is preferable that the precursor represented by is included.
(A) By including the precursor represented by the general formula (5) in the polyimide precursor, the effects of storage stability and imidization rate (chemical resistance) are particularly enhanced.

｛式（６）中、ｎ_１は、２～１５０の整数であり、Ｒ_６及びＲ_７は、それぞれ独立に、水素原子、又は１価の有機基であり、Ｒ_６及びＲ_７の少なくともいずれかは酸、塩基、またはラジカルの作用により重合可能な基、又は、前記一般式（２）で表される基を含む。｝
で表される前駆体を含むことが好ましい。
（Ａ）ポリイミド前駆体が、一般式（５）で表される前駆体に加えて、一般式（５）で表される前駆体を含むことにより、保存安定性とイミド化率（耐薬品性）の効果がさらに高くなる。 Furthermore, (A) the polyimide precursor has the following general formula (6):

{In formula (6), n ₁ is an integer of 2 to 150, R ₆ and R ₇ are each independently a hydrogen atom or a monovalent organic group, and at least one of R ₆ and R ₇ or includes a group polymerizable by the action of an acid, a base, or a radical, or a group represented by the general formula (2). }
It is preferable that the precursor represented by is included.
(A) Polyimide precursor, in addition to the precursor represented by the general formula (5), by containing the precursor represented by the general formula (5), storage stability and imidization rate (chemical resistance ) is more effective.

｛式（７）中、ｎ_２は、２～１５０の整数であり、Ｒ_８及びＲ_９は、それぞれ独立に、水素原子、又は１価の有機基であり、Ｒ_８及びＲ_９の少なくともいずれかは酸、塩基、またはラジカルの作用により重合可能な基、又は、前記一般式（２）で表される基を含む。｝
で表される前駆体を含むことが好ましい。
（Ａ）ポリイミド前駆体が、一般式（５）で表される前駆体に加えて、一般式（７）で表される前駆体を含むことにより、保存安定性とイミド化率（耐薬品性）の効果がさらに高くなる。 Furthermore, (A) the polyimide precursor has the following general formula (7):

{In formula (7), n ₂ is an integer of 2 to 150, R ₈ and R ₉ are each independently a hydrogen atom or a monovalent organic group, and at least one of R ₈ and R ₉ or includes a group polymerizable by the action of an acid, a base, or a radical, or a group represented by the general formula (2). }
It is preferable that the precursor represented by is included.
(A) The polyimide precursor contains a precursor represented by the general formula (7) in addition to the precursor represented by the general formula (5), thereby improving storage stability and imidization rate (chemical resistance ) is more effective.

Furthermore, (A) the polyimide precursor is represented by the general formula (1), and at least one of R ₁ and R ₂ contains a group represented by the general formula (2), and the general formula ( It is preferable to include precursors having double bonds at the ends of R ₁ and R ₂ containing groups represented by 2). By having a double bond at the terminal of R ₃ represented by the general formula (2), a higher effect can be obtained.

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

[(A) Preparation method of polyimide precursor]
The polyimide precursor represented by the general formula (1) in the present embodiment includes, for example, the above-mentioned tetracarboxylic dianhydride containing a tetravalent organic group X ₁ having 6 to 40 carbon atoms, and (a) the above A partially esterified tetracarboxylic acid (hereinafter also referred to as an acid/ester form) is prepared by reacting an alcohol composed of a monovalent organic group represented by the general formula (2) and a hydroxyl group. followed by polycondensation with the aforementioned diamine containing a divalent organic group Y ₁ having 6 to 40 carbon atoms.

(Preparation of acid/ester form)
In the present embodiment, 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 acid dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenylsulfone-3,3' ,4,4′-tetracarboxylic dianhydride, diphenylmethane-3,3′,4,4′-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2, 2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane 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 represented by the general formula (2), such as 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 can be mentioned.

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 preferably 85 mol% or more, preferably 90 mol% or more, of the total content of _R1 and _R2 . Preferably, it is 95 mol % or more.

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 polycondensation product of the acid/ester and diamines, such as N-methyl-2-pyrrolidone, N , N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, gamma-butyrolactone, ketones, esters, lactones, 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)
To the above acid/ester form (typically a solution in the above reaction solvent), under ice cooling, a known dehydration condensation agent such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-Carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate or the like is added and mixed to convert the acid/ester form into a polyanhydride, which is then , Diamines containing a divalent organic group Y ₁ having 6 to 40 carbon atoms separately dissolved or dispersed in a solvent are added dropwise and polycondensed to obtain a polyimide precursor that can be used in the embodiment. can be obtained.

Diamines containing a divalent organic group Y ₁ having 6 to 40 carbon atoms 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-amino phenyl)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-tolysine sulfone, 9,9-bis(4-aminophenyl)fluorene, and hydrogen atoms on their benzene rings. partially substituted with methyl group, ethyl group, hydroxymethyl group, hydroxyethyl group, halogen, etc., such as 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4 ,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenyl phenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof etc., but not limited to these.

In the embodiment, in order to improve the adhesion between the photosensitive resin layer formed on the substrate and various substrates by applying a negative photosensitive resin composition on the substrate, (A) a polyimide precursor Diaminosiloxanes such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane can also be copolymerized during the preparation of .

After the completion of the polycondensation reaction, water-absorbing by-products of the dehydration condensation agent coexisting in the reaction solution are filtered off if necessary, and then a poor solvent such as water, lower aliphatic alcohol, or a mixture thereof is added. , Precipitate the polymer component by putting it into the reaction solution, and repeat re-dissolution, re-precipitation, etc. to purify the polymer, vacuum dry, and polyimide precursor that can be used in the embodiment. Isolate the body. In order to improve the degree of purification, the polymer solution may be passed through a column packed with anion and/or cation exchange resins 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.

(B) Photopolymerization Initiator The (B) photopolymerization initiator in the present embodiment will be described. As the photopolymerization initiator (B), any compound conventionally used as a photopolymerization initiator for UV curing can be selected. For example, (B) photopolymerization initiators include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenylketone, dibenzylketone, and fluorenone; 2,2′-diethoxyacetophenone; , 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenylketone and other acetophenone derivatives; thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone and other thioxanthone derivatives; benzyl, benzyldimethylketal, benzyl- benzyl derivatives such as β-methoxyethyl acetal; benzoin derivatives such as benzoin and benzoin methyl ether; 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione -2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-benzoyl) oximes such as oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime; N such as N-phenylglycine; -arylglycines; peroxides such as benzoyl perchloride; aromatic biimidazoles and the like, but not limited thereto. Moreover, these can be used individually by 1 type or in mixture of 2 or more types. Among the above (B) photopolymerization initiators, oximes are more preferable, particularly in terms of photosensitivity.

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

(C) Compound Containing a Group Polymerizable by the Action of an Acid, a Base, or a Radical The (C) compound containing a group polymerizable by the action of an acid, a base, or a radical in the present embodiment will be described.
In the following description, "a compound containing a group polymerizable by the action of an acid, a base, or a radical" is referred to as a "reactive monomer".
By containing a reactive monomer, the photosensitive resin composition of the present embodiment exhibits enhanced storage stability and imidization rate (chemical resistance).

Such a (C) reactive monomer is not particularly limited, but is preferably a compound having a double bond at at least one terminal, more preferably a compound having double bonds at all terminals.

(C) Reactive monomers include, for example, polyethylene glycol dimethacrylate, ethoxylated bisphenol A dimethacrylate, tricyclodecane dimethanol dimethacrylate, 1,10-decanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1 ,9-nonanediol dimethacrylate, neopentyl glycol dimethacrylate, ethoxylated polypropylene glycol dimethacrylate, glycerine dimethacrylate, polypropylene glycol dimethacrylate, propoxylated ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A diacrylate, 9,9- bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, propoxylated bisphenol A diacrylate, tricyclodecanedimethanol diacrylate, 1,10-decanediol diacrylate, 1,6-hexanediol diacrylate, 1, 9-nonanediol diacrylate, polypropylene glycol diacrylate, polytetramethylene diacrylate, ethoxylated isocyanuric acid triacrylate, ε-caprolactone-modified tris-(2-acryloxyethyl) isocyanenurate, ethoxylated glycerin triacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol polyacrylate, dipentaerythritol hexaacrylate, trimethylolpropane trimethacrylate and mixtures thereof; Examples include, but are not limited to. Among these, polyethylene glycol dimethacrylate is preferred.

Such a (C) reactive monomer reacts there when the (A) polyimide precursor represented by the general formula (1) has a double bond at the end of R ₁ or R ₂ polymerize. Alternatively, (C) the polymerizable groups of the reactive monomer react with each other under the action of an acid, a base, or a radical to polymerize.
(A) Even if the polyimide precursor does not have a double bond at the end of R ₁ or R ₂ in general formula (1), it can be polymerized by light, (C) by the action of an acid, a base, or a radical. Since these groups react with each other and polymerize, photosensitivity can be expressed.

Furthermore, (C) the reactive monomer preferably has an alkylene oxide group.

（式（３）中、Ｒ_４及びＲ_５はそれぞれ独立に炭素数１～６の１価の有機基であり、Ｚ_１及びＺ_２はそれぞれ独立に１価の基であり、複数のＺ_１及びＺ_２はそれぞれ同一でも異なっていてもよく、ｍ_１は２～２００の整数である。）で表される化合物を含むことが好ましい。これにより保存安定性とイミド化率（耐薬品性）の効果が高くなる。
ｍ_１は３以上であってもよく、４以上であってもよく、５以上であってもよく、６以上であってもよく、７以上であってもよく、８以上であってもよく、９以上であってもよく、１０以上であってもよく、１２以上であってもよく、１４以上であってもよい。ｍ_１の上限は１５０以下でもよく、１００以下でもよく、５０以下でも良い。 Specifically, (C) the reactive monomer is
The following general formula (3):

(In formula (3), R ₄ and R ₅ are each independently a monovalent organic group having 1 to 6 carbon atoms, Z ₁ and Z ₂ are each independently a monovalent group, and a plurality of Z ₁ and Z ₂ may be the same or different, and m ₁ is an integer of 2 to 200.). This increases storage stability and imidization rate (chemical resistance).
m ₁ may be 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, or 8 or more , may be 9 or more, 10 or more, 12 or more, or 14 or more. The upper limit of m1 may be ₁₅₀ or less, 100 or less, or 50 or less.

（式（４）中、Ｚ_１及びＺ_２はそれぞれ独立に１価の基であり、複数のＺ_１及びＺ_２はそれぞれ同一でも異なっていてもよく、ｍ_１は２～２００の整数である。）で表される化合物を含むことがより好ましい。これにより保存安定性とイミド化率（耐薬品性）の効果がより高くなる。
ｍ_１は３以上であってもよく、４以上であってもよく、５以上であってもよく、６以上であってもよく、７以上であってもよく、８以上であってもよく、９以上であってもよく、１０以上であってもよく、１２以上であってもよく、１４以上であってもよい。ｍ_１の上限は１５０以下でもよく、１００以下でもよく、５０以下でも良い。 Furthermore, (C) the reactive monomer has the following general formula (4):

(In formula (4), Z ₁ and Z ₂ are each independently a monovalent group, a plurality of Z ₁ and Z ₂ may be the same or different, and m ₁ is an integer of 2 to 200. ) is more preferably included. As a result, the effect of storage stability and imidization rate (chemical resistance) is enhanced.
m ₁ may be 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, or 8 or more , may be 9 or more, 10 or more, 12 or more, or 14 or more. The upper limit of m1 may be ₁₅₀ or less, 100 or less, or 50 or less.

In general formula (3) or (4), the value of m1 (that is, the number of alkylene oxide groups) is preferably from 6 to 25, since a high effect can be obtained. The value of m1 is preferably 7 or more, more preferably 8 or more, more preferably 9 or more, more preferably 10 or more, more preferably 11 or more.
The value of m1 is preferably 24 or less, more preferably 22 or less, more preferably 20 or less, more preferably 18 or less.
Further, in the photosensitive resin composition, the _average value of m1 of all compounds represented by general formula (3) or general formula (4) is preferably 6-25.
_The preferred value for the _average value of m1 is the same as the preferred value for m1.

Other Components In the present embodiment, the negative photosensitive resin composition may further contain components other than the above components (A) to (C). Other components include, for example, a solvent, a resin component other than the (A) polyimide precursor, a sensitizer, a monomer having a photopolymerizable unsaturated bond, an adhesion aid, a thermal polymerization inhibitor, an azole compound, and a hinder. dophenol compounds, organic titanium compounds, and the like.

As the solvent, it is preferable to use a polar organic solvent from the viewpoint of solubility with respect to (A) the polyimide precursor. 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.

Depending on the desired coating film thickness and viscosity of the negative photosensitive resin composition, the solvent is, for example, 30 parts by mass to 1500 parts by mass, preferably 100 parts by mass with respect to 100 parts by mass of the polyimide precursor (A). It can be used in the range of parts by mass to 1000 parts by mass.

Furthermore, solvents containing alcohols are preferable from the viewpoint of improving the storage stability of the negative 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 and ethylene glycol-n-propyl ether; 2-hydroxyisobutyric acid esters; and dialcohols such as ethylene glycol and propylene glycol. 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 that does not have an olefinic double bond, the content of the alcohol that does not have an olefinic double bond in the total solvent is 5% by weight to 50% by weight, based on the weight of the total solvent. % by mass, more 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 negative photosensitive resin composition is improved, while when it is 50% by mass or less, (A ) is preferable because the solubility of the polyimide precursor is improved.

In an embodiment, the negative photosensitive resin composition may further contain a resin component other than the (A) polyimide precursor. 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 parts by mass to 20 parts by mass with respect to 100 parts by mass of the polyimide precursor (A).

In the embodiment, the negative photosensitive resin composition 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, 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 (A) polyimide precursor.

In the embodiment, in order to improve the resolution of the relief pattern, a monomer having a photopolymerizable unsaturated bond can be arbitrarily blended into the negative photosensitive resin composition. 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 tri-acrylates 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 (A) polyimide precursor.

In the embodiment, in order to improve the adhesion between the film formed using the negative photosensitive resin composition and the substrate, an adhesion aid may optionally be blended into the negative photosensitive resin composition. can. 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 promoters, the silane coupling agent is more preferable from the viewpoint of adhesion. 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 (A) polyimide precursor.

In the embodiment, a thermal polymerization inhibitor can be arbitrarily blended in order to improve the stability of the viscosity and photosensitivity of the negative photosensitive resin composition, particularly during storage in the state of a solution containing a solvent. . Thermal polymerization inhibitors include, for example, hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2 , 6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl- N-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 polyimide precursor (A).

For example, when a substrate made of copper or a copper alloy is used, an azole compound can optionally be added to the negative photosensitive resin composition in order to suppress discoloration of the substrate. Azole compounds include, for example, 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl -5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, Hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3, 5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl -2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, Hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5- methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole and the like. Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole and 4-methyl-1H-benzotriazole. In addition, these azole compounds may be used singly or as a mixture of two or more.

The amount of the azole compound compounded is preferably 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, and from the viewpoint of photosensitivity characteristics, it is 0.5 parts by mass to 5 parts by mass. It is more preferable to have When the amount of the azole compound is 0.1 parts by mass or more with respect to 100 parts by mass of the polyimide precursor (A), when the negative photosensitive resin composition is formed on copper or a copper alloy, copper or Discoloration of the copper alloy surface is suppressed, and on the other hand, when the amount is 20 parts by mass or less, the photosensitivity is excellent, which is preferable.

In embodiments, a hindered phenolic compound can optionally be incorporated into the negative-acting photosensitive resin composition to inhibit 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-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2 -methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy -2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6 -diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl -3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3 -hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5 -ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione and the like, but are not limited thereto. . 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 is preferably 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, and from the viewpoint of photosensitivity characteristics, 0.5 parts by mass to 10 parts by mass. Part is more preferred. (A) When the amount of the hindered phenol compound per 100 parts by mass of the polyimide precursor 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 Alternatively, discoloration and corrosion of the copper alloy can be prevented, and on the other hand, when the amount is 20 parts by mass or less, the photosensitivity is excellent, which is preferable.

In embodiments, the negative photosensitive resin composition may contain an organotitanium 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 of about 250°C.

Organotitanium compounds that can be used include, for example, those in which organic chemicals are bound to titanium atoms via covalent or ionic bonds.

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(η ⁵ -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η ⁵ - 2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium;

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(η ⁵ -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-( 1H-pyrrol-1-yl)phenyl)titanium is preferred.

When the organic titanium compound is blended, the blending amount is preferably 0.05 parts by mass to 10 parts by mass, more preferably 0.1 part by mass to 2 parts by mass, relative to 100 parts by mass of the resin (A). more preferred. When the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited.

In the present embodiment, it is possible to realize a negative photosensitive resin composition that has a high imidization rate even if the imidization accelerator (a compound that exhibits basicity) is small, and that has both storage stability and chemical resistance.
Specifically, in the negative photosensitive resin composition of the present embodiment, when the total solid content contained in the negative photosensitive resin composition is 100 parts by mass, is preferably 10 parts by mass or less, more preferably 5 parts by mass or less.

The negative photosensitive resin composition according to this embodiment contains a polyimide precursor, a photopolymerization initiator, and a solvent.
Then, the photosensitive resin composition according to the present embodiment has a viscosity change rate of 5% compared to the initial time when the resin composition is stored at a temperature of 23 ° C. and a humidity of 50% Rh for 4 weeks. within.
Furthermore, the photosensitive resin composition according to the present embodiment has an imidization rate of 70% or more when a cured coating film is obtained by heating the resin composition at 180° C. for 2 hours. It is preferable that the cured coating film has an imidization ratio of 85% or more.
As described above, the negative photosensitive resin composition according to the present embodiment has a high imidization rate and achieves both storage stability and chemical resistance.

Method for Producing Hardened Relief Patterns In an embodiment, the steps (1)-(4) are as follows:
(1) a step of applying the negative photosensitive resin composition of the embodiment 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 the negative photosensitive resin composition of the embodiment onto a substrate to form a photosensitive resin layer on the substrate. In this step, the negative photosensitive resin composition of the embodiment is applied. It is applied onto a substrate and, if necessary, dried afterwards to form a photosensitive resin layer. As the coating method, a method conventionally used for coating a photosensitive resin composition, for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, or the like, or a method of spray coating with a spray coater. method etc. can be used.

If necessary, the coating film composed of the negative photosensitive resin composition can be dried, and drying methods include, for example, air drying, heat drying using an oven or hot plate, vacuum drying, and the like. 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 In an embodiment, there is also provided a semiconductor device comprising a cured relief pattern obtained by the method of manufacturing a cured 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 invention 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 invention 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 method for producing a cured relief pattern 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 According to an embodiment, there is provided a display device comprising a display element and a cured film provided on the display element, wherein the cured film is the cured relief pattern described above. be done. 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 type photosensitive resin composition of the present invention is applied to the semiconductor device as described above, and is also used for interlayer insulation of multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, liquid crystal alignment films, and the like. is also useful.

EXAMPLES Hereinafter, the present embodiment will be specifically described with reference to Examples, but the present embodiment 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.

(1) Weight Average Molecular Weight The weight average molecular weight (Mw) of each polyimide precursor was measured by gel permeation chromatography (converted to standard polystyrene). The column used for the measurement is Shodex 805M/806M series manufactured by Showa Denko Co., Ltd. The standard monodisperse polystyrene is Shodex STANDARD SM-105 manufactured by Showa Denko Co., Ltd. The developing solvent is N-methyl-2- pyrrolidone, and the detector used was Shodex RI-930 manufactured by Showa Denko.
(2) Storage stability test of resin composition After preparing the photosensitive resin composition, the initial state was stirred for 3 days at room temperature (23.0 ° C. ± 0.5 ° C., relative humidity 50% ± 10%), After that, the viscosity change rate of the resin composition was measured when it was allowed to stand at room temperature for 4 weeks. Viscosity was measured at 23.0° C. using an E-type viscometer (RE-80R, manufactured by Toki Sangyo Co., Ltd.). As the evaluation results, those with a viscosity change rate of 5% or less were evaluated as "good", and those with a viscosity change rate exceeding 5% or gelling of the resin composition that could not be measured were evaluated as "bad".

(3) Measurement of imidization rate of cured polyimide coating film On a 6-inch silicon wafer (manufactured by Fujimi Denshi Kogyo Co., Ltd., thickness 625 ± 25 µm), a photosensitive resin composition is applied so that the film thickness after curing is about 10 µm. It is spin-coated, pre-baked on a hot plate at 100° C. for 180 seconds, exposed to ghi radiation with an exposure dose of 600 mJ/cm ² using an aligner (PLA-501F, manufactured by Canon), and then programmed to heat and cured in a curing oven. (VF-2000, manufactured by Koyo Lindbergh Co., Ltd.) and heated at 180° C. or 390° C. for 2 hours in a nitrogen atmosphere to obtain a cured polyimide coating film. The obtained cured polyimide coating film was measured using a Si prism with an ATR-FTIR measurement device (Nicolet Continuum, manufactured by Thermo Fisher Scientific), and the value obtained by dividing the peak intensity at 1380 cm ^-1 by the peak intensity at 1500 cm ^-1 is the imidization index, and the value obtained by dividing the imidization index of the film cured at 180°C by the imidization index of the film cured at 390°C was calculated as the imidization rate.
(4) 5% Weight Loss Temperature Measurement of Cured Polyimide Coating On a 6-inch silicon wafer, the photosensitive resin composition was spin-coated so that the film thickness after curing was about 10 μm, and hot plated at 100 ° C. for 180 seconds. After pre-baking at , using a temperature-rising programmable curing furnace (Model VF-2000, manufactured by Koyo Lindbergh Co., Ltd.), heating was performed at 180° C. for 2 hours in a nitrogen atmosphere to obtain a cured polyimide coating film. The film thickness was measured with a film thickness measuring device, Lambda Ace (manufactured by Dainippon Screen Co., Ltd.). The obtained polyimide coating film was scraped off, and the weight of the film when it reached 180 ° C. when the temperature was raised from room temperature at 10 ° C./min using a thermogravimetric measurement device (manufactured by Shimadzu Corporation, TGA-50). The temperature at which the weight decreases by 5% (5% weight loss temperature) was measured as 100%.

(5) Evaluation of chemical resistance of cured relief pattern (polyimide coating film) On a 6-inch silicon wafer, the photosensitive resin composition was spin-coated so that the film thickness after curing was about 5 μm, and was heated at 100° C. for 180 seconds. Pre-baking was performed on a hot plate to form a coating film. This coating film was exposed to i-rays at an exposure dose of 300 mJ/cm ² using a stepper NSR2005i8A (manufactured by Nikon Corporation) having an exposure wavelength of i-rays (365 nm) through a reticle with a test pattern. Next, in a developing machine D-SPIN (manufactured by SOKUDO Co., Ltd.), using cyclopentanone as a developer at 23° C., the time until the unexposed area completely dissolves and disappears is multiplied by 1.4. It was subjected to rotary spray development, followed by rotary spray rinsing with propylene glycol monomethyl ether acetate for 10 seconds to obtain a relief pattern consisting of a resin film. Subsequently, curing was performed in a nitrogen atmosphere at 180° C. for 2 hours in a vertical curing furnace VF200B (manufactured by Koyo Thermo Systems Co., Ltd.) to obtain a cured relief pattern. These cured relief patterns were obtained by heating a resist stripping film {manufactured by ATMI, product name ST-44, main components being 2-(2-aminoethoxy)ethanol and 1-cyclohexyl-2-pyrrolidone} to 50°C. Soak for 5 minutes, rinse with running water for 1 minute, and air dry. After that, the film surface was visually observed with an optical microscope, and chemical resistance was evaluated based on the presence or absence of damage due to the chemical solution such as cracks and the rate of change in the film thickness after the chemical solution treatment. As evaluation criteria, no cracks or the like occur and the film thickness change rate is within 5% based on the film thickness before immersion in the chemical. Those in which cracks occurred or those in which the film thickness change rate exceeded 15% were evaluated as "failed".

(6) Evaluation of Cu void area after high temperature storage of cured relief pattern on Cu On a 6-inch silicon wafer, a sputtering device (L-440S-FHL type, manufactured by Canon Anelva Co., Ltd.) was used to obtain a thickness of 200 nm. of Ti and 400 nm thick Cu were sputtered in this order. Subsequently, a photosensitive resin composition prepared by the method described below is spin-coated on the wafer using a coater/developer (D-Spin60A type, manufactured by SOKUDO) and dried to form a coating film having a thickness of 10 μm. did. 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 is spray-developed with a coater developer (D-Spin60A type, manufactured by SOKUDO) using cyclopentanone as a developer, and rinsed with propylene glycol methyl ether acetate to form a relief pattern on Cu. Obtained.

The wafer on which the relief pattern is formed on Cu is heated in a nitrogen atmosphere at 180 ° C. for 2 hours using a temperature-rising programmable curing furnace (VF-2000, manufactured by Koyo Lindbergh Co., Ltd.). A hardened relief pattern consisting of resin about 6-7 μm thick was obtained.

The wafer having the cured relief pattern formed on Cu was heated in air at 150° C. for 168 hours using a temperature-rising programmable curing furnace (Model VF-2000, manufactured by Koyo Lindbergh Co., Ltd.). Subsequently, the entire resin layer on the Cu was removed by plasma etching using a plasma surface treatment apparatus (EXAM type, manufactured by Shinko Seiki Co., Ltd.). The plasma etching conditions are as follows.
Output: 133W
Gas type/flow rate: O ₂ : 40 ml/min + CF ₄ : 1 ml/min Gas pressure: 50 Pa
Mode: Hard mode Etching time: 1800 seconds

The Cu surface from which the resin layer has been completely removed is observed by FE-SEM (S-4800 type, manufactured by Hitachi High-Technologies Corporation), and image analysis software (Azo-kun, manufactured by Asahi Kasei Corporation) is used to determine the surface of the Cu layer. The area of voids occupied was calculated. When the total area of voids when evaluating the photosensitive resin composition described in Comparative Example 1 is 100%, the total area ratio of voids of less than 50% is "best", 50% or more and less than 75% Those of 75% or more and less than 100% were judged to be "good", those of 100% or more were judged to be "poor".

<Production Example 1> (Synthesis of polymer A as (A) resin)
3,3′,4,4′-Biphenyltetracarboxylic dianhydride (BPDA) 147 g (0.5 mol) was placed in a 2-liter separable flask, and triethylene glycol monomethyl ether 164 g (1 mol) and γ-butyrolactone were added. 400 ml of the solution was added and stirred at room temperature, 79.1 g of pyridine was added while stirring, and then the temperature of the reaction solution was raised in an oil bath and stirred at 60°C for 4 hours to obtain a reaction mixture. After that, it was allowed to cool to room temperature and allowed to stand for 16 hours.

Next, under ice cooling, a solution of 206 g of dicyclohexylcarbodiimide (DCC) dissolved in 200 ml of γ-butyrolactone was added to the reaction mixture with stirring over 40 minutes, followed by 48.7 g (0.45 mol) of p-phenylenediamine. suspended in 250 ml of γ-butyrolactone was added with stirring over 60 minutes. After further stirring at room temperature for 2 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 resulting precipitate was separated by filtration and vacuum dried to obtain a powdery polymer (polymer A). When the molecular weight of polymer A was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 33,000.

<Production Example 2> (Synthesis of polymer B as (A) resin)
Instead of 164 g of triethylene glycol monomethyl ether in Production Example 1, 19.5 g (0.15 mol) of 2-hydroxyethyl methacrylate (HEMA) and 140 g (0.85 mol) of triethylene glycol monomethyl ether were used, respectively. Polymer B was obtained by carrying out the reaction in the same manner as in Production Example 1. When the molecular weight of polymer B was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 32,000.

<Production Example 3> (Synthesis of polymer C as (A) resin)
Same as the method described in Production Example 1 above, except that 173 g of Blemmer PE-90 (manufactured by NOF Corporation) (hydroxyl value: 325 mg KOH / g) was used instead of 164 g of triethylene glycol monomethyl ether in Production Example 1. Then, the reaction was carried out to obtain Polymer C. When the molecular weight of Polymer C was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 34,000.

<Production Example 4> (Synthesis of polymer D as (A) resin)
Same as the method described in Production Example 1 above, except that 294 g of Blemmer PE-200 (manufactured by NOF Corporation) (hydroxyl value: 191 mg KOH / g) was used instead of 164 g of triethylene glycol monomethyl ether in Production Example 1. Then, the reaction was carried out to obtain a polymer D. When the molecular weight of polymer D was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 38,000.

<Production Example 5> (Synthesis of polymer E as (A) resin)
Same as the method described in Production Example 1 above, except that 452 g of Blemmer PE-350 (manufactured by NOF Corporation) (hydroxyl value: 124 mg KOH / g) was used instead of 164 g of triethylene glycol monomethyl ether in Production Example 1. Then, the reaction was carried out to obtain a polymer E. When the molecular weight of Polymer E was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 48,000.

<Production Example 6> (Synthesis of polymer F as (A) resin)
Except for using 66.7 g (0.333 mol) of ODA in place of 90.1 g (0.45 mol) of ODA in Production Example 5, the reaction was carried out in the same manner as in Production Example 5 to obtain polymer F. rice field. When the molecular weight of polymer F was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 9,500.

<Production Example 7> (Synthesis of polymer G as (A) resin)
Except for using 155 g (0.5 mol) of 4,4′-oxydiphthalic dianhydride (ODPA) instead of 147 g of BPDA in Production Example 4, the reaction was carried out in the same manner as in Production Example 4, Polymer G was obtained. When the molecular weight of polymer G was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 36,000.

<Production Example 8> (Synthesis of polymer H as (A) resin)
The method described in Production Example 4 above, except that 155 g (0.5 mol) of ODPA was used instead of 147 g of BPDA in Production Example 4, and 48.7 g (0.45 mol) of p-phenylenediamine was used instead of 90.1 g of ODA. Polymer H was obtained by performing a reaction in the same manner as above. When the molecular weight of Polymer H was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 27,000.
<Production Example 9> (Synthesis of polymer I as (D) resin)
Except for using 130 g (1 mol) of HEMA instead of 164 g of triethylene glycol monomethyl ether in Production Example 7, the reaction was carried out in the same manner as in Production Example 7 to obtain Polymer I. When the molecular weight of polymer I was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 30,000.
<Production Example 10> (Synthesis of Polymer J)
13.0 g (0.1 mol) of 2-hydroxyethyl methacrylate (HEMA) and 49.3 g (0.3 mol) of triethylene glycol monomethyl ether instead of 65.7 g (0.4 mol) of triethylene glycol monomethyl ether in Production Example 1 Polymer J was obtained by carrying out the reaction in the same manner as described in Production Example 1 above, except that each of the above was used. When the molecular weight of Polymer J was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 31,000.

<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) resin), 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime ((B) photopolymerization initiator) 4.0 g, M9G: polyethylene glycol #400 di 20.0 g of methacrylate (NK Ester 9G, Shin-Nakamura Chemical Co., Ltd.) ((C) a compound containing a group polymerizable by the action of an acid, a base, or a radical) was dissolved in 150 g of γ-butyrolactone (hereinafter referred to as GBL). . The viscosity of the resulting solution was adjusted to about 30 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. Table 2 shows the results.

<Examples 2 to 14>
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 1, and the same evaluation as in Example 1 was performed. Table 2 shows the results.

<Comparative Example 1>
A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that the polymer A corresponding to the (A) resin in the present invention was changed to the polymer I, and the same evaluation as in Example 1 was performed. gone. Table 2 shows the results.

<Comparative Example 2>
A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that the polymer A corresponding to the (A) resin in the present invention was changed to the polymer J, and the same evaluation as in Example 1 was performed. gone. Table 2 shows the results.

<Comparative Example 3>
A negative photosensitive resin composition was prepared in the same manner as in Comparative Example 1 except that 4 g of N-phenyldiethanolamine was further added to Comparative Example 1, and the same evaluation as in Comparative Example 1 was performed. Table 2 shows the results.
<Comparative Example 4>
A negative photosensitive resin composition was prepared in the same manner as in Comparative Example 3 except that 10 g of N-phenyldiethanolamine was used instead of 4 g of N-phenyldiethanolamine, and the same evaluation as in Comparative Example 3 was performed. . Table 2 shows the results.

As is clear from Table 2, in the photosensitive resin composition of Example 1, the storage stability test result was "good", the imidization rate was 78%, and the 5% weight loss temperature was 287°C. . The chemical resistance test result was "good". Similarly, all of the photosensitive resin compositions of Examples 2 to 14 had a "good" storage stability, a high imidization rate of 70% or higher, and a 5% weight loss temperature of 274°C or higher. As a result of the chemical resistance test, the occurrence of cracks in the film was suppressed, and the film thickness change rate was low, giving an evaluation of "good" or better. In addition, the void area evaluation was also good at "fair" or higher.
In particular, in the (A) polyimide precursor represented by the general formula (1), Examples 3 and 4 using polymers C and D having a double bond at the end of R ₃ represented by the general formula (2) , 13 and 14 have particularly excellent storage stability _, imidization rate and chemical resistance compared to the examples using polymers A and B having a double bond at the end of R3. Recognize.

On the other hand, in Comparative Example 1, although the storage stability was "good", the imidization rate was 52% and the 5% weight loss temperature was 258°C. As a result of the chemical resistance test, cracks occurred in the film, and the film thickness change rate was 35%, and the evaluation was "improper". Moreover, void area evaluation was "impossible."
In Comparative Example 2, the storage stability was "good", but the imidization rate was 67% and the 5% weight loss temperature was 273°C. As a result of the chemical resistance test, cracks occurred in the film, and the film thickness change rate was 19%, and the evaluation was "improper". Also, the void area evaluation was "good".
In Comparative Example 3, the storage stability was "good", but the imidization rate was 65% and the 5% weight loss temperature was 267°C. As a result of the chemical resistance test, cracks occurred in the film, and the film thickness change rate was 22%, and the evaluation was "improper". Also, the void area evaluation was "good".
In Comparative Example 4, the resin composition gelled after being left to stand for 4 weeks, and the viscosity could not be measured. When another evaluation was performed using a separately prepared photosensitive resin composition, the imidization rate was 72% and the 5% weight loss temperature was 272°C. As a result of the chemical resistance test, no cracks occurred in the film, but the film thickness change rate was 17%, and the evaluation was "improper". Also, the void area evaluation was "good".

Although the embodiment of the present invention has been described above, the present invention is not limited to this, and can be modified as appropriate without departing from the gist of the invention.

By using the negative photosensitive resin composition according to the present invention, it is possible to achieve a high imidization rate while maintaining storage stability, and furthermore, to achieve high chemical resistance, such as semiconductor devices, multilayer wiring boards, etc. It can be suitably used in the field of photosensitive materials useful for the production of electrical and electronic materials.

Claims (13)

(A) a polyimide precursor;
(B) a photoinitiator;
(C) a compound containing a group polymerizable by the action of an acid, base, or radical;
A negative photosensitive resin composition comprising
The (A) polyimide precursor has the following general formula (1):

{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, n ₁ is 2 to 150 and 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 has the following general formula (2):
-R3 ₍ 2)
(In formula (2), R ₃ is a monovalent organic group having an alkylene oxide group.). }, and
of the monovalent organic group represented by the general formula (2) for all of R ₁ and R ₂ of the precursor represented by the general formula (1) contained in the polyimide precursor (A) the proportion exceeds 80 mol%,
The compound (C) containing a group polymerizable by the action of an acid, a base, or a radical has the following general formula (4):

(In formula (4), Z ₁ and Z ₂ are (meth)acrylate groups , a plurality of Z ₁ and Z ₂ may be the same or different, and m ₁ is 6 to 25.) A negative photosensitive resin composition characterized by comprising a compound of 2. The negative photosensitive resin composition according to claim 1, wherein the average value of m ₁ of all the compounds represented by the general formula (4) in the photosensitive resin composition is 6-25. 3. The negative photosensitive resin composition according to claim 1, wherein (C) the compound containing a group polymerizable by the action of an acid, a base, or a radical has a double bond on at least one end. The (A) polyimide precursor has the following general formula (5):

{In formula (5), n ₂ is an integer of 2 to 150, R ₄ and R ₅ are each independently a hydrogen atom or a monovalent organic group, and at least one of R ₄ and R ₅ or includes a group polymerizable by the action of an acid, a base, or a radical, or a group represented by the general formula (2). }
The negative photosensitive resin composition according to any one of claims 1 to 3, comprising a precursor represented by. The (A) polyimide precursor has the following general formula (6):

{In formula (6), n ₁ is an integer of 2 to 150, R ₆ and R ₇ are each independently a hydrogen atom or a monovalent organic group, and at least one of R ₆ and R ₇ or includes a group polymerizable by the action of an acid, a base, or a radical, or a group represented by the general formula (2). }
The negative photosensitive resin composition according to any one of claims 1 to 4, comprising a precursor represented by. The (A) polyimide precursor is
The following general formula (7):

{In formula (7), n ₂ is an integer of 2 to 150, R ₈ and R ₉ are each independently a hydrogen atom or a monovalent organic group, and at least one of R ₈ and R ₉ or includes a group polymerizable by the action of an acid, a base, or a radical, or a group represented by the general formula (2). }
The negative photosensitive resin composition according to any one of claims 1 to 5, comprising a precursor represented by. The (A) polyimide precursor is
represented by the general formula (1), and at least one of the R ₁ and R ₂ contains a group represented by the general formula (2), and
7. The negative photosensitive resin according to any one of claims 1 to 6, comprising a precursor having double bonds at the ends of R ₁ and R ₂ containing the group represented by the general formula (2). Composition. When the total solid content contained in the negative photosensitive resin composition is 100 parts by mass, the amount of the compound exhibiting basicity contained in the negative photosensitive resin composition is 10 parts by mass or less. , The negative photosensitive resin composition according to any one of claims 1 to 7. 9. The negative photosensitive resin composition according to claim 8, wherein the amount of said compound exhibiting basicity contained in said negative photosensitive resin composition is 5 parts by mass or less. The following steps:
(1) a step of applying the photosensitive resin composition according to any one of claims 1 to 9 onto a substrate to form a photosensitive resin layer on the substrate;
(2) exposing the photosensitive resin layer;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a hardened relief pattern, comprising the step of heat-treating the relief pattern to form a hardened relief pattern. A cured relief pattern produced by the method of claim 10. A semiconductor device comprising a semiconductor element and a cured film provided on top of the semiconductor element, wherein the cured film is the cured relief pattern according to claim 11 . 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 according to claim 11 .