JP2021117442A - Photosensitive resin composition - Google Patents

Abstract

To provide a photosensitive resin composition that can produce a resin film having high Tg and thermal weight loss temperature, and excellent chemical resistance, while preventing a decrease in the resolution of a relief pattern.SOLUTION: A photosensitive resin composition contains (A) a polyimide precursor, (B) compound having a hydroxyl group and a polymerizable unsaturated bond, (C) a photosensitizer, (D) a solvent, (E) free chlorine, the amount of the free chlorine being 0.0001-2 ppm relative to the total mass of the photosensitive resin composition.SELECTED DRAWING: None

Description

The present invention relates to a photosensitive resin composition.

Conventionally, a polyimide resin having excellent heat resistance, electrical properties, and mechanical properties has been used as an insulating material for electronic components, a passivation film, a surface protective film, an interlayer insulating film, and the like of a semiconductor device. Among these polyimide resins, those provided in the form of a photosensitive polyimide precursor easily form a heat-resistant relief pattern film by coating, exposing, developing, and thermally imidizing the precursor. be able to.

On the other hand, there are various semiconductor packaging methods in semiconductor devices. As a semiconductor packaging method, a semiconductor packaging method called Fan-Out has become the mainstream in recent years. In a funout type semiconductor package, a chip encapsulant larger than the chip size of the semiconductor chip is formed by covering the semiconductor chip with an encapsulant. Further, a rewiring layer extending to the area of the semiconductor chip and the encapsulant is formed. The rewiring layer is formed with a thin film thickness. Further, since the rewiring layer can be formed up to the area of the sealing material, the number of external connection terminals can be increased.

For example, the following Patent Document 1 is known as a funout type semiconductor device.

Japanese Patent No. 5563814

On the other hand, in recent years, the method of mounting a semiconductor device on a printed wiring board has changed from the viewpoint of improving the degree of integration and the calculation function and reducing the chip size. In a structure such as SiP that can be mounted at a higher density, a structure in which the polyimide film is in direct contact with the solder bump is being used. When forming such a bump structure, the polyimide film is required to have high heat resistance and chemical resistance, and in the case of a resin composition having no heat resistance, it is mounted on a substrate together with a semiconductor chip through a solder reflow process. Occasionally, a cured film with low heat resistance is produced. A cured film having low heat resistance is prone to degassing and shrinkage due to temperature changes, and is prone to cracking and peeling.

More recently, there has been an increasing demand for thermosetting materials (low temperature curing materials) capable of low temperature curing treatment. Phenol resins have been widely developed as low-temperature curing materials for insulating film applications, but it is desirable to use polyimide resins from the viewpoint of chemical resistance and heat resistance. In order to cure a polyimide resin that is usually treated at 300 to 400 ° C. at a low temperature, it is common to use chemical imidization by adding a compound that promotes imidization or a soluble polyimide.

On the other hand, when heat-treated at a low temperature, a large amount of small molecule compounds remain in the cured film and the interaction between the resins is weakened, so that it is difficult to maintain the physical characteristics of the film. In particular, in a heating process such as solder reflow in a processing process of a semiconductor device, cracks and peeling are likely to occur due to degassing and shrinkage.

In order to suppress the peeling of the resin film from the Cu wiring in the reflow process, it is required to raise the glass transition point (Tg) and the weight reduction temperature of the resin film. Since the curing treatment is performed at a temperature lower than the reflow temperature, there is a problem that the Tg becomes lower than the reflow temperature and the low molecular weight compound remains without volatilizing. Tg tends to increase by lowering the molecular weight between the cross-linking points of the cured film, however, the functional group concentration of the radically polymerizable compound generally used in combination with the polyimide precursor in the negative photosensitive resin composition and the functional group concentration. When the addition amount is increased, the resolution of the relief pattern is lowered, so that it is difficult to improve the Tg of the resin film while maintaining the resolution. Further, in order to raise the thermogravimetric reduction temperature of the resin film, it was necessary to completely volatilize or immobilize the small molecule compound in the resin film.

The present invention has been made in view of the above problems, and is capable of producing a photosensitive resin film having a high Tg and thermogravimetric reduction temperature and excellent chemical resistance while suppressing a decrease in the resolution of the relief pattern. One of the purposes is to provide a sex resin composition.

｛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、ｎ１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、又は炭素数１〜４０の１価の有機基である。ただし、Ｒ_１及びＲ_２の少なくとも一方は、下記一般式（２）：

で表される基であり、式（２）中、Ｒ_３、Ｒ_４及びＲ_５は、それぞれ独立に、水素原子又は炭素数１〜３の１価の有機基であり、そしてｍ１は、２〜１０の整数である。｝
［４］
上記（Ａ）ポリイミド前駆体１００質量部に対し、上記（Ｄ）溶剤を１００〜８６０質量部含む、項目１〜３のいずれか１項に記載の感光性樹脂組成物。
［５］
上記（Ｄ）溶剤が、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチル−２−ピロリドン、Ｎ−エチル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド、ジメチルスルホキシド、ジエチレングリコールジメチルエーテル、シクロペンタノン、γ−ブチロラクトン、α−アセチル−γ−ブチロラクトン、テトラメチル尿素、１，３−ジメチル−２−イミダゾリノン、Ｎ−シクロヘキシル−２−ピロリドン、及び２−オクタノンからなる群から選択される一つ又は複数の化合物を含む、項目１〜４のいずれか１項に記載の感光性樹脂組成物。
［６］
上記（Ｂ）ヒドロキシル基及び重合性不飽和結合を有する化合物が、２つ以上の重合性不飽和結合を有する、項目１〜５のいずれか１項に記載の感光性樹脂組成物。
［７］
上記（Ｂ）ヒドロキシル基及び重合性不飽和結合を有する化合物が、エポキシ樹脂と（メタ）アタクリル酸との反応物である、項目１〜５のいずれか１項に記載の感光性樹脂組成物。
［８］
上記（Ｂ）ヒドロキシル基及び重合性不飽和結合を有する化合物が、下記一般式（３）または（４）で表される、項目１〜５のいずれか１項に記載の感光性樹脂組成物。

｛式（３）中、Ｒ_１は、炭素数１〜４０の１価の有機基である。｝

｛式（４）中、Ｒ_２は、炭素数１〜４０の１価の有機基である。｝
［９］
上記（Ｂ）ヒドロキシル基及び重合性不飽和結合を有する化合物が、下記一般式（５）または（６）で表される、項目１〜５のいずれか１項に記載の感光性樹脂組成物。

｛式（５）中、Ｒ_３は、炭素数１〜４０の１価の有機基である。｝

｛式（６）中、Ｒ_４は、炭素数１〜４０の１価の有機基である。｝
［１０］
上記（Ｂ）ヒドロキシル基及び重合性不飽和結合を有する化合物が、下記一般式（７）で表される化合物を含む、項目１〜５のいずれか１項に記載の感光性樹脂組成物。

｛式（７）中、Ｒ₂は、炭素数１〜４０の２価の有機基である。｝
［１１］
上記（Ｂ）ヒドロキシル基及び重合性不飽和結合を有する化合物が、下記一般式（８）で表される化合物を含む、項目１〜５のいずれか１項に記載の感光性樹脂組成物。

｛式（８）中、Ｒ₆は、炭素数１〜４０の２価の有機基である。｝
［１２］
（Ａ）ポリイミド前駆体と、
（Ｂ）ヒドロキシル基及び重合性不飽和結合を有する化合物と、
（Ｃ）感光剤と、
（Ｄ）溶剤と、
（Ｅ）遊離塩素と
を含む感光性樹脂組成物であって、
上記感光性樹脂組成物を、硬化後の膜厚が約１０μｍとなるように回転法で基板上に塗布し、１１０℃で１８０秒間ホットプレートで加熱して硬化させたとき、得られる塗膜に含まれる上記遊離塩素の量が、上記塗膜の全質量を基準として、０．０００１〜５ｐｐｍである、感光性樹脂組成物。
［１３］
（Ｇ）エポキシ樹脂を更に含む、項目１〜１２のいずれか１項に記載の感光性樹脂組成物。
［１４］
上記（Ｇ）エポキシ樹脂の量は、上記（Ａ）ポリイミド前駆体１００質量部に対して０．１〜１０質量部である、項目１３に記載の感光性樹脂組成物。
［１５］
ネガ型感光性樹脂組成物である、項目１〜１４のいずれか１項に記載の感光性樹脂組成物。
［１６］
（Ａ）ポリイミド前駆体と、
（Ｂ）ヒドロキシル基及び複数の重合性不飽和結合を有する化合物と、
（Ｃ）感光剤と、
（Ｄ）溶剤と、
（Ｅ）遊離塩素及び／又は共有結合性塩素と、
を含む感光性樹脂組成物であって、
上記感光性樹脂組成物を調整後、２３℃±０．５℃、相対湿度５０％±１０％で３日静置した際の上記感光性樹脂組成物中の全塩素量が、上記感光性樹脂組成物の全質量を基準として０．０００１〜２５０ｐｐｍである、感光性樹脂組成物。 The present inventors can solve the above-mentioned problems with a resin composition containing a compound having a hydroxyl group and a polymerizable unsaturated bond and free chlorine and / or covalent chlorine adjusted to a specific amount. We have found and completed the present invention. Examples of embodiments of the present invention are listed below.
[1]
(A) Polyimide precursor and
(B) A compound having a hydroxyl group and a polymerizable unsaturated bond,
(C) Photosensitizer and
(D) Solvent and
(E) Free chlorine and
A photosensitive resin composition containing
The photosensitive resin composition has an amount of free chlorine of 0.0001 to 2 ppm based on the total mass of the photosensitive resin composition.
[2]
The photosensitive resin composition according to item 1, wherein the photosensitive agent (C) is a photopolymerization initiator.
[3]
The photosensitive resin composition according to item 1 or 2, wherein the polyimide precursor (A) is 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, and n1 is 2 to 150. It is an integer, and R ₁ and R ₂ are independently hydrogen atoms or monovalent organic groups having 1 to 40 carbon atoms. However, _{at least one of R 1} and R ₂ has the following general formula (2):

In formula (2), R ₃ , R ₄ and R ₅ are independently hydrogen atoms or monovalent organic groups having 1 to 3 carbon atoms, and m1 is 2 It is an integer of -10. }
[4]
The photosensitive resin composition according to any one of items 1 to 3, which contains 100 to 860 parts by mass of the solvent (D) with respect to 100 parts by mass of the polyimide precursor (A).
[5]
The solvent (D) is N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone. , Α-Acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, and one or more compounds selected from the group consisting of 2-octanone. The photosensitive resin composition according to any one of items 1 to 4, which comprises.
[6]
The photosensitive resin composition according to any one of Items 1 to 5, wherein the compound having the hydroxyl group and the polymerizable unsaturated bond (B) has two or more polymerizable unsaturated bonds.
[7]
The photosensitive resin composition according to any one of Items 1 to 5, wherein the compound having the hydroxyl group and the polymerizable unsaturated bond (B) is a reaction product of an epoxy resin and (meth) atacryllic acid.
[8]
The photosensitive resin composition according to any one of items 1 to 5, wherein the compound (B) having a hydroxyl group and a polymerizable unsaturated bond is represented by the following general formula (3) or (4).

{In formula (3), R ₁ is a monovalent organic group having 1 to 40 carbon atoms. }

{In formula (4), R ₂ is a monovalent organic group having 1 to 40 carbon atoms. }
[9]
The photosensitive resin composition according to any one of items 1 to 5, wherein the compound (B) having a hydroxyl group and a polymerizable unsaturated bond is represented by the following general formula (5) or (6).

{In formula (5), R ₃ is a monovalent organic group having 1 to 40 carbon atoms. }

{Wherein (6), _{R 4} is a monovalent organic group having 1 to 40 carbon atoms. }
[10]
The photosensitive resin composition according to any one of Items 1 to 5, wherein the compound having a hydroxyl group and a polymerizable unsaturated bond (B) contains a compound represented by the following general formula (7).

{In formula (7), R ₂ is a divalent organic group having 1 to 40 carbon atoms. }
[11]
The photosensitive resin composition according to any one of Items 1 to 5, wherein the compound having a hydroxyl group and a polymerizable unsaturated bond (B) contains a compound represented by the following general formula (8).

{In formula (8), R ₆ is a divalent organic group having 1 to 40 carbon atoms. }
[12]
(A) Polyimide precursor and
(B) A compound having a hydroxyl group and a polymerizable unsaturated bond,
(C) Photosensitizer and
(D) Solvent and
(E) A photosensitive resin composition containing free chlorine.
The above-mentioned photosensitive resin composition is applied onto a substrate by a rotation method so that the film thickness after curing is about 10 μm, and is heated at 110 ° C. for 180 seconds on a hot plate to be cured. A photosensitive resin composition in which the amount of free chlorine contained is 0.0001 to 5 ppm based on the total mass of the coating film.
[13]
(G) The photosensitive resin composition according to any one of items 1 to 12, further comprising an epoxy resin.
[14]
The photosensitive resin composition according to item 13, wherein the amount of the (G) epoxy resin is 0.1 to 10 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.
[15]
The photosensitive resin composition according to any one of items 1 to 14, which is a negative type photosensitive resin composition.
[16]
(A) Polyimide precursor and
(B) A compound having a hydroxyl group and a plurality of polymerizable unsaturated bonds,
(C) Photosensitizer and
(D) Solvent and
(E) Free chlorine and / or covalent chlorine,
A photosensitive resin composition containing
After adjusting the photosensitive resin composition, the total amount of chlorine in the photosensitive resin composition when left to stand at 23 ° C. ± 0.5 ° C. and a relative humidity of 50% ± 10% for 3 days is the photosensitive resin. A photosensitive resin composition which is 0.0001 to 250 ppm based on the total mass of the composition.

According to the present invention, there is provided a photosensitive resin composition capable of producing a resin film having high glass transition temperature and thermogravimetric reduction temperature and excellent chemical resistance while maintaining the resolution of the formed relief pattern. can do. In one embodiment, the crosslink density of the polymer in the resin can be improved after the relief pattern is formed, and the glass transition temperature of the cured film tends to increase while maintaining the resolution. Further, in one embodiment, the low boiling point compound in the membrane can be immobilized by a reaction, and the thermogravimetric reduction temperature can be improved. Furthermore, in one embodiment, the high crosslink density and the specific amount of free chlorine prevent the chemical solution from entering the cured film, so that the chemical resistance of the relief pattern can be improved.

Hereinafter, embodiments for carrying out the present invention (hereinafter, abbreviated as “embodiments”) will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof. Throughout the present specification, when a plurality of structures represented by the same reference numerals in the general formula are present in a molecule, they are independently selected unless otherwise specified, and may be the same or different from each other. Further, the structures represented by the common reference numerals in different general formulas are also independently selected unless otherwise specified, and may be the same or different from each other.

[Photosensitive resin composition]
The photosensitive resin composition of the present embodiment contains (A) a polyimide precursor, (B) a compound having a hydroxyl group and a polymerizable unsaturated bond, (C) a photosensitizer, (D) a solvent, and (E). ) Contains certain amounts of free chlorine and / or covalent chlorine. If desired, the photosensitive resin composition comprises other components. Each component will be described below in order.

The photosensitive resin composition may be either a negative type or a positive type depending on the desired use, and is preferably a negative type from the viewpoint of the physical properties of the (A) polyimide precursor described later.

｛式（１）中、Ｘ₁は、炭素数６〜４０の４価の有機基であり、Ｙ₁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、又は炭素数１〜４０の１価の有機基である。ただし、Ｒ_１及びＲ_２の少なくともいずれかは、下記一般式（２）：

で表される基であり、式（２）中、Ｒ_３、Ｒ_４及びＲ_５は、それぞれ独立に、水素原子又は炭素数１〜３の１価の有機基であり、そしてｍ_１は２〜１０の整数である。} (A) Polyimide precursor In the present embodiment, the (A) polyimide precursor is a resin component contained in the photosensitive resin composition and is a polyamide having a structural unit represented by the following general formula (1). Is preferable.

{In formula (1), X ₁ is a tetravalent organic group _{having 6 to 40 carbon atoms, Y 1} is a divalent organic group having 6 to 40 carbon atoms, and n ₁ is 2 to 150. R ₁ and R ₂ are independently hydrogen atoms or monovalent organic groups having 1 to 40 carbon atoms. However, _{at least one of R 1} and R ₂ is the following general formula (2):

In formula (2), R ₃ , R ₄ and R ₅ are independently hydrogen atoms or monovalent organic groups having 1 to 3 carbon atoms, and m ₁ is 2. It is an integer of -10. }

(A) The ratio of the monovalent organic group represented by the general formula (2) to all _{of R 1} and R ₂ of the precursor represented by the general formula (1) contained in the polyimide precursor is From the viewpoint of high resolution, 50 mol% to 100 mol% is preferable, and from the viewpoint of high chemical resistance and sensitivity, 75 mol% to 100 mol% is more preferable.

N1 in the general formula (1) is preferably an integer of 3 to 100, more preferably an integer of 5 to 70, from the viewpoint of the photosensitive characteristics and mechanical characteristics of the photosensitive resin composition.

｛式（２０）中、Ｒ６は水素原子、フッ素原子、Ｃ１〜Ｃ１０の炭化水素基、及びＣ１〜Ｃ１０の含フッ素炭化水素基から成る群から選ばれる１価の基であり、ｌは０〜２から選ばれる整数であり、ｍは０〜３から選ばれる整数であり、そしてｎは０〜４から選ばれる整数である。｝
で表される構造を有する基が挙げられるが、これらに限定されるものではない。また、Ｘ_１の構造は１種でも２種以上の組み合わせでもよい。上記式（２０）で表される構造を有するＸ_１基は、耐熱性と感光特性とを両立するという点で特に好ましい。 In the above general formula (1), the _{tetravalent organic group represented by X 1} is preferably an organic group having 6 to 40 carbon atoms, and more preferably, in terms of achieving both heat resistance and photosensitive characteristics. , -COOR ₁ group and -COOR ₂ group and -CONH- group are aromatic groups or alicyclic aliphatic groups in which the ortho positions are located with each other. As the _{tetravalent organic group represented by X 1} , specifically, an organic group having 6 to 40 carbon atoms containing an aromatic ring, for example, the following general formula (20):

{In formula (20), R6 is a monovalent group selected from the group consisting of hydrogen atoms, fluorine atoms, hydrocarbon groups C1 to C10, and fluorine-containing hydrocarbon groups C1 to C10, and l is 0 to 0. It is an integer chosen from 2, m is an integer chosen from 0 to 3, and n is an integer chosen from 0 to 4. }
Examples thereof include, but are not limited to, groups having a structure represented by. Further, _{the structure of X 1} may be one kind or a combination of two or more kinds. X ₁ group having the structure represented by the above formula (20) are particularly preferred in that they both the photosensitive characteristic heat resistance.

｛式（２１）中、Ｒ６は水素原子、フッ素原子、Ｃ１〜Ｃ１０の炭化水素基、及びＣ１〜Ｃ１０の含フッ素炭化水素基から成る群から選ばれる１価の基であり、そしてｎは０〜４から選ばれる整数である。｝
で表される構造が挙げられるが、これらに限定されるものではない。また、Ｙ_１の構造は１種でも２種以上の組み合わせでもよい。上記式（２１）で表される構造を有するＹ_１基は、耐熱性及び感光特性を両立するという点で特に好ましい。 In the general formula (1), the divalent organic group represented by Y ₁ in that they both heat resistance and sensitivity characteristics, is preferably an aromatic group having 6 to 40 carbon atoms, for example, The following formula (21):

{In formula (21), R6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group of C1 to C10, and a fluorine-containing hydrocarbon group of C1 to C10, and n is 0. It is an integer selected from ~ 4. }
The structure represented by is mentioned, but is not limited to these. Further, _{the structure of Y 1} may be one kind or a combination of two or more kinds. _One Y group having a structure represented by the above formula (21) is particularly preferable in that it has both heat resistance and photosensitive characteristics.

で表される構造は、低温加熱時のイミド化率、脱ガス性、銅密着性、及び耐薬品性の観点から好ましい。 The Y ₁ group, among other structure represented by the above formula (21), the following equation:

The structure represented by is preferable from the viewpoint of imidization rate at low temperature heating, degassing property, copper adhesion, and chemical resistance.

_{R 3} in the general formula (2) is preferably a hydrogen atom or a methyl group, and R ₄ and R ₅ are preferably hydrogen atoms from the viewpoint of photosensitive characteristics. Further, m ₁ is an integer of 2 or more and 10 or less, preferably an integer of 2 or more and 4 or less from the viewpoint of photosensitive characteristics.

｛式（９）中、Ｒ_１、Ｒ_２、及びｎ_１は上記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を含むことが好ましい。 In one embodiment, the (A) polyimide precursor is represented by the following general formula (9):

{In equation (9), R ₁ , R ₂ , and n ₁ are defined above. }
It is preferable to contain a polyimide precursor having a structural unit represented by.

In the general formula (9), _{it is more preferable that at least one of R 1} and R ₂ is a monovalent organic group represented by the general formula (2).

｛式（１０）中、Ｒ_１、Ｒ_２、及びｎ_１は上記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を含むことが好ましい。 In one embodiment, the (A) polyimide precursor is represented by the following general formula (10):

{In equation (10), R ₁ , R ₂ , and n ₁ are defined above. }
It is preferable to include a polyimide precursor having a structural unit represented by.

In the general formula (10), _{it is more preferable that at least one of R 1} and R ₂ is a monovalent organic group represented by the general formula (2).

(A) a polyimide precursor containing a structure represented by the general formula (1) in the preparation method embodiment of the polyimide precursor, for example, a tetravalent organic group X ₁ of the above-mentioned carbon number 6 to 40 Tetracarboxylic acid dianhydride, (a) alcohols having a structure in which a monovalent organic group represented by the above general formula (2) and a hydroxyl group are bonded, and optionally (b) the above general formula (2). To prepare a partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid / ester form) by reacting with an alcohol having a structure other than the group represented by (hereinafter, also referred to as an acid / ester form); subsequently, the obtained acid and / esters, obtainable by a method comprising the the polycondensation of a diamine containing organic group Y ₁ of the divalent aforementioned carbon atoms 6-40.

(Preparation of acid / ester)
In the present embodiment, the _{tetracarboxylic acid dianhydride containing a tetravalent organic group X 1} having 6 to 40 carbon atoms includes, for example, pyromellitic anhydride, diphenyl ether-3,3', 4,4'-tetracarboxylic. Acid dianhydride, benzophenone-3,3', 4,4'-tetracarboxylic acid dianhydride, biphenyl-3,3', 4,4'-tetracarboxylic acid dianhydride, diphenylsulfone-3,3' , 4,4'-tetracarboxylic acid dianhydride, diphenylmethane-3,3', 4,4'-tetracarboxylic acid 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. In addition, these can be used alone or in combination of two or more.

(B) Examples of alcohols having a structure other than the group represented by the general formula (2) include aliphatic alcohols having 5 to 30 carbon atoms or aromatic alcohols having 6 to 30 carbon atoms, for example, 1-pen. Tanol, 2-pentanol, 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, Examples thereof include triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, and benzyl alcohol.

The content of the organic group of the general formula (2) in the polyimide precursor is preferably 50 mol% or more with respect to all the contents of _{R 1} , R ₂ , R ₆ and R _7. When the content of the organic group of the general formula (2) exceeds 50 mol%, desired photosensitive characteristics can be obtained, which is preferable.
The content of the organic group of the general formula (2) in the photosensitive resin composition is preferably 75 mol% or more with _{respect to all the contents of R 1} , R ₂ , R ₆ and R _7.

By dissolving and mixing the above-mentioned tetracarboxylic dianhydride and the above-mentioned alcohols (a) in a reaction solvent in the presence of a basic catalyst such as pyridine, a half-esterification reaction of the acid dianhydride can be carried out. It can proceed and the desired acid / ester form can be obtained. The reaction conditions are preferably stirring at a reaction temperature of 20 to 50 ° C. for 4 to 10 hours.

As the reaction solvent, those that dissolve the acid / ester and the polyimide precursor which is a polycondensation product of the acid / ester and diamines are preferable. Reaction solvents include, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, gamma butyrolactone, ketones, esters, lactones, ethers, etc. 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, Examples thereof include 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene and xylene. These may be used alone or in combination of two or more, if necessary.

(Preparation of polyimide precursor)
The acid / ester compound (typically the solution in the reaction solvent) is mixed with a known dehydration condensate agent under ice-cooling to obtain an acid / ester compound as a polyacid anhydride, and then the acid / ester compound has a carbon number of carbon atoms. A polyimide precursor can be obtained by dropping and adding a diamine containing 6 to 40 divalent organic groups Y _{1 separately dissolved or dispersed in a solvent and polycondensing it.} Examples of the dehydration condensing agent include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N'. -Discusin imidyl carbonate and the like can be mentioned.

_{Examples of diamines containing a divalent organic group Y 1} having 6 to 40 carbon atoms include p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and 3,3. ′ -Diaminodiphenyl ether, 4,4′-diaminodiphenylsulfide, 3,4′-diaminodiphenylsulfide, 3,3′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 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-trizine sulfone, 9,9-bis (4-aminophenyl) fluorene, and hydrogen atoms on these benzene rings. Partially substituted with methyl group, ethyl group, hydroxymethyl group, hydroxyethyl group, halogen, etc., for example, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4 , 4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenyl Enylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethitoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and these. Mixtures and the like can also be mentioned. However, diamines are not limited to these.

In order to improve the adhesion between the photosensitive resin layer formed on the substrate and various substrates by applying the photosensitive resin composition of the present embodiment on the substrate, (A) at the time of preparing the polyimide precursor. , 1,3-Bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (3-aminopropyl) tetraphenyldisiloxane and other diaminosiloxanes can also be copolymerized.

After completion of the polycondensation reaction, the water-absorbing by-products of the dehydration condensate coexisting in the reaction solution are filtered out as necessary, and then a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is added. , The polymer component may be precipitated by adding it to the reaction solution. Further, the polymer may be purified by repeating the above-mentioned redissolution and reprecipitation operations. Then, the polymer can be vacuum dried to isolate the polyimide precursor. In order to improve the degree of purification, a solution of this polymer may be passed through a column filled with anions and / or cation exchange resins swollen with an appropriate organic solvent to remove ionic impurities.

The molecular weight of the (A) polyimide precursor is preferably 8,000 to 150,000, preferably 9,000 to 50,000, as measured by the polystyrene-equivalent weight average molecular weight by gel permeation chromatography. Is more preferable, and 18,000 to 40,000 is particularly preferable. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, which is preferable. On the other hand, when the weight average molecular weight is 150,000 or less, the dispersibility in the developing solution and the resolution performance of the relief pattern are good. It is preferable because it is good. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The molecular weight is obtained from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from Showa Denko's organic solvent-based standard sample STANDARD SM-105.

｛上記式（３）〜（６）中、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４は、炭素数１〜４０の１価の有機基である。｝ (B) Compound having a hydroxyl group and a polymerizable unsaturated bond In this embodiment, (B) a compound having a hydroxyl group and a polymerizable unsaturated bond (hereinafter, also simply referred to as “(B) compound”) will be described. .. The compound (B) has at least one hydroxyl group and at least one polymerizable unsaturated bond in the molecule. The polymerizable unsaturated bond is not limited as long as it is a radically polymerizable functional group, and examples thereof include an acrylic group, a methacrylic group, an acryloyloxy group, a methacryloyloxy group, a vinyl group, and an allyl group, and an acryloyloxy group. Alternatively, a methacryloyloxy group (referred to as "(meth) acryloyloxy group" in the present specification) is preferable. Examples of the compound (B) having a (meth) acryloyloxy group as a polymerizable unsaturated bond include acrylic acid or a reaction product of a methacrylic acid group (referred to as “(meth) acrylic acid” in the present specification) and an epoxy resin. Alternatively, it may be a reaction product of (meth) acrylic acid and a ring-opening body of an epoxy resin. Among them, from the viewpoint of chemical resistance and thermal physical characteristics, a reaction product of (meth) acrylic acid and an epoxy resin represented by the following general formulas (3) to (6), or a ring-opening of (meth) acrylic acid and an epoxy resin. A reactant with the ring is preferred.

{In the above formulas (3) to (6), R ₁ , R ₂ , R ₃ and R ₄ are monovalent organic groups having 1 to 40 carbon atoms. }

｛上記一般式中、Ｒ₂、Ｒ_３は、炭素数１〜４０の２価の有機基である。｝
で表される化合物が挙げられる。 The compound (B) may have one, two or more, or three or more polymerizable unsaturated bonds in the same molecule. When there are two polymerizable unsaturated bonds, the following general formula:

{In the above general formula, R ₂ and R ₃ are divalent organic groups having 1 to 40 carbon atoms. }
Examples thereof include compounds represented by.

More specifically, the compound (B) having two polymerizable unsaturated bonds includes, but is not limited to, the following compound group:

｛上記式中、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４は、それぞれ独立して、炭素数１〜４０の２価の有機基である。｝で表される化合物が挙げられる。これらの中でも、下記一般式：

｛上記式（８）中、Ｒ_６は、炭素数１〜４０の２価の有機基である。｝で表される化合物が好ましい。 The compound (B) having two or more polymerizable unsaturated bonds can be produced by reacting (meth) acrylic acid with a bifunctional or higher functional epoxy resin. In that case, a compound having a monofunctional or higher functional oxacycloopropyl group may be produced as a reaction impurity. The reaction impurities include the following general formula:

{In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are independently divalent organic groups having 1 to 40 carbon atoms. } Can be mentioned. Among these, the following general formula:

{In the above formula (8), R ₆ is a divalent organic group having 1 to 40 carbon atoms. } Is preferred.

Examples of the compound (B) include, but are not limited to, the following compound group when there is one polymerizable unsaturated bond:

(B) Method for preparing a compound having a hydroxyl group and a polymerizable unsaturated bond (B) A method for producing a compound is as long as a compound having at least one hydroxyl group and at least one polymerizable unsaturated bond is obtained in the molecule. There is no particular limitation. The compound (B) is preferably a compound derived from an epoxy resin from the viewpoint of adjusting the amount of free chlorine and / or covalent chlorine to a specific amount. For example, the compound (B) can be produced by reacting an epoxy resin or a ring-opening body thereof with a compound having a polymerizable unsaturated bond. Preferably, a solution obtained by adding and mixing a basic catalyst and a polymerization inhibitor to an epoxy resin or a ring-opening body thereof is obtained, and methacrylic acid or acrylic acid is added to the solution and reacted to obtain the compound (B). It may be manufactured. The reaction may be continued, for example, at 100 ° C. until the acid value falls below a certain value. After the synthesis, the compound (B) can be obtained by stirring the mixture with an anion exchange resin for one day and filtering the mixture. As the anion exchange resin, for example, IRA96SB can be used.

Examples of the epoxy resin used in the compound synthesis reaction include, but are not limited to, structures represented by the following general formulas:

｛上記式中、Ｒ_１及びＲ_２は、それぞれ独立して、炭素数１〜４０の１価の有機基である。｝
で表される構造に変換された化合物であることが好ましい。 (B) The ring-opening body of the epoxy resin used in the compound synthesis reaction includes the following general formula in which the epoxy group is ring-opened.

{In the above formula, R ₁ and R ₂ are independently monovalent organic groups having 1 to 40 carbon atoms. }
It is preferable that the compound is converted into the structure represented by.

By containing the above compound (B), the photosensitizer resin composition of the present embodiment has a high glass transition temperature and thermogravimetric reduction temperature while maintaining storage stability, and further has excellent chemical resistance. Can be provided. Although not bound by theory, the reason why the glass transition temperature rises is that the polymerizable unsaturated bond that remains without polymerization during exposure proceeds with the hydroxy group during high-temperature curing, resulting in the normal polymerizable unsaturated bond. It is considered that this is because a cured film crosslinked with a higher density than the bond-containing compound is obtained, which hinders the movement of the polymer constituting the resin. When the polymerizable unsaturated bond is a (meth) acrylic group, the Michael addition reaction proceeds. The reason for the improvement in chemical resistance is that the solubility in chemicals decreases due to the high crosslink density, and that the amount of free chlorine and / or covalent chlorine is within a specific range. It is considered that the formation of ion pairs with the chemical solution having a dissolution promoting action is suppressed and the chemical resistance is improved. The reason why the thermal weight reduction temperature rises is that the polymerizable unsaturated bond and the hydroxy group undergo an additional reaction with the side chain of the polyimide precursor, which is a factor that lowers the thermal weight reduction temperature, especially during low-temperature curing. It is considered that this is because the components derived from the side chains of the polyimide precursor do not volatilize and remain even when the temperature is raised above this, and the weight loss due to heating is prevented.

When a bifunctional or higher functional epoxy resin is used for the synthesis of the compound (B), the compound (B) may have an unreacted epoxy group. In this case, since anionic polymerization proceeds with the hydroxy group as the starting species during thermosetting, the crosslink density further increases.

The blending amount of the compound (B) is 1 part by mass to 60 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, preferably 1 part by mass to 30 parts by mass from the viewpoint of storage stability, and from the viewpoint of resolution. From 4 parts by mass to 20 parts by mass is more preferable.

(C) Photosensitizer The photosensitive resin composition of the present embodiment contains a photosensitizer. In one embodiment, the photosensitizer may be a photopolymerization initiator. The photopolymerization initiator is preferable because it accelerates the curing of the relief pattern by light irradiation. The photopolymerization initiator is preferably a photoradical polymerization initiator, and benzophenone derivatives such as benzophenone, methyl o-benzoyl benzoate, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, and fluorenone, 2, Acetphenone derivatives such as 2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenylketone, thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, Benzyl derivatives such as benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal, benzoin derivatives such as benzoin and benzoin methyl ether, 1-phenyl-1,2-butandion-2- (o-methoxycarbonyl) oxime, 1-phenyl- 1,2-Propandione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2 Oximes such as − (o-benzoyl) oxime, 1,3-diphenylpropanthrion-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanthrion-2- (o-benzoyl) oxime, N Light such as N-arylglycines such as −phenylglycine, peroxides such as benzoylparkloride, aromatic biimidazoles, titanocenes, α- (n-octanesulfonyloxyimino) -4-methoxybenzylocyanide, etc. Acid generators and the like are preferably mentioned, but are not limited thereto. Among the above-mentioned photopolymerization initiators, oximes are more preferable in terms of photosensitivity.

The blending amount of the photopolymerization initiator is preferably 0.1 part by mass or more and 20 parts by mass, and more preferably 1 part by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the (A) polyimide precursor. The blending amount is preferably 0.1 part by mass or more from the viewpoint of light sensitivity 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 photosensitive resin composition.

(D) Solvent The photosensitive resin composition of the present embodiment contains a solvent. As the solvent, it is preferable to use a polar organic solvent from the viewpoint of solubility in the (A) polyimide precursor. Specific examples of the solvent include N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, and γ. -Butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, 2-octanone and the like can be mentioned, and these may be used alone or in combination of two or more. Can be used in combination.

The solvent is, for example, 30 parts by mass to 1500 parts by mass, preferably 100 parts by mass to 1000 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, depending on the desired coating film thickness and viscosity of the photosensitive resin composition. It can be used in the range of 100 parts by mass to 860 parts by mass, more preferably 100 parts by mass.

From the viewpoint of improving the storage stability of the photosensitive resin composition, a solvent containing alcohols is preferable. Alcohols that can be preferably used are typically alcohols that have an alcoholic hydroxyl group in the molecule and do not have an olefin-based double bond, and specific examples thereof include methyl alcohol, ethyl alcohol, and n-. Alkyl alcohols such as propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol; lactic acid esters such as ethyl lactate; propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol Protinic 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 , Monoalcohols such as ethylene glycol ethyl ether and ethylene glycol-n-propyl ether; 2-hydroxyisobutyric acid esters; 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 preferable, and ethyl lactate, propylene glycol-1-methyl ether, and propylene glycol-1-ethyl ether are particularly preferable. And propylene glycol-1- (n-propyl) ether are more preferred.

When the solvent contains an alcohol having no olefin-based double bond, the content of the alcohol having no olefin-based double bond in the total solvent is 5% by mass to 50% based on the mass of the total solvent. It is preferably mass%, more preferably 10 mass% to 30 mass%. When the content of the alcohol having no olefin-based double bond is 5% by mass or more, the storage stability of the photosensitive resin composition is good, while when it is 50% by mass or less, (A) polyimide This is preferable because the solubility of the precursor is improved.

(E) Free chlorine and / or covalent chlorine The photosensitive resin composition of the present embodiment contains chlorine in the form of free chlorine and / or covalent chlorine. Free chlorine refers to anionized chlorine, and covalent chlorine refers to chlorine that forms a covalent bond and is present in the molecule.

In one embodiment, the amount of free chlorine is 0.0001 to 10 ppm, preferably 0.0001 to 5 ppm, more preferably 0.0001 to 2.0 ppm, and even more, based on the total mass of the photosensitive resin composition. It is preferably 0.0001 to 0.5 ppm. In another embodiment, the photosensitive resin composition was applied onto the substrate by a rotary method so that the film thickness of the resin film after curing was about 10 μm, and heated at 110 ° C. for 180 seconds on a hot plate to cure. When, the amount of free chlorine contained in the obtained coating film is 0.0001 to 15 ppm, preferably 0.0001 to 10 ppm, more preferably 0.0001 to 5 ppm, still more preferably 0.0001 to 5 ppm, based on the total mass of the coating film. It is 0.0001 to 0.8 ppm. In still another embodiment, the total amount of chlorine in the photosensitive resin composition after adjusting the photosensitive resin composition and allowing it to stand at 23 ° C. ± 0.5 ° C. and a relative humidity of 50% ± 10% for 3 days ( The total amount of free chlorine and covalent chlorine) is 0.0001 to 600 ppm, preferably 0.0001 to 420 ppm, more preferably 0.0001 to 250 ppm, still more preferably, based on the total mass of the photosensitive resin composition. Is 0.0001 to 40 ppm.

The source of chlorine is not limited, for example, the photosensitive resin composition contains a compound capable of generating free chlorine and / or a compound having covalent chlorine, so that the amount of chlorine is within the above range. Can be adjusted within. Epoxy resins are generally derived from their raw material, epichlorohydrin, and contain a large amount of chlorine in the form of free chlorine and / or covalent chlorine in the resin. Therefore, when the compound (B) is a compound derived from an epoxy resin, chlorine is contained in the compound (B), and as a result, chlorine is also contained in the photosensitive resin composition. It is easier to adjust the amount within the above range. However, conventionally, when the compound (B) derived from the epoxy resin is used as such, the amount of chlorine is much larger than the above amount. Traditionally, the presence of such chlorine has been tolerated, and those skilled in the art have not focused on the amount of chlorine. However, in the preferred embodiment of the present invention, when the compound (B) derived from the epoxy resin is used, the inventors remove chlorine present in the compound and appropriately control the amount of chlorine. Found to be preferable.

The method for removing chlorine present in the compound (B) derived from the epoxy resin is not particularly limited. For example, chlorine can be removed by stirring the compound (B) in a mixed phase with an anion exchange resin. Examples of the anion exchange resin used for removing chlorine include, but are not limited to, IRA96SB.

Other Components The photosensitive resin composition of the present embodiment may further contain components other than the above components (A) to (E). Other components include, for example, (A) a resin component other than the polyimide precursor; a sensitizer; (F) a monomer other than the (B) compound having a photopolymerizable unsaturated bond; an aid; (G). Epoxy resins; thermal polymerization inhibitors; azole compounds; hindered phenol compounds; and organic titanium compounds.

The photosensitive resin composition may further contain (G) epoxy resin from the viewpoint of obtaining a cured film having a high degree of cross-linking. The amount of the epoxy resin (G) is preferably 0.01 to 25 parts by mass, more preferably 0.1 to 15 parts by mass, and even more preferably 0.1 with respect to 100 parts by mass of the (A) polyimide precursor. It is 10 parts by mass. When the compound (B) derived from the epoxy resin is used, the raw material epoxy resin may be contained in the photosensitive resin composition, and it is easier to adjust the amount of the epoxy resin within the above range.

In one embodiment, the photosensitive resin composition may further contain a resin component other than the (A) polyimide precursor. Examples of the resin component that can be contained in the photosensitive resin composition include polyimide, polyoxazole, polyoxazole precursor, phenol resin, polyamide, epoxy resin, siloxane resin, and acrylic resin. 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 (A) polyimide precursor.

(A) When a positive photosensitive resin composition is prepared by using a polyoxazole precursor together with a polyimide precursor, the positive photosensitive material is a compound having a quinonediazide group, for example, a 1,2-benzoquinonediazide structure or 1 , 2-A compound having a naphthoquinonediazide structure or the like may be used in combination.

In one embodiment, the 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, and 2,6-bis (4'-diethylaminobenzal). ) Cyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminocinna Millidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) Isonaftthiazole, 1,3-bis (4'-dimethylaminobenzal) acetone, 1,3-bis (4'-diethylaminobenzal) acetone, 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3-Acetone-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) Examples thereof include styryl) naphtho (1,2-d) thiazole and 2- (p-dimethylaminobenzoyl) styrene. These can be used alone or in combination of a plurality (for example, 2 to 5 types).

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

In one embodiment, in order to improve the resolution of the relief pattern, the photosensitive resin composition can optionally contain a monomer other than (F) a compound having a photopolymerizable unsaturated bond (B). As such a monomer, a (meth) acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferable, and is not particularly limited to the following, but ethylene glycol such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate. Or polyethylene glycol mono or diacrylate and methacrylate, propylene glycol or polypropylene glycol mono or diacrylate and methacrylate, glycerol mono, di or triacrylate and methacrylate, cyclohexane diacrylate and dimethacrylate, 1,4-butanediol di. Acrylate and dimethacrylate, diacrylate and dimethacrylate of 1,6-hexanediol, diacrylate and dimethacrylate of neopentyl glycol, mono or diacrylate and methacrylate of bisphenol A, benzenetrimethacrylate, isobornyl acrylate and methacrylate, acrylamide And derivatives thereof, methacrylicamides and derivatives thereof, trimethylolpropane triacrylates and methacrylates, di or triacrylates and methacrylates of glycerol, di, tri, or tetraacrylates and methacrylates of pentaerythritol, and ethylene oxide or propylene oxide additions of these compounds. Examples of compounds such as substances can be mentioned.

The blending 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 one embodiment, the photosensitive resin composition may optionally contain an adhesion aid in order to improve the adhesion between the film formed using the photosensitive resin composition and the substrate. Examples of the adhesion aid include γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and the like. 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) ) Succinimide, N- [3- (triethoxysilyl) propyl] phthalamide 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) propylsuccinic hydride, N-phenylaminopropyltrimethoxysilane Examples thereof include a coupling agent and an aluminum-based adhesive aid such as aluminum tris (ethylacetacetate), aluminumtris (acetylacetonate), and ethylacetacetate aluminum diisopropylate.

Among these adhesive aids, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength. The blending amount of the adhesion aid 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 one embodiment, the photosensitive resin composition optionally contains a thermal polymerization inhibitor in order to improve the viscosity and photosensitivity stability of the photosensitive resin composition, especially when stored in a solvent-containing solution. Can include. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, and 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-Sulphopropylamino) phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt and the like are used.

The blending amount 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 (A) polyimide precursor.

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

The blending amount of the azole compound is preferably 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, and is 0.5 parts by mass to 5 parts by mass from the viewpoint of light sensitivity characteristics. More preferably. When the blending amount of the azole compound with respect to 100 parts by mass of the (A) polyimide precursor is 0.1 parts by mass or more, when the photosensitive resin composition is formed on the copper or the copper alloy, the copper or the copper alloy is formed. When the discoloration of the surface is suppressed, while the amount is 20 parts by mass or less, the light sensitivity is excellent, which is preferable.

In this embodiment, the photosensitive resin composition can contain a hindered phenol compound in order to suppress discoloration on copper. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, and 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 blending amount of the hindered phenol compound is preferably 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, and 0.5 parts by mass to 10 parts by mass from the viewpoint of light sensitivity characteristics. More preferably, it is a part. Copper or copper when the blending amount of the hindered phenol compound with respect to 100 parts by mass of the (A) polyimide precursor is 0.1 parts by mass or more, for example, when a photosensitive resin composition is formed on copper or a copper alloy. Discoloration and corrosion of the alloy are prevented, while when the amount is 20 parts by mass or less, the light sensitivity is excellent, which is preferable.

In one embodiment, the photosensitive resin composition may contain an organic titanium compound. By containing the 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.

Examples of the organic titanium compound that can be used include those in which an organic chemical substance is bonded to a titanium atom via a covalent bond or an ionic bond.

Specific examples of the organic titanium compound are shown in I) to VII) below:
I) As the titanium chelate compound, a titanium chelate having two or more alkoxy groups is more preferable because the storage stability of the photosensitive resin composition and a good pattern can be obtained. Specific examples of titanium chelate compounds include titanium bis (triethanolamine) diisopropoxyside, titanium di (n-butoxide) bis (2,4-pentanedionate), and titanium diisopropoxyside bis (2,4). -Pentane dionate), titanium diisopropoxyside bis (tetramethylheptandionate), titanium diisopropoxyside bis (ethylacetacetate) and the like.

II) Examples of the tetraalkoxytitanium compound include titanium tetra (n-butoxide), titanium tetraethoxide, titanium tetra (2-ethylhexoxyside), titanium tetraisobutoxide, titanium tetraisopropoxyside, and titanium tetra. Metoxide, Titanium Tetramethoxypropoxyside, Titanium Tetramethylphenoxide, Titanium Tetra (n-Nonirokiside), Titanium Tetra (n-Propoxide), Titanium Tetrasteer Lokiside, Titanium Tetrakiss [Bis {2,2- (Aryloxy) Methyl) butoxide}] and the like.

The III) titanocene compounds such as pentamethylcyclopentadienyltitanium tri methoxide, bis (eta ^{5-2,4-cyclopentadiene-1-yl)} bis (2,6-difluorophenyl) titanium, bis (eta ⁵ -2,4-cyclopentadiene-1-yl) bis (2,6-difluoro-3-(1H-pyrrol-1-yl) phenyl) titanium, and the like.

IV) Examples of the monoalkoxytitanium compound include titaniumtris (dioctylphosphate) isopropoxyside and titaniumtris (dodecylbenzenesulfonate) isopropoxyside.

V) Examples of the titanium oxide compound include titanium oxide bis (pentanionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide and the like.

VI) Examples of the titanium tetraacetylacetonate compound include titaniumtetraacetylacetoneate and the like.

Examples of the VII) titanate coupling agent include isopropyltridodecylbenzenesulfonyl titanate and the like.

Among the above I) to VII), the organic titanium compound is more preferably at least one compound selected from the group consisting of the above I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanocene compound. It is preferable from the viewpoint of exhibiting good chemical resistance. In particular, titanium di isopropoxide bis (ethylacetoacetate), titanium tetra (n- butoxide), and bis (eta ^{5-2,4-cyclopentadiene-1-yl)} bis (2,6-difluoro-3- ( 1H-pyrrole-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, and 0.1 parts by mass to 2 parts by mass with respect 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, while when it is 10 parts by mass or less, storage stability is excellent, which is preferable.

A compound having a structure similar to that of the imidization accelerator (compound showing basicity) may be introduced into the polymer side chain, whereby a higher imidization rate than when the imidization accelerator is used as an additive can be obtained. Therefore, a photosensitive resin composition having both storage stability and chemical resistance can be obtained.

The photosensitive resin composition preferably has a viscosity change rate of 5% or less as compared with the initial stage when the resin composition is stored at a temperature of 23 ° C. and a humidity of 50% Rh for 4 weeks. Further, the photosensitive resin composition preferably has an imidization ratio of 70% or more when the resin composition is heated at 170 ° C. for 2 hours to obtain a cured coating film. It is more preferable that the imidization ratio of the cured coating film is 85% or more. As described above, in one embodiment, the photosensitive resin composition can provide a polyimide having a high imidization rate and excellent storage stability and chemical resistance.

｛一般式（１１）中、Ｘ^１及びＹ^１は、一般式（１）中のＸ_１及びＹ_１と同じであり、ｍは正の整数である。｝
一般式（１）中の好ましいＸ_１とＹ_１は、同じ理由により、一般式（１１）のポリイミドにおいても好ましい。一般式（１１）の繰り返し単位数ｍは、特に限定は無いが、２〜１５０の整数であってもよい。
本発明によれば、上記で説明された感光性樹脂組成物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も提供することができる。 [Polyimide]
The structure of the polyimide formed from the polyimide precursor composition and contained in the cured relief pattern is preferably represented by the following general formula (11).

{In the general formula (11), ^{X 1} and ^{Y 1} in formula (1) is the same as _{X 1} and _{Y 1} in, m is a positive integer. }
_{The preferred X 1} and Y ₁ in the general formula (1) are also preferable in the polyimide of the general formula (11) for the same reason. The number of repeating units m in the general formula (11) is not particularly limited, but may be an integer of 2 to 150.
According to the present invention, it is also possible to provide a method for producing polyimide, which comprises a step of converting the photosensitive resin composition described above into polyimide.

[Curing relief pattern]
According to the present invention, it is possible to provide a cured relief pattern using the photosensitive resin composition described above, and a method for producing the same. In one embodiment, the method for producing the cured relief pattern is described in the following steps (1) to (4):
(1) A step of applying the photosensitive resin composition according to the present embodiment on a substrate to form a photosensitive resin layer on the substrate.
(2) A step of exposing the photosensitive resin layer,
This method includes (3) a step of developing the photosensitive resin layer after the exposure to form a relief pattern, and (4) a step of heat-treating the relief pattern to form a cured relief pattern.

Hereinafter, each step will be described.
(1) Step of applying the photosensitive resin composition of the present embodiment on a substrate and forming a photosensitive resin layer on the substrate In this step, the photosensitive resin composition according to the present embodiment is applied on a substrate. And, if necessary, dried afterwards to form a photosensitive resin layer. As a 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 printing machine, or the like, or spray coating with a spray coater. A method or the like can be used.

If necessary, the coating film composed of the photosensitive resin composition can be dried, and as the drying method, for example, air drying, heat drying in an oven or a hot plate, vacuum drying and the like are used. Further, it is desirable that the coating film is dried under conditions that do not cause imidization of the (A) polyimide precursor in the 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, the 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 to a photomask having a pattern using an exposure device such as a contact aligner, a mirror projection, or a stepper. Alternatively, it is exposed through a reticle or directly with an ultraviolet light source or the like.

After that, post-exposure bake (PEB) and / or pre-development bake at any combination of temperature and time may be applied, if necessary, for the purpose of improving light sensitivity and the like. The range of baking conditions is preferably a temperature of 40 ° C. to 120 ° C. and a time of preferably 10 seconds to 240 seconds, but as long as it does not interfere with various properties of the negative photosensitive resin composition. Not limited to this range.

(3) Step of developing the photosensitive resin layer after exposure to form a relief pattern In this step, when the photosensitive resin composition is a negative type, the photosensitive resin layer after exposure is unexposed. The part is developed and removed. As a developing method for developing the photosensitive resin layer after exposure (irradiation), any of the conventionally known photoresist developing methods, for example, a rotary spray method, a paddle method, a dipping method accompanied by ultrasonic treatment, and the like. The method can be selected and used. Further, after development, post-development baking may be performed at an arbitrary combination of temperature and time, if necessary, for the purpose of adjusting the shape of the relief pattern. As the developing solution used for development, for example, a good solvent for a negative photosensitive resin composition or a combination of the good solvent and a poor solvent is preferable. As a good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone and the like are preferable. .. As the poor solvent, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water and the like are preferable. 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 by the solubility of the polymer in the negative photosensitive resin composition. Further, two or more kinds of each solvent, 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 above development is heated to disperse the photosensitive component, and (A) the polyimide precursor is used. By imidization, it is converted into a cured relief pattern made of polyimide. As a method of heat curing, various methods can be selected, for example, a method using a hot plate, a method using an oven, a method using a temperature-increasing oven in which a temperature program can be set, and the like. The heating can be performed, for example, at 170 ° C. to 400 ° C. for 30 minutes to 5 hours. Air may be used as the atmospheric gas at the time of heat curing, or an inert gas such as nitrogen or argon may be used.

[Semiconductor device]
The photosensitive resin composition of the present embodiment can also provide a semiconductor device having a cured relief pattern obtained by the above-mentioned method for producing a cured relief pattern. 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 method for manufacturing a semiconductor device, which uses a semiconductor element as a base material and includes the above-mentioned method for manufacturing a cured relief pattern as a part of a 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 of a cured relief pattern formed by the above-mentioned cured relief pattern manufacturing method. It can be manufactured by forming it as a protective film or the like of the above and combining it with a known manufacturing method of a semiconductor device.

[Display device]
The photosensitive resin composition of the present embodiment is a display body device including a display body element and a cured film provided on the display body element, and the cured film is a display body having the above-mentioned cured relief pattern. Equipment can also be provided. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer sandwiched between them. For example, examples of the cured film include a surface protective film, an insulating film, and a flattening film of 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 an organic EL element cathode. ..

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

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 characteristics of the photosensitive resin composition were measured and evaluated according to the following methods.

[Measurement and evaluation method]
(1) Weight Average Molecular Weight The weight average molecular weight (Mw) of each resin was measured by a gel permeation chromatography method (standard polystyrene conversion). The column used for the measurement was the trade name "Shodex 805M / 806M series" manufactured by Showa Denko KK, and the standard monodisperse polystyrene was the trade name "Shodex STANDARD SM-105" manufactured by Showa Denko KK. The developing solvent was N-methyl-2-pyrrolidone, and the detector used was the brand name "Shodex RI-930" manufactured by Showa Denko KK.

(2) Measurement of Free Chlorine Amount of Resin Composition After preparing the photosensitive resin composition, it is allowed to stand at room temperature (23.0 ° C ± 0.5 ° C, relative humidity 50% ± 10%) for 3 days, and then the resin composition. The amount of free chlorine in the substance was measured. The ion concentration measurement was performed at 23.0 ° C. using ICS-3000 manufactured by ThermoFicher. Based on the measurement results, the content of chloride ions in the resin composition was determined under the following measurement conditions.
2 g of the photosensitive resin composition was weighed, added to 4 mL of NMP, and stirred with a shaker for 10 minutes to dissolve. Further, 30 mL of ion-exchanged water was added and stirred with a shaker for 10 minutes, and the insoluble matter was removed by a centrifuge (CF15RN manufactured by HIMAC) and filtered through a disc filter (JP050AN manufactured by DISMIC). 1 mL of the treated sample solution is automatically inserted into the column with an autosampler.
-Guard column for anion analysis: IonPac AS4A-SC (4 mm x 250 mm)
・ Guard column pump flow rate: 0.500 mL / min
-Separation column for anion analysis: IonPac AS4A-SZ (4 mm x 50 mm)
-Sample introduction line pump flow rate: 0.500 mL / min
・ Anion chemical suppressor: ACRS-500 (for 4 mm)

(3) Measurement of Free Chlorine Amount of Cured Polyimide Coating Film A photosensitive resin composition is rotary-coated on a 6-inch silicon wafer so that the film thickness after curing is about 10 μm, and heated at 110 ° C. for 180 seconds on a hot plate. Then, a cured polyimide coating film was obtained. The film thickness was measured with a film thickness measuring device, Lambda Ace (manufactured by Dainippon Screen). The amount of free chlorine in the obtained polyimide coating film was measured under the following measurement conditions.
2 g of the polyimide coating film was weighed, and the mixture added to 4 mL of NMP was stirred with a shaker for 10 minutes to dissolve it. Further, 30 mL of ion-exchanged water was added and stirred with a shaker for 10 minutes, and the insoluble matter was removed by a centrifuge (CF15RN manufactured by HIMAC) and filtered through a disc filter (JP050AN manufactured by DISMIC). 1 mL of the treated sample solution is automatically inserted into the column with an autosampler.
-Guard column for anion analysis: IonPac AS4A-SC (4 mm x 250 mm)
・ Guard column pump flow rate: 0.500 mL / min
-Separation column for anion analysis: IonPac AS4A-SZ (4 mm x 50 mm)
-Sample introduction line pump flow rate: 0.500 mL / min
・ Anion chemical suppressor: ACRS-500 (for 4 mm)

(4) Measurement of glass transition temperature of cured polyimide coating film A photosensitive resin composition is rotationally coated on a 6-inch silicon wafer so that the film thickness after curing is about 10 μm, and a hot plate is used at 110 ° C. for 180 seconds. After prebaking, a cured polyimide coating film was obtained by heating at 170 ° C. for 2 hours in a nitrogen atmosphere using a heating program type curing furnace (VF-000 type, manufactured by Koyo Lindbergh Co., Ltd.). The film thickness was measured with a film thickness measuring device, Lambda Ace (manufactured by Dainippon Screen). The obtained polyimide coating film is taken out in a strip shape, ^{measured by a thermomechanical test device (TMA-50 manufactured by Shimadzu Corporation) in a range of a load of 200 g / mm 2} , a heating rate of 10 ° C./min, and 20 to 500 ° C., and the temperature is measured. Was defined as the glass transition temperature (Tg) at the tangent intersection of the thermal yield points of the polyimide film in the measurement chart with the horizontal axis and the displacement amount on the vertical axis.

(5) Measurement of Thermogravimetric Reduction Temperature (5% Weight Reduction Temperature) of Cured Polyimide Coating A photosensitive resin composition is rotationally coated on a 6-inch silicon wafer so that the film thickness after curing is about 10 μm. After prebaking on a hot plate at 110 ° C. for 180 seconds, it is heated at 170 ° C. for 2 hours in a nitrogen atmosphere using a temperature rise program type cure furnace (VF-2000 type, manufactured by Koyo Lindbergh Co., Ltd.) to cure polyimide. A coating was obtained. The film thickness was measured with a film thickness measuring device, Lambda Ace (manufactured by Dainippon Screen). When the obtained polyimide coating film is scraped off and the temperature is raised from room temperature to 10 ° C./min using a thermogravimetric measuring device (manufactured by Shimadzu Corporation, TGA-50), the weight of the film when it reaches 170 ° C. is measured. The temperature at which the weight was reduced by 5% as 100% (5% weight loss temperature) was measured.

(6) Chemical resistance test of cured relief pattern on Cu A sputtering device (L-440S-FHL type, manufactured by Canon Anerva) is placed 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. Subsequently, the photosensitive resin composition prepared by the method described later is rotationally applied onto this wafer using a coater developer (D-Spin 60A type, manufactured by SOKUDO), and dried to form a coating film having a thickness of 10 μm. did. This coating film was irradiated with energy ^{of 500 mJ / cm 2} by Prisma GHI (manufactured by Ultratech) using a mask with a test pattern. Next, this coating film was spray-developed with a coater developer (D-Spin 60A type, manufactured by SOKUDO) using cyclopentanone as a developing solution, and rinsed with propylene glycol methyl ether acetate to obtain a relief pattern on Cu. Obtained.
A wafer having the relief pattern formed on Cu is heat-treated at 170 ° C. for 2 hours in a nitrogen atmosphere using a heating program curing furnace (VF-2000 type, manufactured by Koyo Lindbergh Co., Ltd.) on Cu. A cured relief pattern made of a resin having a thickness of about 6 to 7 μm was obtained.
The prepared relief pattern was prepared by heating a resist stripping film (manufactured by ATMI, product name ST-44, main component 2- (2-aminoethoxy) ethanol, 1-cyclohexyl-2-pyrrolidone) to 50 ° C. 5 It was soaked for minutes, washed with running water for 30 minutes, and air-dried. Then, the surface of the film was visually observed with an optical microscope, and the 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 film thickness after the chemical solution treatment. Chemical resistance was evaluated based on the following criteria.
Film thickness change rate (%) = (Film thickness after chemical treatment)-(Membrane pressure before chemical treatment) / (Film thickness before chemical treatment) x 100
"Excellent": Film thickness change rate is less than 5% based on the film thickness before immersion in the chemical solution "Good": Film thickness change rate is 5% or more and less than 10% based on the film thickness before immersion in the chemical solution "Yes": Film Thickness change rate is 10% or more and less than 15% based on the film thickness before immersion in chemical solution "No": Film thickness change rate is 15% or more based on the film thickness before immersion in chemical solution

(7) Resolution of cured relief pattern on Cu 200 nm on a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625 ± 25 μm) using a sputtering device (L-440S-FHL type, manufactured by Canon Anerva). Thick Ti and 400 nm thick Cu were sputtered in this order. Subsequently, the photosensitive resin composition prepared by the method described later is rotationally applied onto this wafer using a coater developer (D-Spin 60A type, manufactured by SOKUDO), and dried to form a coating film having a thickness of 10 μm. did. This coating film was irradiated with energy ^{of 500 mJ / cm 2} by Prisma GHI (manufactured by Ultratech) using a mask with a test pattern. Next, this coating film was spray-developed with a coater developer (D-Spin 60A type, manufactured by SOKUDO) using cyclopentanone as a developing solution, and rinsed with propylene glycol methyl ether acetate to obtain a relief pattern on Cu. Obtained.
A wafer having the relief pattern formed on Cu is heat-treated at 170 ° C. for 2 hours in a nitrogen atmosphere using a heating program curing furnace (VF-2000 type, manufactured by Koyo Lindbergh Co., Ltd.) on Cu. A cured relief pattern made of a resin having a thickness of about 6 to 7 μm was obtained.
The prepared relief pattern was observed under an optical microscope to determine the size of the minimum aperture pattern. At this time, if the area of the opening of the obtained pattern is ½ or more of the corresponding pattern mask opening area, it is considered to be resolved, and the one having the minimum area among the resolved openings is selected. The length of the corresponding mask opening side was taken as the resolution.
"Excellent": The size of the minimum opening pattern is less than 10 μm "Good": The size of the minimum opening pattern is 10 μm or more and less than 14 μm “Yes”: The size of the minimum opening pattern is 14 μm or more and less than 18 μm “No”: The size of the minimum opening pattern is 18 μm or more

(8) Measurement of total chlorine content of the resin composition After preparing the photosensitive resin composition, it is allowed to stand at room temperature (23.0 ° C ± 0.5 ° C, relative humidity 50% ± 10%) for 3 days, and then the resin composition. The total amount of chlorine in the product (total amount of free chlorine and covalent chlorine) was measured. The photosensitive resin composition was burned and decomposed at 800 ° C., the decomposed gas was absorbed by ultrapure water, and the total amount of chlorine in the resin composition was determined by ion chromatography. Ion chromatography consisted of a Dionex IC-1000 and an IonPac AS12A (4 mm) column, and the eluate _{was measured as a 0.3 mM NaHCO 3 /} 2.7 _{mM Na 2} CO ₃ aqueous solution at a flow rate of 1.5 mL / min. ..

[(A) Production of polyimide precursor]
<Production Example 1> Synthesis of Polyimide Precursor A-1 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a separable flask having a capacity of 2 L, and 131.2 g of 2-hydroxyethyl methacrylate (HEMA) was placed. 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 exotherm by the reaction, the reaction mixture was allowed to cool to room temperature and left for 16 hours.
Next, under ice-cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 4,4'-oxydianiline (ODA). ) 93.0 g suspended in 350 mL of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 mL of ethyl alcohol was added and the mixture was 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 obtained reaction solution was added to 3 L of ethyl alcohol to form a precipitate composed of a crude polymer. The produced crude polymer was filtered off and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 L of water to precipitate a polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain a powdery polymer (polymer A-1). When the molecular weight of the polymer (A-1) was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000.

The weight average molecular weight of the resin obtained in each production example was measured by gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight in terms of standard polystyrene was determined.
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40 ° C
Column: Shodex KD-806M Two in series Mobile phase: 0.1 mol / L LiBr / NMP
Flow velocity: 1 mL / min.

<Production Example 2> Synthesis of Polyimide Precursor A-2 3,3', 4,4'-biphenyltetracarboxylic instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 1. The reaction was carried out in the same manner as in Production Example 1 described above except that 147.1 g of acid dianhydride (BPDA) was used to obtain a polymer (A-2). When the molecular weight of the polymer (A-2) was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 26,000.

<Production Example 3> Synthesis of Polyimide Precursor A-3 As described above, except that 48.7 g of p-phenylenediamine was used instead of 93.0 g of 4,4'-oxydianiline (ODA) of Production Example 1. The reaction was carried out in the same manner as in Production Example 1 to obtain a polymer (A-3). When the molecular weight of the polymer (A-3) was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 24,000.

<Production Example 4> Synthesis of Polyimide Precursor A-4 Instead of 93.0 g of 4,4'-oxydianiline (ODA) in Production Example 1, 4,4'-diamino-2,2'-dimethylbiphenyl 98 The reaction was carried out in the same manner as in Production Example 1 described above except that 0.6 g was used to obtain a polymer (A-4). When the molecular weight of the polymer (A-4) was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 26,000.

[Production of (B) compound]
<Production Example 5> Synthesis of Epoxy (Meta) Acrylate Compound B-1 34.0 g of bisphenol A diglycidyl ether was placed in a 1 L volume separable flask, and 0.4 g of dimethylaniline, 0.04 g of p-methoxyphenol, and methacrylic acid were placed. 15.5 g was added and reacted at 100 ° C. After confirming that the reaction proceeded by measuring the acid value, it was mixed with 40.5 g of the ion exchange resin IRA96SB, stirred overnight, and the process of removing the ion exchange resin by filtration was repeated three times. Propane-2,2-diyl bis (4,1-phenylene)] bis (oxy)} bis (2-hydroxypropane-3,1-diyl) = B-1 containing dimethacrylate as a main component was obtained.

<Production Example 6> Synthesis of Epoxy (Meta) Acrylate Compound B-2 The reaction was carried out in the same manner as in Production Example 5 described above, except that 13.0 g of acrylic acid was used instead of 15.5 g of methacrylic acid. Then, {[propane-2,2-diylbis (4,1-phenylene)] bis (oxy)} bis (2-hydroxypropane-3,1-diyl) = B-2 containing diacrylate as a main component was obtained. rice field.

<Production Example 7> Synthesis of Epoxy (Meta) Acrylate Compound B-3 The method according to Production Example 5 above, except that 17.42 g of ethylene glycol diglycidyl ether was used instead of 34.0 g of bisphenol A diglycidyl ether. The reaction was carried out in the same manner as in the above to obtain B-3 containing 1,2-bis (3-methacryloyloxy-2-hydroxyproproxy) ethane as a main component.

<Production Example 8> Synthesis of Epoxy (Meta) Acrylate Compound B-4 17.42 g of ethylene glycol diglycidyl ether was used in place of 34.0 g of bisphenol A diglycidyl ether, and acrylic acid 13. The reaction was carried out in the same manner as in Production Example 5 described above except that 0 g was used to obtain B-4 containing 1,2-bis (3-acryloyloxy-2-hydroxypropoxy) ethane as a main component. rice field.

<Production Example 9> Synthesis of Epoxy (Meta) Acrylate Compound B-5 The method according to Production Example 5 described above, except that 23.23 g of glycerin diglycidyl ether was used instead of 34.0 g of bisphenol A diglycidyl ether. The reaction was carried out in the same manner to obtain B-5 containing glycerol 1,3-diglycerolate dimethacrylate as a main component.

<Production Example 10> Synthesis of Epoxy (meth) Acrylate Compound B-6 23.23 g of glycerin diglycidyl ether is used instead of 34.0 g of bisphenol A diglycidyl ether, and 13.0 g of acrylic acid is used instead of 15.5 g of methacrylic acid. The reaction was carried out in the same manner as in Production Example 5 described above, except that B-6 containing glycerol 1,3-diglycerolate diacrylate as a main component was obtained.

<Production Example 11> Synthesis of Epoxy (Meta) Acrylate Compound B-7 With the method described in Production Example 5 above, except that 31.24 g of bisphenol F type epoxy was used instead of 34.0 g of bisphenol A diglycidyl ether. The reaction was carried out in the same manner to obtain B-7 containing bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl)] methane as a main component.

<Production Example 12> Synthesis of Epoxy (Meta) Aacrylate Compound B-8 Same as the method described in Production Example 5 above, except that 15.02 g of glycidyl phenyl ether was used instead of 34.0 g of bisphenol A diglycidyl ether. The reaction was carried out to obtain B-8 containing 2-hydroxy-3-phenoxypropyl methacrylate as a main component.

<Production Example 13> Synthesis of Epoxy (Meta) Acrylate Compound B-9 15.02 g of glycidyl phenyl ether is used instead of 34.0 g of bisphenol A diglycidyl ether, and 13.0 g of acrylic acid is used instead of 15.5 g of methacrylic acid. The reaction was carried out in the same manner as in Production Example 5 described above except that it was used to obtain B-9 containing 2-hydroxy-3-phenoxypropyl acrylate as a main component.

<Production Example 14> Synthesis of Epoxy (Meta) Acrylic Compound B-10 In Production Example 5 above, except that 35.3 g of bisphenol A diglycidyl ether hydrogenated product was used instead of 34.0 g of bisphenol A diglycidyl ether. The reaction was carried out in the same manner as described to obtain B-10 containing 2,2-bis [4- (2-hydroxy-3-methacryloxy-1-propoxy) phenyl] propane as a main component.

<Production Example 15> Synthesis of epoxy (meth) acrylate compound B-11 46.25 g of 9,9-bis [4- (2-glycidylethoxy) phenyl] fluorene was used instead of 34.0 g of bisphenol A diglycidyl ether. Except for this, the reaction was carried out in the same manner as in Production Example 5 described above, and B-11 containing 4,4'-(9-fluorenelilidene) bis (2-hydroxy-3-phenoxypropyl methacrylate) as a main component. Got

<Production Example 16> Synthesis of Epoxy (Meta) Acrylate Compound B-12 The above-mentioned production example except that 24.30 g of 1,6-bis (glycidyloxy) naphthalene was used instead of 34.0 g of bisphenol A diglycidyl ether. The reaction was carried out in the same manner as in No. 5 to obtain B-12 containing 1,6-bis (3-methacryloyloxy-2-hydroxyproproxy) naphthalene as a main component.

<Production Example 17> Synthesis of Epoxy (Meta) Acrylate Compound B-13 34.0 g of bisphenol A diglycidyl ether was placed in a separable flask having a capacity of 1 L, and 0.4 g of dimethylaniline, 0.04 g of p-methoxyphenol, and methacrylic acid were placed. 17.4 g was added and reacted at 100 ° C. It was confirmed by measuring the acid value that the reaction had proceeded, and {[propane-2,2-diylbis (4,1-phenylene)] bis (oxy) without removing free chlorine with an ion exchange resin. } Bis (2-hydroxypropane-3,1-diyl) = B-13 containing dimethacrylate as a main component was obtained.

[Manufacturing of photosensitive resin composition]
<Example 1>
A negative photosensitive resin composition was prepared using the polyimide precursor A-1 by the following method, and the prepared composition was evaluated. (A) A-1: 100 g as a polyimide precursor, (B) B-1: 10 g as an epoxy (meth) acrylate compound, (C) 1-phenyl-1,2-propanedione-2- as a photopolymerization initiator. (O-ethoxycarbonyl) -oxime (hereinafter referred to as PDO): 5 g, (F) tetraethylene glycol dimethacrylate as a monomer (hereinafter referred to as M4G): 5 g, and (D) γ-butyrolactone (hereinafter referred to as GBL). Notation): Dissolved in 100 g. The viscosity of the obtained solution was adjusted to about 40 poise by further adding a small amount of GBL to obtain a negative photosensitive resin composition. From the above procedure, (E) the amount of free chlorine and the amount of total chlorine in the photosensitive resin composition, and the amount of free chlorine contained in the cured film were adjusted. The composition was evaluated according to the method described above. The results are shown in Table 1.

<Examples 2 to 18, Comparative Examples 1 to 4>
A negative photosensitive resin composition similar to that of Example 1 was prepared except that the compounding ratio was prepared as shown in Table 1, and the same evaluation as that of Example 1 was performed. The results are shown in Tables 1 and 2.

As is clear from Tables 1 and 2, in the photosensitive resin composition of Example 1, the glass transition temperature is 210 ° C., the 5% weight loss temperature is 300 ° C., the resolution is “excellent”, and the chemical resistance test result. Was "excellent". Similarly, in each of the photosensitive resin compositions of Examples 2 to 10, the glass transition temperature is 195 ° C. or higher, the 5% weight loss temperature is 290 ° C. or higher, the resolution result is “OK” or higher, and the chemical resistance test. The result of was more than "OK".

On the other hand, in Comparative Example 1, the resolution was "excellent", but the glass transition temperature was 170 ° C. and the 5% weight loss temperature was 260 ° C. As a result of the chemical resistance test, the film thickness change rate changed by 20% based on the film thickness before immersion, and the evaluation was "impossible". In Comparative Example 2, the glass transition temperature was 210 ° C., the 5% weight loss temperature was 300 ° C., and the resolution was “good”, but the chemical resistance changed by 15%, and the evaluation was “impossible”. .. In Comparative Example 3, the glass transition temperature was 200 ° C. and the 5% weight loss temperature was 300 ° C., but the resolution was “impossible”. In Comparative Example 4, the chemical resistance was "impossible".

Although the embodiments of the present invention have been described above, the present invention is not limited to this, and can be appropriately changed without departing from the spirit of the invention.

By using the photosensitive resin composition according to the present invention, it is possible to improve the glass transition temperature and the 5% weight loss temperature and improve the chemical resistance while maintaining high resolution in the cured film treated at a low temperature. be. Therefore, the photosensitive resin composition according to the present invention can be suitably used in the field of photosensitive materials useful for producing electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims (16)

(A) Polyimide precursor and
(B) A compound having a hydroxyl group and a polymerizable unsaturated bond,
(C) Photosensitizer and
(D) Solvent and
(E) Free chlorine and
A photosensitive resin composition containing
The photosensitive resin composition has an amount of free chlorine of 0.0001 to 2 ppm based on the total mass of the photosensitive resin composition. The photosensitive resin composition according to claim 1, wherein the photosensitive agent (C) is a photopolymerization initiator. The photosensitive resin composition according to claim 1 or 2, wherein the polyimide precursor (A) is 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, and n ₁ is 2 to 150. R ₁ and R ₂ are independently hydrogen atoms or monovalent organic groups having 1 to 40 carbon atoms. However, _{at least one of R 1} and R ₂ has the following general formula (2):

In formula (2), R ₃ , R ₄ and R ₅ are independently hydrogen atoms or monovalent organic groups having 1 to 3 carbon atoms, and m ₁ is a group represented by. It is an integer of 2 to 10. } The photosensitive resin composition according to any one of claims 1 to 3, which contains 100 to 860 parts by mass of the solvent (D) with respect to 100 parts by mass of the polyimide precursor (A). The solvent (D) is N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone. , Α-Acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, and one or more compounds selected from the group consisting of 2-octanone. The photosensitive resin composition according to any one of claims 1 to 4, which comprises. The photosensitive resin composition according to any one of claims 1 to 5, wherein the compound having the hydroxyl group and the polymerizable unsaturated bond (B) has two or more polymerizable unsaturated bonds. The photosensitive resin composition according to any one of claims 1 to 5, wherein the compound having the (B) hydroxyl group and a polymerizable unsaturated bond is a reaction product of an epoxy resin and (meth) atacryllic acid. .. The photosensitive resin composition according to any one of claims 1 to 5, wherein the compound (B) having a hydroxyl group and a polymerizable unsaturated bond is represented by the following general formula (3) or (4). ..

{In formula (3), R ₁ is a monovalent organic group having 1 to 40 carbon atoms. }

{In formula (4), R ₂ is a monovalent organic group having 1 to 40 carbon atoms. } The photosensitive resin composition according to any one of claims 1 to 5, wherein the compound (B) having a hydroxyl group and a polymerizable unsaturated bond is represented by the following general formula (5) or (6). ..

{In formula (5), R ₃ is a monovalent organic group having 1 to 40 carbon atoms. }

{Wherein (6), _{R 4} is a monovalent organic group having 1 to 40 carbon atoms. } The photosensitive resin composition according to any one of claims 1 to 5, wherein the compound (B) having a hydroxyl group and a polymerizable unsaturated bond contains a compound represented by the following general formula (7).

{In formula (7), R ₂ is a divalent organic group having 1 to 40 carbon atoms. } The photosensitive resin composition according to any one of claims 1 to 5, wherein the compound (B) having a hydroxyl group and a polymerizable unsaturated bond contains a compound represented by the following general formula (8).

{In formula (8), R ₆ is a divalent organic group having 1 to 40 carbon atoms. } (A) Polyimide precursor and
(B) A compound having a hydroxyl group and a polymerizable unsaturated bond,
(C) Photosensitizer and
(D) Solvent and
(E) A photosensitive resin composition containing free chlorine.
The photosensitive resin composition is applied onto a substrate by a rotation method so that the film thickness after curing is about 10 μm, and is heated on a hot plate at 110 ° C. for 180 seconds to be cured. A photosensitive resin composition in which the amount of free chlorine contained is 0.0001 to 5 ppm based on the total mass of the coating film. (G) The photosensitive resin composition according to any one of claims 1 to 12, further comprising an epoxy resin. The photosensitive resin composition according to claim 13, wherein the amount of the (G) epoxy resin is 0.1 to 10 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor. The photosensitive resin composition according to any one of claims 1 to 14, which is a negative type photosensitive resin composition. (A) Polyimide precursor and
(B) A compound having a hydroxyl group and a plurality of polymerizable unsaturated bonds,
(C) Photosensitizer and
(D) Solvent and
(E) Free chlorine and / or covalent chlorine,
A photosensitive resin composition containing
After adjusting the photosensitive resin composition, the total amount of chlorine in the photosensitive resin composition when the photosensitive resin composition is allowed to stand at 23 ° C. ± 0.5 ° C. and a relative humidity of 50% ± 10% for 3 days is the photosensitive resin. A photosensitive resin composition which is 0.0001 to 250 ppm based on the total mass of the composition.