JP6958332B2 - Photosensitive resin composition, manufacturing method of pattern cured film, cured film, interlayer insulating film, cover coat layer, surface protective film and electronic components - Google Patents

Description

The present invention relates to a photosensitive resin composition, a method for producing a pattern cured film, a cured film, an interlayer insulating film, a cover coat layer, a surface protective film, and an electronic component.

Conventionally, polyimide or polybenzoxazole having excellent heat resistance, electrical properties, mechanical properties, etc. has been used as the surface protective film and the interlayer insulating film of a semiconductor element. In recent years, photosensitive resin compositions in which photosensitive properties have been imparted to these resins themselves have been used, and by using this, the manufacturing process of a pattern cured film can be simplified and complicated manufacturing processes can be shortened (for example, Patent Documents). 1).

In recent years, the miniaturization of transistors, which has supported the high performance of computers, is facing the limit of the scaling law, and the laminated device structure in which semiconductor elements are three-dimensionally laminated for further high performance and high speed is attracting attention. (See, for example, Non-Patent Document 1). Among the laminated device structures, the multi-die fan-out wafer level package (Multi-die Fanout Wafer Level Packaging) is a package manufactured by collectively encapsulating a plurality of dies in one package, and has been conventionally proposed. It is attracting attention because it can be expected to have lower cost and higher performance than the fan-out wafer level package (manufactured by sealing one die in one package).

In the production of multi-die fan-out wafer level packages, low-temperature curability of resins such as polyimide and polybenzoxazole is used from the viewpoint of protecting high-performance dies, protecting encapsulants with low heat resistance, and improving yield. There is a strong demand (see, for example, Patent Document 2).

As a conventional resin composition, for example, Patent Document 3 describes a polyimide precursor composition containing a polyamic acid, a thermal base generator that generates a primary or secondary amine by heating at 200 ° C. or lower, and a solvent. It is disclosed. Patent Document 4 discloses a thermosetting resin composition containing a specific acidic compound and a thermosetting agent containing at least one selected from an ammonium salt having an anion having pKa1 of 0 to 4 and an ammonium cation. ing.

Patent Document 5 discloses a polyimide precursor resin composition containing a photobase generator that produces a primary or secondary amine having an alcoholic hydroxyl group and a polyimide precursor in order to improve the low temperature curability of the polyimide. Has been done. Patent Document 6 discloses a resin composition containing a compound that produces an imidazole derivative by light irradiation or heating, and a polyimide precursor, an epoxy cross-linking agent, polyurethane, or polyurea.

Japanese Unexamined Patent Publication No. 2009-265520 International Publication No. 2008/111470 Japanese Unexamined Patent Publication No. 2007-56196 International Publication No. 2015/199219 Japanese Unexamined Patent Publication No. 2012-102237 Japanese Unexamined Patent Publication No. 2013-139566

"Semiconductor Technology Yearbook 2013 Packaging / Mounting", Nikkei BP Co., Ltd., December 2012, p. 41-50

When a cured film of a polyimide precursor or a polyamide-imide precursor is used for the rewiring layer, it is required to lower the curing temperature in order to suppress thermal loss of electronic parts. In addition, as the degree of integration, functional improvement, and chip size are reduced, the package is multi-layered, so that the cured film is required to have high resistance to chemical solutions such as organic solvents, strong acids, and strong bases. Furthermore, CSP (chip size packaging) and the like capable of high-density mounting have a structure in which the cured film contacts the solder bumps, so that the cured film contacts the flux in the reflow process of the solder bumps, so that high flux resistance is achieved. Required.
However, a resin composition satisfying all of these has not been obtained.

An object of the present invention is to provide a photosensitive resin composition capable of forming a cured film having excellent chemical solution resistance, flux resistance and elongation at break even when cured at a low temperature of 200 ° C. or lower. It also includes a method for producing a pattern cured film using the photosensitive resin composition, a cured film of the photosensitive resin composition, an interlayer insulating film produced using the cured film, and the like, and the interlayer insulating film and the like. To provide electronic components.

（式（１）中、Ｘ^１は４価の芳香族基である。Ｙ^１は２価の芳香族基である。Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、下記式（２）で表される基又は炭素数１〜４の脂肪族炭化水素基であり、Ｒ^１及びＲ^２の少なくとも一方は下記式（２）で表される基である。−ＣＯＯＲ^１基と−ＣＯＮＨ−基とは、互いにオルト位置にあり、−ＣＯＯＲ^２基と−ＣＯ−基とは、互いにオルト位置にある。）

（式（２）中、Ｒ^３〜Ｒ^５は、それぞれ独立に、水素原子又は炭素数１〜３の脂肪族炭化水素基である。ｍは１〜１０の整数である。）
３．前記（Ｂ）成分が、示差走査熱量測定による測定において、１００℃から２００℃の間に塩基発生温度を有する化合物を含む、１又は２に記載の感光性樹脂組成物。
４．前記（Ｂ）成分が、アニオンとカチオンを含むイオン型構造を有する化合物を含む、１〜３のいずれかに記載の感光性樹脂組成物。
５．前記（Ｂ）成分が、下記式（２１）又は（２２）で表される化合物を含む、４に記載の感光性樹脂組成物。

（式（２１）及び（２２）中、Ｒ^２１〜Ｒ^２９は、それぞれ独立に、水素原子、１価の有機基又は２価の有機基である。Ｒ^２１とＲ^２２、Ｒ^２３とＲ^２４、Ｒ^２５とＲ^２９、及びＲ^２６とＲ^２７は、互いに結合して環を形成してもよい。Ｘ^ｎ−は、下記式（２３）〜（２６）のいずれかで表される化合物からｎ個の水素原子を除いたアニオンである。ｎは１〜４の整数である。）

（式（２３）〜（２６）中、Ｒ^３１〜Ｒ^３３は、それぞれ独立に、水素原子、炭素数１〜１０の脂肪族炭化水素基又は炭素数６〜１０の芳香族炭化水素基である。Ｒ^３４は、炭素数１〜１０の脂肪族炭化水素基又は炭素数６〜１０の芳香族基である。Ｒ^３５は、水酸基又はメルカプト基である。ｅ〜ｈは、それぞれ独立に、１〜４の整数である。）
６．前記（Ｂ）成分が、前記アニオンとしてフェノール由来構造又はオルトフタル酸由来構造を含み、前記カチオンとして１，５−ジアザビシクロ［４．３．０］ノン−５−エン由来構造又は１，８−ジアザビシクロ［５．４．０］ウンデカ−７−エン由来構造を含む、４又は５に記載の感光性樹脂組成物。
７．１〜６のいずれかに記載の感光性樹脂組成物を基板上に塗布、乾燥して感光性樹脂膜を形成する工程と、
前記感光性樹脂膜をパターン露光して、樹脂膜を得る工程と、
前記パターン露光後の樹脂膜を、有機溶剤を用いて現像し、パターン樹脂膜を得る工程と、
前記パターン樹脂膜を加熱処理する工程と、
を含むパターン硬化膜の製造方法。
８．前記加熱処理の温度が２００℃以下である７に記載のパターン硬化膜の製造方法。
９．１〜６のいずれかに記載の感光性樹脂組成物を硬化した硬化膜。
１０．パターン硬化膜である９に記載の硬化膜。
１１．９又は１０に記載の硬化膜を用いて作製された層間絶縁膜、カバーコート層又は表面保護膜。
１２．１１に記載の層間絶縁膜、カバーコート層又は表面保護膜を含む電子部品。 As a result of diligent studies in view of the above problems, the present inventors have conducted a combination of a specific polyimide precursor, a thermobase generator and a photopolymerization initiator, and even when cured at a low temperature of 200 ° C. or lower. The present invention has been completed by finding that a cured film satisfying all the above-mentioned characteristics can be obtained.
According to the present invention, the following photosensitive resin compositions and the like are provided.
1. 1. (A) A polyimide precursor having a polymerizable unsaturated bond and
(B) Thermal base generator and
(C) Photopolymerization initiator and
A photosensitive resin composition containing.
2. The photosensitive resin composition according to 1, wherein the component (A) is a polyimide precursor having a structural unit represented by the following formula (1).

(In the formula (1), X ¹ is a tetravalent aromatic group. Y ¹ is a divalent aromatic group. R ¹ and R ² are independently hydrogen atoms, and the following formula (2) It is a group represented by or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and ^{at least one of R 1} and R ² is a group represented by the following formula (2) ^{.-COOR 1} group and -CONH- The groups are in ortho positions with each other, and the ^two -COOR groups and -CO- groups are in ortho positions with each other.)

(In the formula (2), R ^{3 to} R ⁵ are independently hydrogen atoms or aliphatic hydrocarbon groups having 1 to 3 carbon atoms. M is an integer of 1 to 10.)
3. 3. The photosensitive resin composition according to 1 or 2, wherein the component (B) contains a compound having a base generation temperature between 100 ° C. and 200 ° C. in the measurement by differential scanning calorimetry.
4. The photosensitive resin composition according to any one of 1 to 3, wherein the component (B) contains a compound having an ionic structure containing an anion and a cation.
5. The photosensitive resin composition according to 4, wherein the component (B) contains a compound represented by the following formula (21) or (22).

(In formulas (21) and (22), R ^{21 to} R ²⁹ are independently hydrogen atoms, monovalent organic groups or divalent organic groups. R ²¹ and R ²² , R ²³ and R ^{24, respectively.} , R ²⁵ and R ²⁹ , and R ²⁶ and R ²⁷ may be bonded to each other to form a ring. X ⁿ⁻ is derived from a compound represented by any of the following formulas (23) to (26). It is an anion excluding n hydrogen atoms. N is an integer of 1 to 4.)

In formulas (23) to (26), R ^{31 to} R ³³ are independently hydrogen atoms, aliphatic hydrocarbon groups having 1 to 10 carbon atoms, or aromatic hydrocarbon groups having 6 to 10 carbon atoms. R ³⁴ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic group having 6 to 10 carbon atoms. R ³⁵ is a hydroxyl group or a mercapto group. E to h are independently 1 each. It is an integer of ~ 4.
6. The component (B) contains a phenol-derived structure or an orthophthalic acid-derived structure as the anion, and 1,5-diazabicyclo [4.3.0] non-5-ene-derived structure or 1,8-diazabicyclo [as the cation. 5.4.0] The photosensitive resin composition according to 4 or 5, which comprises a structure derived from Undec-7-ene.
A step of applying the photosensitive resin composition according to any one of 7.1 to 6 onto a substrate and drying it to form a photosensitive resin film.
A step of pattern-exposing the photosensitive resin film to obtain a resin film, and
A step of developing the resin film after the pattern exposure with an organic solvent to obtain a pattern resin film, and
The step of heat-treating the pattern resin film and
A method for producing a pattern cured film including.
8. 7. The method for producing a pattern cured film according to 7, wherein the heat treatment temperature is 200 ° C. or lower.
A cured film obtained by curing the photosensitive resin composition according to any one of 9.1 to 6.
10. 9. The cured film according to 9, which is a pattern cured film.
An interlayer insulating film, a cover coat layer or a surface protective film produced by using the cured film according to 11.9 or 10.
An electronic component including the interlayer insulating film, cover coat layer or surface protective film according to 12.11.

According to the present invention, it is possible to provide a photosensitive resin composition having excellent chemical solution resistance, flux resistance and elongation at break even when cured at a low temperature of 200 ° C. or lower. It also includes a method for producing a pattern cured film using the photosensitive resin composition, a cured film of the photosensitive resin composition, an interlayer insulating film produced using the cured film, and the like, and the interlayer insulating film and the like. Electronic components can be provided.

It is the schematic which shows the manufacturing process of the electronic component which concerns on one Embodiment of this invention.

Hereinafter, embodiments of the photosensitive resin composition of the present invention, a method for producing a pattern cured film, a cured film, an interlayer insulating film, a cover coat layer, a surface protective film, and an electronic component will be described in detail. The present invention is not limited to the following embodiments.

As used herein, the term "A or B" may include either A or B, or both. In the present specification, the term "process" is included in this term not only as an independent process but also as long as the desired action of the process is achieved even if it cannot be clearly distinguished from other processes. .. The numerical range indicated by using "~" in the present specification indicates a range including the numerical values before and after "~" as the minimum value and the maximum value, respectively. In the present specification, the content of each component in the composition is the total amount of the plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. means. In the present specification, the exemplary materials may be used alone or in combination of two or more unless otherwise specified. As used herein, the term "(meth) acrylic group" means "acrylic group" and "methacrylic group", and "(meth) acrylate" means "methacrylate" or "acrylate".

[Photosensitive resin composition]
The photosensitive resin composition of the present invention comprises (A) a polyimide precursor having a polymerizable unsaturated bond (hereinafter, also referred to as “component (A)”), and (B) a thermobase generator (hereinafter, “(”. It also contains "B) component") and (C) photopolymerization initiator (hereinafter, also referred to as "(C) component"). The photosensitive resin composition of the present invention is preferably a negative photosensitive resin composition.

Since the photosensitive resin composition of the present invention has the above-mentioned components, it has excellent photosensitive characteristics, and even if it is cured at 200 ° C. or lower, it has excellent chemical resistance and flux equivalent to those of a cured film obtained at high temperature curing. A cured film having resistance and elongation at break can be formed.
Hereinafter, each component will be described.

(Component (A): Polyimide precursor having a polymerizable unsaturated bond)
The component (A) is not particularly limited as long as it is a polyimide precursor having a polymerizable unsaturated bond, but has high transmittance when i-ray is used as a light source at the time of patterning, and when cured at a low temperature of 200 ° C. or lower. A polyimide precursor showing high cured film properties is preferable.
Examples of the polymerizable unsaturated bond include a double bond between carbon atoms.

（式（１）中、Ｘ^１は４価の芳香族基である。Ｙ^１は２価の芳香族基である。Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、下記式（２）で表される基、又は炭素数１〜４の脂肪族炭化水素基であり、Ｒ^１及びＲ^２の少なくとも一方は下記式（２）で表される基である。−ＣＯＯＲ^１基と−ＣＯＮＨ−基とは、互いにオルト位置にあり、−ＣＯＯＲ^２基と−ＣＯ−基とは、互いにオルト位置にある。）

（式（２）中、Ｒ^３〜Ｒ^５は、それぞれ独立に、水素原子又は炭素数１〜３の脂肪族炭化水素基である。ｍは１〜１０の整数（好ましくは２〜１０の整数、より好ましくは２〜５の整数、さらに好ましくは２又は３）である。） The component (A) is preferably a polyimide precursor having a structural unit represented by the following formula (1). As a result, the i-ray transmittance is high, and a good cured film can be formed even when the curing is performed at a low temperature of 200 ° C. or lower.

(In the formula (1), X ¹ is a tetravalent aromatic group. Y ¹ is a divalent aromatic group. R ¹ and R ² are independently hydrogen atoms, and the following formula (2) It is a group represented by, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and ^{at least one of R 1} and R ² is a group represented by the following formula (2): -COOR ¹ group and -CONH. -Groups are in ortho position with each other, and -COOR ² groups and -CO- groups are in ortho position with each other.)

(In the formula (2), R ^{3 to} R ⁵ are independently hydrogen atoms or aliphatic hydrocarbon groups having 1 to 3 carbon atoms. M is an integer of 1 to 10 (preferably an integer of 2 to 10). , More preferably an integer of 2-5, even more preferably 2 or 3)).

^{The tetravalent aromatic group of X 1} of the formula (1) may be a tetravalent aromatic hydrocarbon group (for example, 6 to 20 carbon atoms), or a tetravalent aromatic heterocyclic group (atom). The number may be, for example, 5 to 20). X ¹ is preferably a tetravalent aromatic hydrocarbon group.

（式中、Ｚ^１及びＺ^２は、それぞれ独立に、各々が結合するベンゼン環と共役しない２価の基又は単結合である。Ｚ^３は、エーテル結合（−Ｏ−）又はスルフィド結合（−Ｓ−）である。） Examples of the tetravalent aromatic hydrocarbon group of X ¹ include, but are not limited to, the groups shown below.

(In the formula, Z ¹ and Z ² are independently divalent groups or single bonds that are not conjugated to the benzene ring to which they are bonded. Z ³ is an ether bond (-O-) or a sulfide bond (-O-). S-).)

The ^{divalent groups of Z 1} and Z ² are preferably -O-, -S-, a methylene group, a bis (trifluoromethyl) methylene group, or a difluoromethylene group, more preferably -O-.
Z ³ is preferably −O−.

^{The divalent aromatic group of Y 1 in} the formula (1) may be a divalent aromatic hydrocarbon group (for example, 6 to 20 carbon atoms), or a divalent aromatic heterocyclic group (atom). The number may be, for example, 5 to 20). Y ¹ is preferably a divalent aromatic hydrocarbon group.

（式（３）中、Ｒ^４１〜Ｒ^４８は、それぞれ独立に、水素原子、１価の脂肪族炭化水素基又はハロゲン原子を有する１価の有機基である。） Examples of the divalent aromatic hydrocarbon group of Y ¹ include, but are not limited to, a group represented by the following formula (3).

(In the formula (3), R ^{41 to} R ⁴⁸ are monovalent organic groups each independently having a hydrogen atom, a monovalent aliphatic hydrocarbon group or a halogen atom.)

As the ^{monovalent aliphatic hydrocarbon group of R 41 to} R ⁴⁸ (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), a methyl group is preferable.

The ^{monovalent organic group having a halogen atom (preferably a fluorine atom) of R 41 to} R ⁴⁸ is a monovalent aliphatic hydrocarbon group having a halogen atom (preferably 1 to 10 carbon atoms, more preferably 1 carbon atom). ~ 6) is preferable, and a trifluoromethyl group is preferable.

In formula (3), for example, R ⁴² and R ⁴³ may be monovalent aliphatic hydrocarbon groups (for example, methyl groups), and R ⁴¹ and R ^{44 to} R ⁴⁸ may be hydrogen atoms.

Further, as Y ¹ , a divalent group obtained by removing two hydrogen atoms from diphenyl ether or a divalent group obtained by removing two hydrogen atoms from benzene can also be used.

^{Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms (preferably 1 or 2) of R 1} and R ² of the formula (1) include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group and an n-. Examples include a butyl group.

In formula (1), ^{at least one of R 1} and R ² is a group represented by formula (2), and preferably ^{both R 1} and R ² are groups represented by formula (2).

^{Examples of the aliphatic hydrocarbon group having 1-3 (preferably 1 or 2) carbon atoms of R 3 to} R ⁵ of the formula (2) include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group and the like. Be done. Methyl groups are preferred.

（式（４）中、Ｘ^１は式（１）のＸ^１に対応する基である。式（５）中、Ｙ^１は式（１）で定義した通りである。式（６）中、Ｒ^３〜Ｒ^５及びｍは式（２）で定義した通りである。） The polyimide precursor having the structural unit represented by the formula (1) is, for example, a tetracarboxylic acid dianhydride represented by the following formula (4) and a diamino compound represented by the following formula (5). A polyamic acid is produced by reacting in an organic solvent such as N-methylpyrrolidone, a compound represented by the following formula (6) is added, and the reaction is carried out in an organic solvent to introduce an ester group wholly or partially. It can be manufactured by doing so.

(In the formula (4), ^{X 1} is a group corresponding to ^{X 1} of the formula (1). Equation in (5), ^{Y 1} is as defined in formula (1). Equation (6), R ^{3 to} R ⁵ and m are as defined by equation (2).)

The polyimide precursor having the structural unit represented by the formula (1) can be prepared, for example, by reacting the tetracarboxylic dianhydride represented by the formula (4) with the compound represented by the formula (6) to form an ester. It can also be produced and then reacted with a diamino compound represented by the formula (5).

The tetracarboxylic dianhydride represented by the formula (4) and the diamino compound represented by the formula (5) may be used alone or in combination of two or more.

The content of the structural unit represented by the formula (1) is preferably 50% mol or more, more preferably 80 mol% or more, and 90 mol% or more with respect to all the structural units of the component (A). More preferred. The upper limit is not particularly limited, and may be 100 mol%.

（式（７）中、Ｘ^２は４価の芳香族基である。Ｙ^２は２価の芳香族基である。Ｒ^５１及びＲ^５２は、それぞれ独立に、水素原子又は炭素数１〜４の脂肪族炭化水素基である。−ＣＯＯＲ^５１基と−ＣＯＮＨ−基とは、互いにオルト位置にあり、−ＣＯＯＲ^５２基と−ＣＯ−基とは、互いにオルト位置にある。） The component (A) may have a structural unit other than the structural unit represented by the formula (1). Examples of the structural unit other than the structural unit represented by the formula (1) include the structural unit represented by the following formula (7).

(In the formula (7), X ² is a tetravalent aromatic group. Y ² is a divalent aromatic group. R ⁵¹ and R ⁵² are independently hydrogen atoms or 1 to 4 carbon atoms, respectively. ^{-COOR 51} groups and -CONH- groups are in ortho positions with each other, and -COOR ⁵² groups and -CO- groups are in ortho positions with each other.)

Examples of the X ^{2 tetravalent aromatic group of the formula (7) include the same groups as the X 1} tetravalent aromatic group of the formula (1). Examples of the divalent aromatic group of Y ^2, include the same groups as the divalent aromatic group Y ¹ of the formula (1). Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms of R ⁵¹ and R ⁵² include the same group as the aliphatic hydrocarbon group having 1 to 4 carbon atoms ^{of R 1} and R ^{2 of the formula (1).}

The content of the structural unit other than the structural unit represented by the formula (1) is preferably less than 50 mol% with respect to the total structural unit of the component (A).
As the structural unit other than the structural unit represented by the formula (1), one type may be used alone, or two or more types may be combined.

In the component (A), the ratio of the carboxy group esterified with the group represented by the formula (2) to the total carboxy group and the total carboxy ester in the polyimide precursor is 50 mol% or more. Preferably, 60 to 100 mol% is more preferable, and 70 to 90 mol% is more preferable.

The molecular weight of the component (A) is not particularly limited, but the number average molecular weight is preferably 10,000 to 200,000.
The number average molecular weight is determined by measuring by gel permeation chromatography and converting using a standard polystyrene calibration curve.

(Component (B): Thermal base generator)
A thermobase generator is a compound that generates a base by heat.
The component (B) is preferably a compound having a base generation temperature between 100 ° C. and 200 ° C. in differential scanning calorimetry (hereinafter, also referred to as “DSC”).

The base generation temperature is preferably 200 ° C. or lower, more preferably 180 ° C. or lower. The base generation temperature is preferably 100 ° C. or higher, more preferably 120 ° C. or higher.
When the base generation temperature is 200 ° C. or lower, the base is generated without any problem even when the photosensitive resin composition is cured at a low temperature of 200 ° C. or lower, and the addition effect can be sufficiently exhibited. When the base generation temperature is 100 ° C. or higher, the photosensitive resin composition having excellent stability and handling can be obtained without generating bases during storage or in the process of forming the photosensitive resin film.

The base generation temperature is determined as follows using differential scanning calorimetry. That is, the thermobase generator and the polyimide precursor (polymer I synthesized in Synthesis Example 1 of the present application) are uniformly mixed in tetrahydrofuran (THF, manufactured by Tokyo Kasei Kogyo Co., Ltd.) at a mass ratio of 10:90, and this is mixed. It is applied on a glass substrate and dried at 80 ° C. for 10 minutes to prepare a sample. This sample is placed in a metal pan and heated to 300 ° C. at 10 ° C./min, and the peak temperature of the reaction heat of the polyimide precursor at that time is measured to determine the base generation temperature of the thermal base generator. Specifically, among the measured peaks, the peak temperature attributable to the reaction between the polyimide precursor and the base is defined as the temperature at which the base reacts with the polyimide precursor, that is, the base generation temperature. The lowest peak among the observed peaks is attributed to the reaction between the polyimide precursor and the base. The peak temperature to be read may be exothermic or endothermic depending on the type of reaction between the polyimide precursor and the base.

The base generated from the component (B) is preferably an organic base, more preferably a primary amine, a secondary amine or a tertiary amine, and even more preferably an organic strong base such as amidine or guanidine. The boiling point (1 atm) of the base generated from the component (B) is preferably 100 ° C. or higher, more preferably 140 ° C. or higher.

As the component (B), a compound having an ionic structure containing an anion and a cation is preferable.
As the anion of the compound having an ionic structure, an anion selected from the group consisting of a carboxylic acid anion, a phenol anion, a phosphate anion and a sulfate anion is preferable. Further, from the viewpoint of the base generation temperature, a carboxylic acid anion or a phenol anion is preferable. That is, the thermal base generator is preferably a salt with a carboxylic acid anion or a salt with a phenol anion.
Further, the number of the functional groups (carboxy group, phenolic hydroxyl group, phosphoric acid group and sulfate group) in the anion may be one or two or more.

（式（２３）〜（２６）中、Ｒ^３１〜Ｒ^３３は、それぞれ独立に、水素原子、炭素数１〜１０の脂肪族炭化水素基又は炭素数６〜１０の芳香族炭化水素基である。Ｒ^３４は、炭素数１〜１０の脂肪族炭化水素基又は炭素数６〜１０の芳香族基である。Ｒ^３５は、水酸基又はメルカプト基である。ｅ〜ｈは、それぞれ独立に、１〜４の整数（好ましくは１又は２）である。） As the compound that can be an anion, the compounds represented by the following formulas (23) to (26) are preferable.

In formulas (23) to (26), R ^{31 to} R ³³ are independently hydrogen atoms, aliphatic hydrocarbon groups having 1 to 10 carbon atoms, or aromatic hydrocarbon groups having 6 to 10 carbon atoms. R ³⁴ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic group having 6 to 10 carbon atoms. R ³⁵ is a hydroxyl group or a mercapto group. E to h are independently 1 each. An integer of ~ 4 (preferably 1 or 2).

Examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms of R ^{31 to} R ³⁴ include an alkyl group (for example, a methyl group, an ethyl group, an n-butyl group, an isopropyl group, an ethylhexyl group, an octyl group, etc.) or the alkyl. Examples thereof include a 2- to 4-valent group obtained by removing 1 to 3 hydrogen atoms from the group. Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group, a naphthyl group, and a 2- to tetravalent group obtained by removing 1 to 3 hydrogen atoms from these groups.

（式（２７）及び（２８）中、Ｒ^２１〜Ｒ^２９は、それぞれ独立に、水素原子、１価の有機基又は２価の有機基である。Ｒ^２１とＲ^２２、Ｒ^２３とＲ^２４、Ｒ^２５とＲ^２９、及びＲ^２６とＲ^２７は、互いに結合して環を形成してもよい。） As the compound that becomes a cation of the compound having an ionic structure, a compound represented by the following formula (27) or (28) is preferable.

(In formulas (27) and (28), R ^{21 to} R ²⁹ are independently hydrogen atoms, monovalent organic groups or divalent organic groups. R ²¹ and R ²² , R ²³ and R ^{24, respectively.} , R ²⁵ and R ²⁹ , and R ²⁶ and R ²⁷ may combine with each other to form a ring.)

Examples of the monovalent or divalent organic group of R ^{21 to} R ²⁹ include an aliphatic hydrocarbon group (for example, 1 to 10 carbon atoms) or an aromatic group (for example, 6 to 10 carbon atoms). Examples of the aliphatic hydrocarbon group include an alkyl group (for example, a methyl group, an ethyl group, and a propyl group), an alkylene group obtained by removing one hydrogen atom from the alkyl group, and the like.

When R ²¹ and R ²² , R ²³ and R ²⁴ , R ²⁵ and R ²⁹ , and R ²⁶ and R ²⁷ are bonded to each other to form a ring, the ring is an aliphatic ring (non-aromatic hydrocarbon ring). ), Aromatic ring, heterocycle and the like. The ring may be a single ring or a double ring.
When the above groups are bonded to form a ring, a linking group may be contained, and the linking group includes -CO-, -O-, -NH-, and a divalent aliphatic group (for example, from an alkyl group). 2 selected from the group consisting of a divalent aromatic ring group (for example, a group obtained by removing one hydrogen atom from an aromatic hydrocarbon group such as a phenyl group) and a combination thereof. A valuation linking group can be mentioned. The ring is, for example, a 4- to 8-membered ring, preferably a 5- to 7-membered ring.

Specific examples of the ring include, for example, a pyrrolidine ring, a pyrrol ring, a piperidine ring, a pyridine ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a pyrazine ring, a pyrimidine ring, a hydropyrimidine ring (for example, a tetrahydropyrimidine ring), and a morpholine. Examples thereof include a ring, a thiazine ring, an indole ring, an isoindole ring, a benzimidazole ring, a purine ring, a quinoline ring, an isoquinoline ring, a quinoxalin ring, a cinnoline ring, a carbazole ring, an azepine ring, and a diazepine ring.

式（２１）及び（２２）中、Ｒ^２１〜Ｒ^２９は、それぞれ独立に、水素原子、１価の有機基又は２価の有機基である。Ｒ^２１とＲ^２２、Ｒ^２３とＲ^２４、Ｒ^２５とＲ^２９、及びＲ^２６とＲ^２７は、互いに結合して環を形成してもよい。Ｘ^ｎ−は、上記式（２３）〜（２６）のいずれかで表される化合物からｎ個の水素原子を除いたアニオンである。ｎは１〜４の整数（好ましくは１又は２）である。 As the component (B), a compound represented by the following formula (21) or (22) is preferable.

In formulas (21) and (22), R ^{21 to} R ²⁹ are independently hydrogen atoms, monovalent organic groups or divalent organic groups, respectively. R ²¹ and R ²² , R ²³ and R ²⁴ , R ²⁵ and R ²⁹ , and R ²⁶ and R ²⁷ may combine with each other to form a ring. X ⁿ⁻ is an anion obtained by removing n hydrogen atoms from the compound represented by any of the above formulas (23) to (26). n is an integer of 1 to 4 (preferably 1 or 2).

As a cation of a compound having an ionic structure, 1,8- from the viewpoint that a cured film having excellent chemical resistance and flux resistance can be obtained when the photosensitive resin composition is cured at a low temperature of 200 ° C. or lower. A structure derived from diazabicyclo [5.4.0] undeca-7-ene or a structure derived from 1,5-diazabicyclo [4.3.0] non-5-ene is preferable, and a structure derived from 1,8-diazabicyclo [5.4.0] is preferable. Undec-7-ene-derived structures are particularly preferred.

The component (B) preferably contains a phenol-derived structure or an orthophthalic acid-derived structure as an anion, and a 1,5-diazabicyclo [4.3.0] non-5-ene-derived structure or a cation (generated base species). Includes structure derived from 1,8-diazabicyclo [5.4.0] undec-7-ene. As the cation, a structure derived from 1,8-diazabicyclo [5.4.0] undec-7-ene is particularly preferable.
A thermobase generator having this combination tends to generate an organic strong base when heated at 100 ° C. to 200 ° C.

The content of the component (B) is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the component (A). From the viewpoint of improving the chemical resistance of the cured film and the film forming property, it is more preferably 1 to 20 parts by mass, and further preferably 1 to 10 parts by mass.
When it is within the above range, a practical relief pattern can be easily obtained, and post-development residue in the unexposed portion can be easily suppressed.

式（３１）中、Ｒ^６１は、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、炭素数４〜１０のシクロアルキル基、フェニル基又はトリル基であり、Ｒ^６２は、炭素数１〜１２のアルキル基、炭素数４〜１０のシクロアルキル基、フェニル基又はトリル基である。Ｒ^６１及びＲ^６２は、炭素数１〜８のアルキル基、炭素数４〜６のシクロアルキル基、フェニル基又はトリル基であることが好ましく、炭素数１〜４のアルキル基、炭素数４〜６のシクロアルキル基、フェニル基又はトリル基であることがより好ましく、メチル基、シクロペンチル基、フェニル基又はトリル基であることがさらに好ましい。 (Component (C): Photopolymerization Initiator)
Examples of the photopolymerization initiator include an oxime compound, an acylphosphine oxide compound, an acyldialkoxymethane compound and the like. From the viewpoint of sensitivity, an oxime compound is preferable. As the oxime compound, a compound represented by the following formula (31) is preferable.

In the formula (31), R ⁶¹ is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group, and R ⁶² is It is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group. R ⁶¹ and R ⁶² are preferably an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, a phenyl group or a tolyl group, and an alkyl group having 1 to 4 carbon atoms and 4 to 4 carbon atoms. It is more preferably a cycloalkyl group, a phenyl group or a tolyl group of No. 6, and further preferably a methyl group, a cyclopentyl group, a phenyl group or a tolyl group.

R ⁶³ is a substituted or unsubstituted benzoyl group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted carbazolyl group, and the compound represented by the following formulas (34) to (40) has the formula ( It is preferably a group corresponding to ^{R 63} of 31).

Substituents of a substituted or unsubstituted benzoyl group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted carbazolyl group (hereinafter, also referred to as an arbitrary substituent) include a phenylthio group, an ethyloloxy group, and a carbon number of carbon atoms. Alkyl groups 1 to 20 (eg, methyl group, ethyl group, n-propyl group), halogenated (preferably fluorinated) may have 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1). Examples of the alkoxy group to 8), 2,2-dimethyl-1,3-dioxolan-4-yl) methoxy group, benzoyl group and the like can be mentioned.
Any substituent may further have any of the above-mentioned substituents.

式（３２）中、Ｒ^６１及びＲ^６２は上記式（３１）と同じである。
Ｒ^６４は、−Ｈ、−ＯＨ、−ＣＯＯＨ、−Ｏ（ＣＨ_２）ＯＨ、−Ｏ（ＣＨ_２）_２ＯＨ、−ＣＯＯ（ＣＨ_２）ＯＨ、又は−ＣＯＯ（ＣＨ_２）_２ＯＨであり、−Ｈ、−Ｏ（ＣＨ_２）ＯＨ、−Ｏ（ＣＨ_２）_２ＯＨ、−ＣＯＯ（ＣＨ_２）ＯＨ、又は−ＣＯＯ（ＣＨ_２）_２ＯＨであることが好ましく、−Ｈ、−Ｏ（ＣＨ_２）_２ＯＨ、又は−ＣＯＯ（ＣＨ_２）_２ＯＨであることがより好ましい。

式（３３）中、Ｒ^６１及びＲ^６２は上記式（３１）と同じである。
Ｒ^６５は、炭素数１〜６のアルキル基であり、エチル基であることが好ましい。Ｒ^６６は、炭素数１〜１２のアルキル基、又はアセタール結合を有する有機基であり、メチル基又は後述する式（３７）で表される化合物が有する、式（３３）のＲ^６６に対応する置換基であることが好ましい。ｉは１〜３の整数であり、１又は２であることが好ましい。 The photopolymerization initiator is preferably a compound represented by the following formula (32) or formula (33) from the viewpoint of improving the photocurability.

In the formula (32), R ⁶¹ and R ⁶² are the same as the above formula (31).
R ⁶⁴ is -H, -OH, -COOH, -O (CH ₂ ) OH, -O (CH ₂ ) ₂ OH, -COO (CH ₂ ) OH, or -COO (CH ₂ ) ₂ OH. -H, -O (CH ₂ ) OH, -O (CH ₂ ) ₂ OH, -COO (CH ₂ ) OH, or -COO (CH ₂ ) ₂ OH is preferable, and -H, -O (CH 2) _{2) 2} OH, or -COO _{(CH 2)} and more preferably 2 OH.

In the formula (33), R ⁶¹ and R ⁶² are the same as the above formula (31).
R ⁶⁵ is an alkyl group having 1 to 6 carbon atoms, and is preferably an ethyl group. R ⁶⁶ is an alkyl group having 1 to 12 carbon atoms or an organic group having an acetal bond, and corresponds to ^{R 66} of the formula (33) possessed by a methyl group or a compound represented by the formula (37) described later. It is preferably a substituent. i is an integer of 1 to 3, preferably 1 or 2.

Examples of the compound represented by the above formula (32) include compounds represented by the following formula (34) and the following formula (35). The compound represented by the following formula (34) is available as IRGACURE OXE-01 (manufactured by BASF Japan Ltd.).

Examples of the compound represented by the above formula (33) include compounds represented by the following formula (36) or (37), IRGACURE OXE-02 (manufactured by BASF Japan Ltd.), ADEKA OPTMER N- It is available as 1919 (manufactured by ADEKA CORPORATION).

Further, as the photopolymerization initiator, compounds represented by the following formulas (38) to (40) can also be used.

The content of the component (C) is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and further preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the component (A). 5 parts by mass. Within the above range, photocrosslinking tends to be about the same in the film thickness direction, and a practical relief pattern can be easily obtained.

(Component (D): Cross-linking agent)
Examples of the cross-linking agent include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropandi (meth) acrylate, trimethylolpropantri (meth) acrylate, 1, 4-Butandiol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, styrene, Divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl (meth) acrylate, 1,3- (meth) acryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N- Examples thereof include dimethyl acrylamide and N-methylol acrylamide.

When a cross-linking agent is contained, the content of the cross-linking agent is preferably 1 to 100 parts by mass, more preferably 1 to 75 parts by mass, and 1 to 50 parts by mass with respect to 100 parts by mass of the component (A). It is more preferable to use parts by mass.

(Component (E): Thermal polymerization initiator)
The photosensitive resin composition of the present invention may further contain (E) a thermal polymerization initiator (hereinafter, also referred to as “component (E)”).
The component (E) is not decomposed by heating (drying) for removing the solvent when the photosensitive resin film is formed, but is decomposed by heating during curing to generate radicals, and the polymerization reaction of the component (A) is performed. A compound that promotes is preferred. Therefore, the component (E) is preferably a compound having a decomposition point of 110 ° C. or higher and 200 ° C. or lower, and more preferably a compound having a decomposition point of 110 ° C. or higher and 175 ° C. or lower from the viewpoint of promoting the polymerization reaction at a lower temperature.
Examples of the component (E) include bis (1-phenyl-1-methylethyl) peroxide and the like.

When the component (E) is contained, the content of the component (E) is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the component (A), and 1 for ensuring good flux resistance. ~ 20 parts by mass is more preferable, and 1 to 10 parts by mass is further preferable from the viewpoint of suppressing a decrease in solubility due to decomposition during drying.

(solvent)
The photosensitive resin composition of the present invention usually contains a solvent. Examples of the solvent include the following compounds.
Examples of esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone δ-valerolactone, alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)) , 3-Oxypropionate alkyl esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, etc.) 3-Ethyl propionate, etc.)), 2-oxypropionate alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, 2-methoxypropionate) Methyl, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate))), 2-oxy-2-methylmethyl propionate and 2-oxy-2-methyl Ethyl propionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, Methyl 2-oxobutate, ethyl 2-oxobutate, etc .; as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc .; as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, etc. 3-Heptano , N-methyl-2-pyrrolidone, etc .; as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc .; as sulfoxides, for example, dimethyl sulfoxide, etc .; 3-butoxy-N, N-dimethylpropanamide, etc. Examples thereof include organic solvents such as 3-methoxy-N, N-dimethylpropaneamide and N, N-dimethylacetamide.
The content of the solvent is not particularly limited, but is generally 50 to 1000 parts by mass with respect to 100 parts by mass of the component (A).

(Other ingredients)
In addition to the above components, the photosensitive resin composition of the present invention may contain a coupling agent, a surfactant or a leveling agent, a rust preventive agent, a polymerization inhibitor and the like.

(Coupling agent)
The coupling agent usually reacts with the component (A) to crosslink in the heat treatment after development, or the coupling agent itself polymerizes in the step of heat treatment. Thereby, the adhesiveness between the obtained cured film and the substrate can be further improved.

（式（４１）中、Ｒ^７１及びＲ^７２は、それぞれ独立に、炭素数１〜５のアルキル基である。ｊは１〜１０の整数であり、ｋは１〜３の整数である。） As the coupling agent, a silane coupling agent is preferable.
Preferred silane coupling agents include compounds having a urea bond (-NH-CO-NH-). As a result, the adhesiveness to the substrate can be further improved even when the curing is performed at a low temperature of 200 ° C. or lower.
The compound represented by the following formula (41) is more preferable in that it is excellent in developing adhesiveness when cured at a low temperature.

(In formula (41), R ⁷¹ and R ⁷² are independently alkyl groups having 1 to 5 carbon atoms. J is an integer of 1 to 10, and k is an integer of 1 to 3.)

Specific examples of the compound represented by the formula (41) include ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, and 3-ureidopropyltrimethoxysilane. , 3-Ureidopropyltriethoxysilane, 4-ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane and the like, preferably 3-ureidopropyltriethoxysilane.

As the silane coupling agent, a silane coupling agent having a hydroxy group or a glycidyl group may be used. When a silane coupling agent having a hydroxy group or a glycidyl group and a silane coupling agent having a urea bond in the molecule are used in combination, the adhesiveness of the cured film to the substrate during low temperature curing can be further improved.

Examples of the silane coupling agent having a hydroxy group or a glycidyl group include methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, and tert-. Butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenyl Silanol, Ethylisopropylphenylsilanol, n-butylethylphenylsilanol, Isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, Isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol, 1,4-bis (trihydroxysilyl) benzene, 1,4-bis (methyldihydroxysilyl) benzene, 1,4-bis (ethyldihydroxysilyl) benzene, 1,4-Bis (propyldihydroxysilyl) benzene, 1,4-bis (butyldihydroxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, 1, Examples thereof include 4-bis (dipropylhydroxysilyl) benzene, 1,4-bis (dibutylhydroxysilyl) benzene, and a compound represented by the following formula (42). Among them, the compound represented by the formula (42) is particularly preferable in order to further improve the adhesiveness to the substrate.

（式（４２）中、Ｒ^７３はヒドロキシ基又はグリシジル基を有する１価の有機基であり、Ｒ^７４及びＲ^７５は、それぞれ独立に、炭素数１〜５のアルキル基である。ｏは１〜１０の整数であり、ｐは１〜３の整数である。）

(In formula (42), R ⁷³ is a monovalent organic group having a hydroxy group or a glycidyl group, and R ⁷⁴ and R ⁷⁵ are independently alkyl groups having 1 to 5 carbon atoms. O is 1 It is an integer of 10 and p is an integer of 1 to 3.)

Examples of the compound represented by the formula (42) include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-. Hydroxypropyltriethoxysilane, 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2- Glycydoxyethyl triethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybutyltriethoxysilane, etc. Be done.

The silane coupling agent having a hydroxy group or a glycidyl group preferably further contains a nitrogen atom, and a silane coupling agent having an amino group or an amide bond is preferable.
Examples of the silane coupling agent having an amino group include bis (2-hydroxymethyl) -3-aminopropyltriethoxysilane, bis (2-hydroxymethyl) -3-aminopropyltrimethoxysilane, and bis (2-glycidoxy). Examples thereof include methyl) -3-aminopropyltriethoxysilane and bis (2-hydroxymethyl) -3-aminopropyltrimethoxysilane.

Examples of the silane coupling agent having an amide bond include compounds represented by the following formula (43).
R ^76- (CH ₂ ) _q- CO-NH- (CH ₂ ) _r- Si (OR ⁷⁷ ) ₃ (43)
(In formula (43), R ⁷⁶ is a hydroxy group or a glycidyl group, q and r are independently integers of 1 to 3, and R ⁷⁷ is a methyl group, an ethyl group or a propyl group.)

When a silane coupling agent is used, the content of the silane coupling agent is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and 0.3 by mass with respect to 100 parts by mass of the component (A). 10 parts by mass is more preferable.

(Surfactant or leveling agent)
By containing a surfactant or a leveling agent, coatability (for example, suppression of striation (unevenness of film thickness)) and developability can be improved.

Examples of the surfactant or leveling agent include polyoxyethylene uralyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like. F171 "," F173 "," R-08 "(above, manufactured by DIC Co., Ltd.), product name" Florard FC430 "," FC431 "(above, 3M Japan Co., Ltd.), trade name" Organosiloxane Polymer KP341 "," Examples thereof include "KBM303", "KBM403", and "KBM803" (all manufactured by Shin-Etsu Chemical Industry Co., Ltd.).

When a surfactant or a leveling agent is contained, the content of the surfactant or the leveling agent is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the component (A). It is preferable, and more preferably 0.05 to 3 parts by mass.

(anti-rust)
By containing a rust preventive, it is possible to suppress corrosion and prevent discoloration of copper and copper alloys.
Examples of the rust preventive include a triazole derivative and a tetrazole derivative.
When a rust inhibitor is used, the content of the rust inhibitor is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and 0.5 to 5 parts by mass with respect to 100 parts by mass of the component (A). 3 parts by mass is more preferable.

(Polymerization inhibitor)
By containing a polymerization inhibitor, good storage stability can be ensured.
Examples of the polymerization inhibitor include a radical polymerization inhibitor, a radical polymerization inhibitor and the like.
Examples of the polymerization inhibitor include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, and N-phenyl-2-. Examples thereof include naphthylamine, cuperon, 2,5-torquinone, tannic acid, parabenzylaminophenol, nitrosoamines and the like.

When a polymerization inhibitor is contained, the content of the polymerization inhibitor is 0 with respect to 100 parts by mass of the component (A) from the viewpoint of storage stability of the photosensitive resin composition and heat resistance of the obtained cured film. 0.01 to 30 parts by mass is preferable, 0.01 to 10 parts by mass is more preferable, and 0.05 to 5 parts by mass is further preferable.

Except for the solvent, the photosensitive resin composition of the present invention essentially contains the components (A) to (C), as well as the components (D) and (E), a coupling agent, a surfactant, and a leveling agent. It is composed of one or more components selected from the group consisting of a rust preventive and a polymerization inhibitor, and may contain other unavoidable impurities as long as the effects of the present invention are not impaired.
For example, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, 99% by mass or more, 99.5% by mass or more, 99.9% by mass or more of the photosensitive resin composition of the present invention. Or 100% by mass, excluding the solvent,
Ingredients (A) to (C),
From components (A) to (D) or components (A) to (C), as well as components (D), (E), coupling agents, surfactants, leveling agents, rust inhibitors and polymerization inhibitors. It may consist of one or more components selected from the group.

[Cured film]
The cured film of the present invention can be obtained by curing the above-mentioned photosensitive resin composition. The cured film of the present invention may be used as a pattern cured film or may be used as a cured film without a pattern. The film thickness of the cured film of the present invention is preferably 5 to 20 μm.

[Manufacturing method of pattern cured film]
In the method for producing a pattern cured film of the present invention, the above-mentioned photosensitive resin composition is applied onto a substrate and dried to form a photosensitive resin film, and the photosensitive resin film is pattern-exposed to form a resin film. It includes a step of obtaining, a step of developing the resin film after pattern exposure with an organic solvent to obtain a pattern resin film, and a step of heat-treating the pattern resin film. Thereby, a pattern cured film can be obtained.

A method for producing a cured film without a pattern includes, for example, a step of forming the above-mentioned photosensitive resin film and a step of heat treatment. Further, an exposure step may be provided.

Examples of the substrate include a glass substrate, a semiconductor substrate such as a Si substrate (silicon wafer), _{a metal oxide insulator substrate such as a TiO 2} substrate and a SiO ₂ substrate, a silicon nitride substrate, a copper substrate, and a copper alloy substrate.

The coating method is not particularly limited, but it can be applied using a spinner or the like.

Drying can be performed using a hot plate, an oven, or the like.
The drying temperature is preferably 90 to 150 ° C., and more preferably 90 to 120 ° C. in order to suppress the reaction between the component (A) and the component (B) from the viewpoint of ensuring the dissolution contrast.
The drying time is preferably 30 seconds to 5 minutes.
Drying may be performed twice or more.
As a result, a photosensitive resin film obtained by forming the above-mentioned photosensitive resin composition into a film can be obtained.

The film thickness of the photosensitive resin film is preferably 5 to 100 μm, more preferably 8 to 50 μm, and even more preferably 10 to 30 μm.

The pattern exposure exposes a predetermined pattern through, for example, a photomask.
Examples of the active light beam to be irradiated include ultraviolet rays such as i-rays, visible rays, and radiation, but i-rays are preferable.
As the exposure apparatus, a parallel exposure machine, a projection exposure machine, a stepper, a scanner exposure machine and the like can be used.

By developing, a patterned resin film (patterned resin film) can be obtained. Generally, when a negative photosensitive resin composition is used, the unexposed portion is removed with a developing solution.
As the organic solvent used as the developing solution, the good solvent of the photosensitive resin film can be used alone, or the good solvent and the poor solvent can be appropriately mixed and used.
Good solvents include N-methylpyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, gamma-butyrolactone, α-acetyl-gamma-butyrolactone, cyclopentanone, cyclohexanone. And so on.
Examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and water.

A surfactant may be added to the developer. The amount to be added is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the developing solution.

The developing time can be, for example, twice the time required to immerse and dissolve the photosensitive resin film.
The developing time varies depending on the component (A) used, but is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and even more preferably 20 seconds to 5 minutes from the viewpoint of productivity.

After development, it may be washed with a rinsing liquid.
As the rinsing liquid, distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and the like may be used alone or in an appropriate mixture, or may be used in a stepwise combination. good.

A pattern cured film can be obtained by heat-treating the pattern resin film.
The polyimide precursor of the component (A) may undergo a dehydration ring closure reaction by a heat treatment step to become a corresponding polyimide.

The temperature of the heat treatment is preferably 250 ° C. or lower, more preferably 120 to 250 ° C., and even more preferably 200 ° C. or lower or 150 to 200 ° C.
Within the above range, damage to the substrate and the device can be suppressed to a small extent, the device can be produced with a high yield, and energy saving of the process can be realized.

The heat treatment time is preferably 5 hours or less, more preferably 30 minutes to 3 hours. Within the above range, the cross-linking reaction or the dehydration ring closure reaction can be sufficiently proceeded.
The atmosphere of the heat treatment may be the atmosphere or an inert atmosphere such as nitrogen, but a nitrogen atmosphere is preferable from the viewpoint of preventing oxidation of the patterned resin film.

Examples of the apparatus used for the heat treatment include a quartz tube furnace, a hot plate, a rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, a microwave curing furnace and the like.

[Interlayer insulating film, cover coat layer, surface protective film, electronic components]
The cured film of the present invention can be used as a passivation film, a buffer coat film, an interlayer insulating film, a cover coat layer, a surface protective film, or the like.
By using one or more selected from the group consisting of the passivation film, the buffer coat film, the interlayer insulating film, the cover coat layer, the surface protective film and the like, a highly reliable semiconductor device, a multilayer wiring board, various electronic devices and the like can be used. It is possible to manufacture electronic parts and the like.

An example of a manufacturing process of a semiconductor device which is an electronic component of the present invention will be described with reference to the drawings.
FIG. 1 is a manufacturing process diagram of a semiconductor device having a multi-layer wiring structure, which is an electronic component according to an embodiment of the present invention.
In FIG. 1, a semiconductor substrate 1 such as a Si substrate having a circuit element is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element, and a first conductor layer 3 is formed on the exposed circuit element. It is formed. After that, the interlayer insulating film 4 is formed on the semiconductor substrate 1.

Next, a photosensitive resin layer 5 such as a rubber chloride type or a phenol novolac type is formed on the interlayer insulating film 4, and the window 6A is provided so that the interlayer insulating film 4 of a predetermined portion is exposed by a known photographic etching technique. Be done.

The interlayer insulating film 4 in which the window 6A is exposed is selectively etched to provide the window 6B.
Next, the photosensitive resin layer 5 is removed using an etching solution that corrodes the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B.

Further, using a known photographic etching technique, the second conductor layer 7 is formed and electrically connected to the first conductor layer 3.
When forming a multi-layer wiring structure having three or more layers, the above steps can be repeated to form each layer.

Next, using the above-mentioned photosensitive resin composition, the window 6C is opened by pattern exposure to form the surface protective film 8. The surface protective film 8 protects the second conductor layer 7 from external stress, α rays, and the like, and the obtained semiconductor device is excellent in reliability.
In the above example, the interlayer insulating film can also be formed by using the photosensitive resin composition of the present invention.

Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples. The present invention is not limited to the following examples.

Synthesis Example 1 (Synthesis of Polymer I)
7.07 g of 3,3', 4,4'-diphenyl ether tetracarboxylic acid dianhydride (ODPA) and 4.12 g of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) are N-methylpyrrolidone. It was dissolved in 30 g of (NMP), stirred at 30 ° C. for 4 hours, and then stirred overnight at room temperature to obtain polyamic acid. To this, 9.45 g of trifluoroacetic anhydride was added under water cooling, the mixture was stirred at 45 ° C. for 3 hours, and 7.08 g of 2-hydroxyethyl methacrylate (HEMA) was added. This reaction solution was added dropwise to distilled water, the precipitate was collected by filtration, and dried under reduced pressure to obtain a polyimide precursor (hereinafter referred to as Polymer I).

Using the gel permeation chromatography (GPC) method, the number average molecular weight was determined under the following conditions by standard polystyrene conversion. The number average molecular weight of Polymer I was 40,000. The number average molecular weight was measured using a solution prepared by adding 1 mL of a solvent [THF / dimethylformamide (DMF) = 1/1 (volume ratio)] to 0.5 mg of polymer I.
Measuring device: Detector L4000UV manufactured by Hitachi, Ltd.
Pump: L6000 manufactured by Hitachi, Ltd.
C-R4A Chromatopac manufactured by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5 x 2 Eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.03 mol / L), H ₃ PO ₄ (0.06 mol / L)
Flow rate: 1.0 mL / min, Detector: UV270 nm

Further, the esterification rate of the polymer I (the reaction rate between the carboxy group in the structural unit derived from ODPA and HEMA) was calculated by performing NMR measurement under the following conditions. The esterification rate was 80 mol% with respect to the total carboxy groups (the remaining 20 mol% was carboxy groups).
Measuring equipment: AV400M manufactured by Bruker Biospin
Magnetic field strength: 400MHz
Reference substance: Tetramethylsilane (TMS)
Solvent: Dimethyl sulfoxide (DMSO)

Synthesis Example 2 (Synthesis of Polymer II)
7.07 g of ODPA was dissolved in 30 g of NMP, 5.93 g of HEMA was added, and the mixture was stirred at room temperature for 2 days to obtain an ODPA diester. Thionyl chloride was added thereto under water cooling, and the mixture was stirred for 2 hours. An amine solution prepared by dissolving 2.28 g of 4,4-diaminodiphenyl ether (ODA) and 1.23 g of 1,3-phenylenediamine (MPD) in 10 g of NMP was added dropwise to this solution, and the mixture was stirred for 3 hours. This was added dropwise to distilled water, the precipitate was collected by filtration, and dried under reduced pressure to obtain a polyimide precursor (hereinafter referred to as Polymer II).
The number average molecular weight of Polymer II was determined by the same method as in Synthesis Example 1. The number average molecular weight of Polymer II was 50,000.

Synthesis Example 3 (Synthesis of Polymer III)
3.60 g of 4,4'-biphthalic dianhydride (s-BPDA) and 2.53 g of ODPA are dissolved in 30 g of NMP, 5.93 g of HEMA is added, and the mixture is stirred at room temperature for 2 days to obtain an ODPA diester and an s-BPDA diester. A mixed solution of the body was obtained. Thionyl chloride was added to this reaction solution under water cooling, and the mixture was stirred for 2 hours. An amine solution prepared by dissolving 4.12 g of DMAP in 10 g of NMP was added dropwise to this solution, and the mixture was stirred for 3 hours. This was added dropwise to distilled water, the precipitate was collected by filtration, and dried under reduced pressure to obtain a polyimide precursor (hereinafter referred to as Polymer III).
The number average molecular weight of Polymer III was determined by the same method as in Synthesis Example 1. The number average molecular weight of Polymer III was 50,000.

Examples 1 to 6 and Comparative Examples 1 to 3
[Preparation of photosensitive resin composition]
The photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3 were prepared with the components and blending amounts shown in Table 1. The blending amount in Table 1 is 100 parts by mass of each of the component (B), the component (C) and the solvent with respect to the component (A).
Although not shown in Table 1, the following cross-linking agent (component (D)) was added in Examples 1 to 6 and Comparative Examples 1 to 3.
-Tetraethylene glycol dimethacrylate (20 parts by mass with respect to 100 parts by mass of component (A))
-A-TMMT (manufactured by Shin Nakamura Chemical Industry Co., Ltd., pentaerythritol tetraacrylate, 15 parts by mass with respect to 100 parts by mass of component (A))

In addition, each component used is as follows.

(Component (A): Polyimide precursor having a polymerizable unsaturated bond)
Polymers I-III: Polymers I-III obtained in Synthesis Examples 1-3

Ｂ２：「Ｕ−ＣＡＴ ＳＡ８１０」（サンアプロ株式会社製、ビス（１，８−ジアザビシクロ［５．４．０］ウンデカ−７−エン）のオルトフタル酸塩、下記式で表される化合物、塩基発生温度：１７６℃、発生する塩基：１，８−ジアザビシクロ［５．４．０］ウンデカ−７−エン、塩基の沸点：２４０℃（１気圧））

(Component (B): Thermal base generator)
B1: "U-CAT SA1" (manufactured by San Apro Co., Ltd., phenol salt of 1,8-diazabicyclo [5.4.0] undec-7-ene, compound represented by the following formula, base generation temperature: 152 ° C., Generated base: 1,8-diazabicyclo [5.4.0] undec-7-ene, boiling point of base: 240 ° C (1 atm))

B2: Orthophthalate of "U-CAT SA810" (manufactured by San Apro Co., Ltd., bis (1,8-diazabicyclo [5.4.0] undec-7-ene), compound represented by the following formula, base generation temperature 176 ° C, base generated: 1,8-diazabicyclo [5.4.0] undec-7-ene, boiling point of base: 240 ° C (1 atm))

(Component (C): Photopolymerization Initiator)
C1: "IRUGCURE OXE 02" (manufactured by BASF Japan Ltd., Etanon, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime) )
C2: "PDO" (manufactured by Rambuson, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime)

(solvent)
NMP: N-methylpyrrolidone

[Manufacturing and evaluation of pattern cured film]
(Manufacturing of pattern cured film)
The obtained photosensitive resin composition is spin-coated on a silicon wafer using a coating device "Act8" (manufactured by Tokyo Electron Limited), dried at 100 ° C. for 2 minutes, and then dried at 110 ° C. for 2 minutes to dry. A photosensitive resin film having a film thickness of 13 μm was formed. The development time was set to twice the time required for the obtained photosensitive resin film to be immersed in cyclopentanone and completely dissolved.
A photosensitive resin film was prepared in the same manner as above, and an i-line stepper "FPA-3000iW" (manufactured by Canon Inc.) was used on the obtained photosensitive resin film to apply an i-line of ^{100 to 600 mJ / cm 2 to 50 mJ.} It was irradiated to the exposure in a predetermined pattern at / cm ² increments dose. The exposed resin film was paddle-developed with cyclopentanone using "Act8" for the above development time, and then rinse-washed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a patterned resin film.
The obtained pattern resin film is heated at 175 ° C. for 2 hours in a nitrogen atmosphere using a vertical diffusion furnace "μ-TF" (manufactured by Koyo Thermo System Co., Ltd.) to obtain a pattern cured film (thickness after curing 10 μm). ) Was obtained.

(Evaluation of chemical resistance: rate of change in film thickness)
The obtained pattern cured film was immersed in "Dynatrip 7700" (manufactured by Dynaloy Co., Ltd.) or NMP (chemical solution) heated to 70 ° C. for 30 minutes. Then, the pattern cured film was cooled, washed with acetone, and dried.
Measure the film thickness of the pattern cured film after drying, and divide the absolute value of "(film thickness before immersion in chemical solution)-(film thickness of pattern cured film after drying)" by the film thickness before immersion in chemical solution to make a percentage. The film thickness change rate was calculated and evaluated as follows. The results are shown in Table 1.
(Dynastrip 7700)
◯: Film thickness change rate is 2% or less ×: Film thickness change rate is more than 2% (NMP)
◯: Film thickness change rate is 1.6% or less ×: Film thickness change rate is more than 1.6%

(Evaluation of chemical resistance: presence or absence of cracks, etc.)
The pattern damage was evaluated as follows by observing the pattern cured film after immersion and drying in the above chemical solution with an optical microscope. The results are shown in Table 1.
◯: No cracks or wrinkles were observed.
X: At least one of cracks and wrinkles was observed.

(Evaluation of flux resistance: rate of change in film thickness)
A water-soluble flux "WS-600" (manufactured by Arent Japan Co., Ltd.) was applied to the pattern-cured film obtained in (Production of pattern-cured film), and the film was heated at 245 ° C. for 1 minute on a hot plate. After cooling, it was washed with water heated to 60 ° C. to remove the flux and dried. By measuring the film thickness of the pattern cured film after drying and dividing the absolute value of (film thickness before flux immersion-film thickness of pattern cured film after drying) by the film thickness before flux immersion to obtain a percentage. The film thickness change rate was calculated and evaluated as follows. The results are shown in Table 1.
◯: Film thickness change rate is 7% or less ×: Film thickness change rate is more than 7%

(Evaluation of flux resistance: presence or absence of cracks, etc.)
The pattern damage after the above flux immersion and drying was observed with an optical microscope and the pattern damage was evaluated as follows. The results are shown in Table 1.
◯: No cracks, wrinkles, pattern shape changes, or pattern surface roughness were observed.
X: At least one of cracks, wrinkles, pattern shape change and pattern surface roughness was observed.

(Evaluation of elongation at break)
The photosensitive resin composition obtained in (Production of a pattern cured film) is applied to a 6-inch silicon wafer having a thickness of 625 μm using a coating device “Act8” (manufactured by Tokyo Electron Limited), and the film thickness after curing is applied. Was spin-coated so that the thickness was about 10 μm. ^{The obtained photosensitive resin film was exposed to 400 mJ / cm 2} using a proximity exposure machine "Mask Aligner MA8" (manufactured by Susu Microtech). The exposed resin film was heat-cured at 175 ° C. for 1 hour in a nitrogen atmosphere using a vertical diffusion furnace (manufactured by Koyo Thermo System Co., Ltd.) to obtain a polyimide film (cured film).
Next, the cured film was peeled off with a 4.9% hydrofluoric acid aqueous solution, washed with water, and dried. For the obtained cured film, the absolute value of (length of cured film at break-length of cured film before measurement) was divided by the length of the cured film before measurement to obtain a percentage, which was the average of three measurements. The value was defined as the elongation at break (%) and measured as follows. The results are shown in Table 1.
◯: Breaking elongation is 50% or more ×: Breaking elongation is less than 50%

In Table 1, "-" indicates that the evaluation has not been performed.

The photosensitive resin composition of the present invention can be used for an interlayer insulating film, a cover coat layer or a surface protective film, and the interlayer insulating film, a cover coat layer or a surface protective film of the present invention can be used for an electronic component or the like. Can be done.

1 Semiconductor substrate 2 Protective film 3 1st conductor layer 4 Interlayer insulating film 5 Photosensitive resin layer 6A, 6B, 6C Window 7 2nd conductor layer 8 Surface protective film

Claims (11)

(A) A polyimide precursor having a polymerizable unsaturated bond and
(B) A thermobase generator which is a compound having an ionic structure containing anions and cations (however, acidic compounds are excluded. Acidic compounds are a mixture of ion-exchanged water and tetrahydrofuran by collecting 1 g of the compound in a container. (Mass ratio is water / tetrahydrofuran = 1/4) is added, and the mixture is stirred at room temperature for 1 hour, and the value of the solution measured at 20 ° C. using a pH meter is less than 7. ) And
(C) Photopolymerization initiator and
(However, a polyimide precursor, a thermobase generator represented by the following formula (X-1), and a photopolymerization initiator are contained in a mass ratio of 34: 5: 1). , A polyimide precursor, a thermobase generator represented by the following formula (X-2), and a photopolymerization initiator having a mass ratio of 34: 5: 1, and a polyimide precursor and the following. Excludes those containing the thermobase generator represented by the formula (X-3) and the photopolymerization initiator in a mass ratio of 34: 5: 1) .

The photosensitive resin composition according to claim 1, wherein the component (A) is a polyimide precursor having a structural unit represented by the following formula (1).

(In the formula (1), X ¹ is a tetravalent aromatic group. Y ¹ is a divalent aromatic group. R ¹ and R ² are independently hydrogen atoms, and the following formula (2) It is a group represented by or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and ^{at least one of R 1} and R ² is a group represented by the following formula (2) ^{.-COOR 1} group and -CONH- The groups are in ortho positions with each other, and the ^two -COOR groups and -CO- groups are in ortho positions with each other.)

(In the formula (2), R ^{3 to} R ⁵ are independently hydrogen atoms or aliphatic hydrocarbon groups having 1 to 3 carbon atoms. M is an integer of 1 to 10.) The photosensitive resin composition according to claim 1 or 2, wherein the component (B) contains a compound having a base generation temperature between 100 ° C. and 200 ° C. as measured by differential scanning calorimetry. The photosensitive resin composition according to any one of claims 1 to 3, wherein the component (B) contains a compound represented by the following formula (21) or (22).

(In formulas (21) and (22), R ^{21 to} R ²⁹ are independently hydrogen atoms, monovalent organic groups or divalent organic groups. R ²¹ and R ²² , R ²³ and R ^{24, respectively.} , R ²⁵ and R ²⁹ , and R ²⁶ and R ²⁷ may be bonded to each other to form a ring. X ⁿ⁻ is derived from a compound represented by any of the following formulas (23) to (26). It is an anion excluding n hydrogen atoms. N is an integer of 1 to 4.)

In formulas (23) to (26), R ^{31 to} R ³³ are independently hydrogen atoms, aliphatic hydrocarbon groups having 1 to 10 carbon atoms, or aromatic hydrocarbon groups having 6 to 10 carbon atoms. R ³⁴ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic group having 6 to 10 carbon atoms. R ³⁵ is a hydroxyl group or a mercapto group. E to h are independently 1 each. It is an integer of ~ 4. The component (B) contains a phenol-derived structure or an orthophthalic acid-derived structure as the anion, and 1,5-diazabicyclo [4.3.0] non-5-ene-derived structure or 1,8-diazabicyclo [as the cation. 5.4.0] The photosensitive resin composition according to any one of claims 1 to 4, which comprises a structure derived from undec-7-ene. A step of applying the photosensitive resin composition according to any one of claims 1 to 5 onto a substrate and drying it to form a photosensitive resin film.
A step of pattern-exposing the photosensitive resin film to obtain a resin film, and
A step of developing the resin film after the pattern exposure with an organic solvent to obtain a pattern resin film, and
The step of heat-treating the pattern resin film and
A method for producing a pattern cured film including. The method for producing a pattern cured film according to claim 6 , wherein the temperature of the heat treatment is 200 ° C. or lower. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 5. The cured film according to claim 8 , which is a pattern cured film. An interlayer insulating film, a cover coat layer or a surface protective film produced by using the cured film according to claim 8 or 9. An electronic component including the interlayer insulating film, cover coat layer or surface protective film according to claim 10.

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