JP7318532B2 - Photosensitive resin composition, method for producing patterned cured film, cured film, interlayer insulating film, cover coat layer, surface protective film and electronic component - Google Patents

Description

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

Conventionally, polyimide and polybenzoxazole, which have excellent heat resistance, electrical properties, mechanical properties, etc., have been used for surface protective films and interlayer insulating films of semiconductor devices. In recent years, photosensitive resin compositions obtained by imparting photosensitive properties to these resins themselves have been used, and the use of these can simplify the production process of the patterned cured film and shorten the complicated production process (see, for example, Patent Documents 1).

In recent years, miniaturization of transistors, which has supported high performance of computers, is facing the limits of the scaling law, and stacked device structures that stack semiconductor elements in three dimensions are attracting attention in order to further improve performance and speed. are collecting. Among stacked device structures, multi-die fanout wafer level packaging is a package manufactured by encapsulating a plurality of dies in one package, and has been proposed in the past. It is attracting attention because it can be expected to have lower cost and higher performance than the existing fan-out wafer level package (manufactured by sealing one die in one package).

In the fabrication of multi-die fan-out wafer-level packages, the low-temperature curing properties of resins such as polyimide and polybenzoxazole are important from the standpoint of protecting high-performance dies and sealing materials with low heat resistance and improving yields. It is strongly demanded (see, for example, Patent Document 2).

As a conventional resin composition, for example, Patent Document 3 discloses 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 less, and a solvent. disclosed. Patent Document 4 discloses a thermosetting resin composition containing a specific acidic compound and a thermal base generator containing at least one selected from ammonium salts having an anion with a pKa1 of 0 to 4 and an ammonium cation. there is

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. It is Patent Document 6 discloses a resin composition containing a compound that produces an imidazole derivative upon irradiation with light or heating, a polyimide precursor, an epoxy cross-linking agent, polyurethane or polyurea.

JP 2009-265520 A International Publication No. 2008/111470 JP 2007-56196 A International Publication No. 2015/199219 JP 2012-102237 A JP 2013-139566 A

When using a cured film of a polyimide precursor or a polyamideimide precursor for the rewiring layer, in addition to high resolution for fine patterning, the curing temperature must be low to suppress thermal loss of electronic components. is required. In addition, as the degree of integration and function is improved and the chip size is becoming smaller, the package is required to have multiple layers of wiring, so that the cured film is required to have high resistance to chemicals such as organic solvents, strong acids, and strong bases. In addition, CSP (Chip Size Packaging), which enables high-density mounting, has a structure in which the cured film contacts the solder bumps. requested.
However, a resin composition that satisfies all these requirements has not yet been obtained.

An object of the present invention is to provide a photosensitive resin composition that has high sensitivity and can form a cured film having high chemical resistance and flux resistance even when cured at a low temperature of 200° C. or less, and having excellent adhesiveness and elongation at break. It is to provide things. It also includes a method for producing a patterned 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 interlayer insulating film. It is 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。＊は結合手である。）
３．前記（Ｂ）成分が、下記式（１１）～（１４）のいずれかで表される化合物を含む、１又は２に記載の感光性樹脂組成物。

（式（１１）～（１４）中、Ｒ^１１～Ｒ^１４は、それぞれ独立に、炭素数１～４の脂肪族炭化水素基又は下記式（１５）で表される基である。ａは１～１０の整数であり、少なくとも１つのＲ^１１は下記式（１５）で表される基である。ｂは１～１２の整数であり、少なくとも１つのＲ^１２は下記式（１５）で表される基である。ｃは１～１６の整数であり、少なくとも１つのＲ^１３は下記式（１５）で表される基である。ｄは１～１６の整数であり、少なくとも１つのＲ^１４は下記式（１５）で表される基である。

（式（１５）中、Ｒ^１５～Ｒ^１７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。ｌは０～１０の整数である。＊は結合手である。）
４．前記（Ｃ）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、１～３のいずれかに記載の感光性樹脂組成物。
５．前記（Ｃ）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、１～４のいずれかに記載の感光性樹脂組成物。
６．前記（Ｃ）成分が、下記式（２１）又は（２２）で表される化合物を含む、５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。）
７．前記（Ｃ）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、５又は６に記載の感光性樹脂組成物。
８．１～７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。
９．前記加熱処理の温度が２００℃以下である８に記載のパターン硬化膜の製造方法。
１０．１～７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。
１１．パターン硬化膜である１０に記載の硬化膜。
１２．１０又は１１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。
１３．１２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。The present inventors have made intensive studies in view of the above problems, and found that by combining a specific polyimide precursor, a polymerizable compound having an aliphatic cyclic skeleton, a thermal base generator and a photopolymerization initiator, sensitivity can be improved. The inventors have found that a cured film which satisfies all of the above properties can be obtained even when cured at a high temperature and a low temperature of 200° C. or less, and have completed the present invention.
According to the present invention, the following photosensitive resin composition and the like are provided.
1. (A) a polyimide precursor having a polymerizable unsaturated bond;
(B) a polymerizable compound having an aliphatic cyclic skeleton;
(C) a thermal base generator;
(D) a photoinitiator;
A photosensitive resin composition comprising:
2. 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 formula (1), X ¹ is a tetravalent aromatic group. Y ¹ is a divalent aromatic group. R ¹ and R ² are each independently a hydrogen atom, and the following formula (2) 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 positions to each other, and -COOR ² groups and -CO- groups are in ortho positions to each other.)

(In formula (2), R ³ to R ⁵ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. m is an integer of 1 to 10. * is a bond. be.)
3. 3. The photosensitive resin composition according to 1 or 2, wherein the component (B) contains a compound represented by any one of the following formulas (11) to (14).

(In formulas (11) to (14), R ¹¹ to R ¹⁴ are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following formula (15). a is 1 is an integer of up to 10, at least one R ¹¹ is a group represented by the following formula (15), b is an integer of 1 to 12, and at least one R ¹² is represented by the following formula (15) c is an integer of 1 to 16, at least one R ¹³ is a group represented by the following formula (15), d is an integer of 1 to 16, and at least one R ¹⁴ is It is a group represented by the following formula (15).

(In formula (15), R ¹⁵ to R ¹⁷ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. l is an integer of 0 to 10. * is a bond. be.)
4. 4. The photosensitive resin composition according to any one of 1 to 3, wherein the component (C) contains a compound having a base generation temperature between 100°C and 200°C as measured by differential scanning calorimetry.
5. 5. The photosensitive resin composition according to any one of 1 to 4, wherein the component (C) contains a compound having an ionic structure containing an anion and a cation.
6. 6. The photosensitive resin composition according to 5, wherein the component (C) contains a compound represented by the following formula (21) or (22).

(In formulas (21) and (22), R ²¹ to R ²⁹ are each independently a hydrogen atom, a monovalent organic group or a divalent organic group. 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, and X ^n- is a compound represented by any of the following formulas (23) to (26) It is an anion excluding n hydrogen atoms, where n is an integer from 1 to 4.)

(In formulas (23) to (26), R ³¹ to R ³³ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group 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, eh each independently represents 1 is an integer between ~4.)
7. The component (C) contains a phenol-derived structure or orthophthalic acid-derived structure as the anion, and a 1,5-diazabicyclo[4.3.0]non-5-ene-derived structure or 1,8-diazabicyclo[4.3.0]non-5-ene-derived structure as the cation. 5.4.0] The photosensitive resin composition according to 5 or 6, which contains an undec-7-ene-derived structure.
8. A step of applying the photosensitive resin composition according to any one of 1 to 7 on 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;
a step of developing the resin film after the pattern exposure using an organic solvent to obtain a patterned resin film;
a step of heat-treating the pattern resin film;
A method for producing a patterned cured film comprising:
9. 9. The method for producing a pattern cured film according to 8, wherein the temperature of the heat treatment is 200° C. or less.
10. A cured film obtained by curing the photosensitive resin composition according to any one of 1 to 7.
11. 11. The cured film according to 10, which is a pattern cured film.
12. An interlayer insulating film, a cover coat layer or a surface protective film produced using the cured film as described in 10 or 11.
13. An electronic component comprising the interlayer insulating film, cover coat layer or surface protective film according to 12.

According to the present invention, there is provided a photosensitive resin composition that has high sensitivity and can form a cured film that is excellent in chemical resistance, flux resistance, adhesiveness and elongation at break even when cured at a low temperature of 200° C. or less. can. It also includes a method for producing a patterned 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 interlayer insulating film. Electronic parts 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, method for producing a patterned cured film, cured film, interlayer insulating film, cover coat layer, surface protective film and electronic component of the present invention will be described in detail. It should be noted that the present invention is not limited by the following embodiments.

As used herein, "A or B" may include either A or B, or may include both. As used herein, the term "process" includes not only an independent process, but also when the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. . In this specification, the numerical range indicated using "to" indicates the range including the numerical values before and after "to" as the minimum and maximum values, respectively. As used herein, the content of each component in the composition refers to the total amount of the multiple substances present in the composition when there are multiple substances corresponding to each component in the composition, unless otherwise specified. means. In this specification, unless otherwise specified, the exemplified materials may be used alone, or two or more of them may be used in combination. "(Meth)acrylic group" as used herein means "acrylic group" and "methacrylic group".

[Photosensitive resin composition]
The photosensitive resin composition of the present invention includes (A) a polyimide precursor having a polymerizable unsaturated bond (hereinafter also referred to as "(A) component"), (B) a polymerizable compound having an aliphatic cyclic skeleton (hereinafter also referred to as "(B) component"), (C) thermal base generator (hereinafter also referred to as "(C) component"), and (D) photopolymerization initiator (hereinafter referred to as "(D) Also referred to as "ingredient"). The photosensitive resin composition of the present invention is preferably a negative photosensitive resin composition.

The photosensitive resin composition of the present invention has excellent photosensitivity because it has the above components, and even if it is cured at 200 ° C. or less, it has equivalent chemical resistance, flux resistance, A cured film having adhesive and breaking elongation properties can be formed. In addition, it is possible to form a cured film exhibiting high adhesiveness even after a durability test under hot and humid conditions.
Each component will be described below.

((A) component: 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. Polyimide precursors that exhibit high cured film properties are preferred.
Examples of polymerizable unsaturated bonds include double bonds 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。＊は結合手であり、具体的には、＊は、式（２）で表される基であるＲ^１又はＲ^２が結合する酸素原子と結合する。）Component (A) is preferably a polyimide precursor having a structural unit represented by the following formula (1). As a result, the transmittance of the i-line is high, and even when curing is performed at a low temperature of 200° C. or less, a good cured film can be formed.

(In formula (1), X ¹ is a tetravalent aromatic group. Y ¹ is a divalent aromatic group. R ¹ and R ² are each independently a hydrogen atom, and the following formula (2) 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 ortho to each other, and the —COOR ² and —CO— groups are ortho to each other.)

(In formula (2), R ³ to R ⁵ are each independently a hydrogen atom or an aliphatic hydrocarbon group 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 to 5, more preferably 2 or 3) * is a bond, specifically, * is a group represented by formula (2) R ¹ or R It bonds with the oxygen atom to which ² bonds.)

The tetravalent aromatic group of X ¹ in formula (1) may be a tetravalent aromatic hydrocarbon group (having, for example, 6 to 20 carbon atoms) or a tetravalent aromatic heterocyclic group (atom The number may be, for example, 5-20). 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 for X ¹ include, but are not limited to, the groups shown below.

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

The divalent group of Z ¹ and Z ² is 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 formula (1) may be a divalent aromatic hydrocarbon group (having, for example, 6 to 20 carbon atoms) or a divalent aromatic heterocyclic group (atom The number may be, for example, 5-20). 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 for Y ¹ include, but are not limited to, groups represented by the following formula (3).

(In Formula (3), R ⁴¹ to R ⁴⁸ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group or a monovalent organic group having a halogen atom.)

The monovalent aliphatic hydrocarbon group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms) represented by R ⁴¹ to R ⁴⁸ is preferably a methyl group.

The monovalent organic group having a halogen atom (preferably a fluorine atom) for R ⁴¹ to R ⁴⁸ is a monovalent aliphatic hydrocarbon group having a halogen atom (preferably 1 to 10 carbon atoms, more preferably 1 to 6) are preferred, and a trifluoromethyl group is preferred.

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

Examples of aliphatic hydrocarbon groups having 1 to 4 carbon atoms (preferably 1 or 2) for R ¹ and R ² in formula (1) include methyl group, ethyl group, n-propyl group, 2-propyl group, n- A butyl group and the like can be mentioned.

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

Examples of aliphatic hydrocarbon groups having 1 to 3 carbon atoms (preferably 1 or 2) for R ³ to R ⁵ in formula (2) include methyl group, ethyl group, n-propyl group and 2-propyl group. 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。）A polyimide precursor having a structural unit represented by the formula (1) is, for example, a tetracarboxylic 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 mixture is reacted in an organic solvent to introduce an ester group wholly or partially. It can be manufactured by

(In formula (4), X ¹ is a group corresponding to X ¹ in formula (1). In formula (5), Y ¹ is as defined in formula (1). In formula (6), R ³ to R ⁵ and m are as defined in Formula (2).)

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

The content of the structural unit represented by formula (1) is preferably 50% by mol or more, more preferably 80% by mol or more, and more preferably 90% by mol or more, based on the total structural units of 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 formula (1). Structural units other than the structural unit represented by formula (1) include structural units represented by the following formula (7).

(In formula (7), X ² is a tetravalent aromatic group. Y ² is a divalent aromatic group. R ⁵¹ and R ⁵² are each independently a hydrogen atom or a C 1-4 —COOR ⁵¹ group and —CONH— group are in ortho position to each other, and —COOR ⁵² group and —CO— group are in ortho position to each other.)

Examples of the tetravalent aromatic group for ^X2 in formula (7) include the same groups as the tetravalent aromatic group for ^X1 in formula (1). The divalent aromatic group for Y ² includes the same divalent aromatic group for Y ¹ in formula (1). Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms for R ⁵¹ and R ⁵² include the same aliphatic hydrocarbon groups having 1 to 4 carbon atoms for R ¹ and R ² in formula (1).

The content of structural units other than the structural units represented by formula (1) is preferably less than 50 mol % of all structural units of component (A).
Structural units other than the structural unit represented by formula (1) may be used singly or in combination of two or more.

In component (A), the proportion of carboxyl groups esterified with the group represented by formula (2) is 50 mol% or more with respect to all carboxyl groups and all carboxyesters in the polyimide precursor. It is preferably 60 to 100 mol %, more preferably 70 to 90 mol %.

The molecular weight of component (A) is not particularly limited, but the number average molecular weight is preferably from 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): Polymerizable compound having an aliphatic cyclic skeleton)
By containing the component (B), the photosensitive resin composition of the present invention can impart hydrophobicity to the resulting cured film, and can suppress deterioration in adhesion between the cured film and the substrate under high temperature and high humidity conditions.

The number of ring-forming carbon atoms in the aliphatic cyclic skeleton is preferably 4-15, more preferably 5-12.

Component (B) preferably has a polymerizable unsaturated double bond-containing group, and contains a polymerizable unsaturated double bond in order to improve crosslink density and photosensitivity and suppress pattern swelling after development. It is preferred to have two or three groups.
Component (B) is preferably a compound having a (meth)acrylic group polymerizable with a photopolymerization initiator.

（式（１１）～（１４）中、Ｒ^１１～Ｒ^１４は、それぞれ独立に、炭素数１～４の脂肪族炭化水素基又は下記式（１５）で表される基である。ａは１～１０の整数であり、少なくとも１つ（好ましくは２つ又は３つ）のＲ^１１は下記式（１５）で表される基である。ｂは１～１２の整数であり、少なくとも１つ（好ましくは２つ又は３つ）のＲ^１２は下記式（１５）で表される基である。ｃは１～１６の整数であり、少なくとも１つ（好ましくは２つ又は３つ）のＲ^１３は下記式（１５）で表される基である。ｄは１～１６の整数であり、少なくとも１つ（好ましくは２つ）のＲ^１４は下記式（１５）で表される基である。式（１３）においてＲ^１３は脂肪族環状骨格の全ての置換位置に結合可能であり、式（１４）においてＲ^１４は脂肪族環状骨格の全ての置換位置に結合可能である。）

（式（１５）中、Ｒ^１５～Ｒ^１７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。ｌは０～１０の整数（好ましくは０、１又は２）である。＊は結合手である。）Examples of the component (B) include, but are not limited to, compounds represented by the following formulas (11) to (14).

(In formulas (11) to (14), R ¹¹ to R ¹⁴ are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following formula (15). a is 1 is an integer of to 10, and at least one (preferably two or three) R ¹¹ is a group represented by the following formula (15), b is an integer of 1 to 12, and at least one ( preferably 2 or 3) R ¹² is a group represented by the following formula (15), c is an integer of 1 to 16, and at least 1 (preferably 2 or 3) R ¹³ is a group represented by the following formula (15), d is an integer of 1 to 16, and at least one (preferably two) R ¹⁴ is a group represented by the following formula (15). In formula (13), R ¹³ can be bonded to all substitution positions of the aliphatic cyclic skeleton, and in formula (14), R ¹⁴ can be bonded to all substitution positions of the aliphatic cyclic skeleton.)

(In formula (15), R ¹⁵ to R ¹⁷ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. l is an integer of 0 to 10 (preferably 0, 1 or 2 ).* is a bond.)

Aliphatic hydrocarbon groups having 1 to 4 carbon atoms for R ¹¹ to R ¹⁴ in formulas (11) to (14) include aliphatic hydrocarbon groups having 1 to 4 carbon atoms for R ¹ and R ² in formula (1). The same group as the group can be mentioned.
The aliphatic hydrocarbon group having 1 to 3 carbon atoms for R ¹⁵ to R ¹⁷ in formula (15) is the same as the aliphatic hydrocarbon group having 1 to 3 carbon atoms for R ³ to R ⁵ in formula (2). is mentioned.

The content of component (B) is preferably 1 to 50 parts by mass with respect to 100 parts by mass of component (A), and more preferably 5 to 50 parts by mass from the viewpoint of improving the hydrophobicity of the cured film. It is preferably 5 to 30 parts by mass. Within the above range, it is easy to obtain a practical relief pattern, and it is easy to suppress the post-development residue in the unexposed area.

((C) component: thermal base generator)
A thermal base generator is a compound that generates a base by heat.
Component (C) is preferably a compound having a base generation temperature between 100° C. and 200° C. in differential scanning calorimetry.

The base generation temperature is preferably 200°C or lower, more preferably 180°C or lower. Moreover, the base generation temperature is preferably 100° C. or higher, more preferably 110° C. or higher.
If the base generation temperature is 200° C. or less, the base is generated without any problem even when the photosensitive resin composition is cured at a low temperature of 200° C. or less, and the effect of addition can be fully exhibited. If the base generating temperature is 100° C. or higher, a photosensitive resin composition excellent in stability and handling can be obtained without generating a base during storage or in the process of forming a photosensitive resin film.

The base generation temperature is determined using differential scanning calorimetry as follows. That is, a thermal base generator and a polyimide precursor (Polymer I synthesized in Synthesis Example 1 of the present application) were uniformly mixed in tetrahydrofuran (THF, manufactured by Tokyo Chemical Industry Co., Ltd.) at a mass ratio of 10:90. It is coated on a glass substrate and dried at 80° C. for 10 minutes to obtain 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 attributed 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. Among the observed peaks, the peak on the lowest temperature side 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 component (C) is preferably an organic base, more preferably a primary amine, a secondary amine or a tertiary amine, and more preferably an organic strong base such as amidine or guanidine. The boiling point (1 atm) of the base generated from component (C) is preferably 100°C or higher, more preferably 140°C or higher.

As component (C), a compound having an ionic structure containing an anion and a cation is preferred.
The anion of the compound having an ionic structure is preferably an anion selected from the group consisting of carboxylate anion, phenol anion, phosphate anion and sulfate anion. Carboxylate anions or phenol anions are preferred from the viewpoint of base generation temperature. That is, the thermal base generator is preferably a salt with a carboxylate anion or a salt with a phenol anion.
Moreover, 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。）Compounds represented by the following formulas (23) to (26) are preferable as compounds that can serve as anions.

(In formulas (23) to (26), R ³¹ to R ³³ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group 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, eh each independently represents 1 An integer of ~4 (preferably 1 or 2).)

The aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by R ³¹ to R ³⁴ includes an alkyl group (eg, methyl group, ethyl group, n-butyl group, isopropyl group, ethylhexyl group, octyl group, etc.), or the alkyl group Examples thereof include an alkylene group obtained by removing one or two hydrogen atoms from the group. Examples of aromatic hydrocarbon groups having 6 to 10 carbon atoms include phenyl group and naphthyl group.

（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。）A compound represented by the following formula (27) or (28) is preferable as a compound that serves as a cation of a compound having an ionic structure.

(In formulas (27) and (28), R ²¹ to R ²⁹ are each independently a hydrogen atom, a monovalent organic group or a divalent organic group. 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.)

The monovalent or divalent organic groups of R ²¹ to R ²⁹ include aliphatic hydrocarbon groups (eg, 1 to 10 carbon atoms) and aromatic groups (eg, 6 to 10 carbon atoms). The aliphatic hydrocarbon group includes an alkyl group (eg, methyl group, ethyl group, propyl group), or an alkylene group obtained by removing one hydrogen atom from the alkyl group.

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 may be an aliphatic ring (non-aromatic hydrocarbon ring ), aromatic rings, heterocyclic rings, and the like. The ring may be monocyclic or polycyclic.
When the above groups combine to form a ring, a linking group may be included, and the linking group includes -CO-, -O-, -NH-, a divalent aliphatic group (e.g., from an alkyl group to a group with two hydrogen atoms removed), a divalent aromatic ring group (e.g., a group with two hydrogen atoms removed from an aromatic hydrocarbon group such as benzene), and a divalent selected from the group consisting of combinations thereof A connecting group of The ring is, for example, a 4- to 8-membered ring, preferably a 5- to 7-membered ring.

Specific examples of rings include pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyrazine ring, morpholine ring, thiazine ring, indole ring, isoindole ring, benzo imidazole ring, purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, cinnoline ring, carbazole ring and the like.

式（２１）及び（２２）中、Ｒ^２１～Ｒ^２９は、上記式（２７）及び（２８）で述べた通りである。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 component (C), a compound represented by the following formula (21) or (22) is preferable.

In formulas (21) and (22), R ²¹ to R ²⁹ are as described for formulas (27) and (28) above. 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- A structure derived from diazabicyclo[5.4.0]undec-7-ene or a structure derived from 1,5-diazabicyclo[4.3.0]non-5-ene is preferred, and 1,8-diazabicyclo[5.4.0] Undec-7-ene derived structures are particularly preferred.

In component (C), the anion part is a structure derived from phenol or orthophthalic acid, and the base species generated is a structure derived from 1,8-diazabicyclo[5.4.0]undec-7-ene or 1,5 -diazabicyclo[4.3.0]non-5-ene derived structures are preferred, and 1,8-diazabicyclo[5.4.0]undec-7-ene derived structures are particularly preferred.
A thermal base generator having this combination tends to generate a strong organic base when heated at 100°C to 200°C.

The content of component (C) is preferably 1 to 50 parts by mass per 100 parts by mass of component (A). From the viewpoint of improving chemical resistance of the cured film and film-forming properties, the amount is more preferably 1 to 20 parts by mass, more preferably 1 to 10 parts by mass. Within this range, it is easy to obtain a practical relief pattern, and it is easy to suppress post-development residues in unexposed areas.

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。((D) component: photopolymerization initiator)
Examples of photopolymerization initiators include oxime compounds, acylphosphine oxide compounds, acyldialkoxymethane compounds, and the like. From the viewpoint of sensitivity, oxime compounds are preferred. As the oxime compound, a compound represented by the following formula (31) is preferable.

In 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; A cycloalkyl group of 6, a phenyl group or a tolyl group is more preferred, and a methyl group, a cyclopentyl group, a phenyl group or a tolyl group is even more preferred.

R ⁶³ is a substituted or unsubstituted benzoyl group, a substituted or unsubstituted fluorenyl group or a substituted or unsubstituted carbazolyl group, and the compounds represented by formulas (34) to (40) described later have 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 optional substituents) include a phenylthio group, an ethyloloxy group, a carbon number 1 to 20 alkyl groups (e.g., methyl group, ethyl group, n-propyl group), optionally halogenated (preferably fluorinated) 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 8) alkoxy group, 2,2-dimethyl-1,3-dioxolan-4-yl)methoxy group, benzoyl group and the like.
Optional substituents may further have any of the substituents described above.

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。From the viewpoint of improving photocurability, the photopolymerization initiator is preferably a compound represented by the following formula (32) or (33).

In formula (32), R ⁶¹ and R ⁶² are the same as in formula (31) above.
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, and —H, —O(CH ₂ ) ₂ OH or -COO(CH ₂ ) ₂ OH is more preferred.

In formula (33), R ⁶¹ and R ⁶² are the same as in formula (31) above.
R ⁶⁵ is an alkyl group having 1 to 6 carbon atoms, 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 formula (33) possessed by a methyl group or a compound represented by 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 formulas (34) and (35). A 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 Optomer N- 1919 (manufactured by ADEKA Corporation).

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

The content of component (D) is preferably from 0.1 to 20 parts by mass, more preferably from 0.1 to 10 parts by mass, still more preferably from 0.1 to 10 parts by mass, relative to 100 parts by mass of component (A). 5 parts by mass. Within the above range, the degree of photocrosslinking tends to be the same in the film thickness direction, making it easier to obtain a practical relief pattern.

((E) component: 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) does not decompose by heating (drying) for removing the solvent during the formation of the photosensitive resin film, but decomposes by heating during curing to generate radicals. A compound that accelerates the polymerization reaction of components (A) and (B) 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.
Component (E) includes bis(1-phenyl-1-methylethyl)peroxide and the like.

When component (E) is contained, the content of component (E) is preferably 0.5 to 20 parts by mass per 100 parts by mass of component (A). It is more preferably 1 to 20 parts by mass, and more preferably 1 to 10 parts by mass from the viewpoint of suppressing a decrease in solubility due to decomposition during drying.

(solvent)
The photosensitive resin composition of the invention usually contains a solvent. Examples of solvents include the following compounds.
Esters such as 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 (e.g., methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)) , 3-oxypropionic acid alkyl esters (e.g., methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxyethyl propionate, etc.), 2-oxypropionate alkyl esters (e.g., methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (e.g., 2-methoxypropionate methyl, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and 2-oxy-2-methyl ethyl propionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate; ethers such as 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; ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like; aromatic hydrocarbons such as toluene, xylene, anisole, limonene and the like; sulfoxides such as dimethylsulfoxide and the like; and N,N-dimethylacetamide and the like.
Although the content of the solvent is not particularly limited, it is generally 50 to 1000 parts by weight per 100 parts by weight of component (A).

(other ingredients)
The photosensitive resin composition of the present invention may contain a coupling agent, a surfactant or a leveling agent, an antirust agent, a polymerization inhibitor, etc., in addition to the above components.

(coupling agent)
The coupling agent is usually crosslinked by reacting with the component (A) in heat treatment after development, or the coupling agent itself polymerizes in the heat treatment step. Thereby, the adhesiveness between the resulting 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。）A silane coupling agent is preferable as the coupling agent.
Preferred silane coupling agents include compounds having a urea bond (--NH--CO--NH--). As a result, even when curing is performed at a low temperature of 200° C. or less, the adhesiveness to the substrate can be further enhanced.
A compound represented by the following formula (41) is more preferable in that it exhibits excellent adhesiveness when cured at a low temperature.

(In formula (41), R ⁷¹ and R ⁷² are each independently an alkyl group 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 formula (41) include ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, and 3-ureidopropyltrimethoxysilane. , 3-ureidopropyltriethoxysilane, 4-ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane and the like, preferably 3-ureidopropyltriethoxysilane.

A silane coupling agent having a hydroxyl group or a glycidyl group may be used as the silane coupling agent. The combined use of a silane coupling agent having a hydroxy group or a glycidyl group and a silane coupling agent having an intramolecular urea bond can further improve the adhesion of the cured film to the substrate during low-temperature curing.

Silane coupling agents having a hydroxy group or a glycidyl group include methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, 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, 4-bis(dipropylhydroxysilyl)benzene, 1,4-bis(dibutylhydroxysilyl)benzene, compounds represented by the following formula (42), and the like. 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; R ⁷⁴ and R ⁷⁵ are each independently an alkyl group having 1 to 5 carbon atoms; o is 1; is an integer from 1 to 10, and p is an integer from 1 to 3.)

Compounds represented by formula (42) include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3- Hydroxypropyltriethoxysilane, 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2- glycidoxyethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybutyltriethoxysilane and the like. be done.

A 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.
Silane coupling agents having an amino group include bis(2-hydroxymethyl)-3-aminopropyltriethoxysilane, bis(2-hydroxymethyl)-3-aminopropyltrimethoxysilane, bis(2-glycidoxy methyl)-3-aminopropyltriethoxysilane, bis(2-hydroxymethyl)-3-aminopropyltrimethoxysilane and the like.

Silane coupling agents 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 each independently an integer 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, more preferably 0.3, per 100 parts by mass of component (A). ~10 parts by mass is more preferable.

(Surfactant or leveling agent)
By containing a surfactant or a leveling agent, it is possible to improve coatability (for example, suppression of striation (unevenness in film thickness)) and developability.

Examples of surfactants or leveling agents include polyoxyethylene uralyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenol ether. F171”, “F173”, “R-08” (manufactured by DIC Corporation), trade names “Fluorard FC430”, “FC431” (manufactured by 3M Japan Ltd.), trade name “organosiloxane polymer KP341”, "KBM303", "KBM403", "KBM803" (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

When a surfactant or leveling agent is included, the content of the surfactant or leveling agent is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of component (A). Preferably, 0.05 to 3 parts by mass is more preferable.

(anti-rust)
Containing a rust inhibitor can suppress corrosion and prevent discoloration of copper and copper alloys.
Rust inhibitors include, for example, triazole derivatives and tetrazole derivatives.
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, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of component (A). 3 parts by mass is more preferable.

(Polymerization inhibitor)
Good storage stability can be ensured by containing a polymerization inhibitor.
Examples of polymerization inhibitors include radical polymerization inhibitors and radical polymerization inhibitors.
Examples of polymerization inhibitors include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N-phenyl-2- naphthylamine, cupferron, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines and the like.

When a polymerization inhibitor is contained, the content of the polymerization inhibitor is 0 per 100 parts by mass of component (A) from the viewpoint of the storage stability of the photosensitive resin composition and the heat resistance of the resulting cured film. 0.01 to 30 parts by weight is preferred, 0.01 to 10 parts by weight is more preferred, and 0.05 to 5 parts by weight is even more preferred.

Except for the solvent, the photosensitive resin composition of the present invention consists essentially of components (A) to (D), component (E), a coupling agent, a surfactant, a leveling agent, an antirust agent and It may consist of one or more components selected from the group consisting of polymerization inhibitors, and may contain other unavoidable impurities within a range that does not impair the effects of the present invention.
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 weight, excluding solvents,
(A) to (D) components,
Selected from the group consisting of (A) to (E) components, or (A) to (D) components, and (E) component, coupling agents, surfactants, leveling agents, rust inhibitors and polymerization inhibitors It may consist of one or more components.

[Cured film]
The cured film of the present invention can be obtained by curing the photosensitive resin composition described above. The cured film of the present invention may be used as a patterned cured film or as a patternless cured film. The film thickness of the cured film of the present invention is preferably 5 to 20 μm.

[Method for producing patterned cured film]
In the method for producing a patterned cured film of the present invention, the above photosensitive resin composition is coated on a substrate and dried to form a photosensitive resin film, and the photosensitive resin film is pattern-exposed to form a resin film. developing the patterned resin film with an organic solvent to obtain a patterned resin film; and heat-treating the patterned resin film. Thereby, a pattern cured film can be obtained.

A method for producing a cured film having no pattern includes, for example, the steps of forming the above-described photosensitive resin film and performing a heat treatment. Furthermore, you may provide the process of exposing.

Examples of the substrate include glass substrates, semiconductor substrates such as Si substrates (silicon wafers), metal oxide insulator substrates such as _TiO2 substrates and _SiO2 substrates, silicon nitride substrates, copper substrates, copper alloy substrates, and the like.

The coating method is not particularly limited, but can be performed 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, more preferably 90 to 120°C in order to suppress the reaction between the components (A) and (D) 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 formed by forming the above 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, even more preferably 10 to 30 μm.

In pattern exposure, for example, a predetermined pattern is exposed through a photomask.
The actinic rays to be irradiated include ultraviolet rays such as i-rays, visible rays, and radiation, but i-rays are preferred.
As an exposure device, a parallel exposure machine, a projection exposure machine, a stepper, a scanner exposure machine, or the like can be used.

By developing, a patterned resin film (patterned resin film) can be obtained. In general, when a negative photosensitive resin composition is used, the unexposed area is removed with a developer.
As the organic solvent used as the developer, a good solvent for the photosensitive resin film can be used alone, or a good solvent and a poor solvent can be appropriately mixed and used.
Good solvents include N-methylpyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, gamma-butyrolactone, α-acetyl-gamma-butyrolactone, cyclopentanone, cyclohexanone. etc.
Poor solvents 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, per 100 parts by mass of the developer.

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

After development, washing may be performed with a rinse liquid.
As the rinse liquid, distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. may be used singly 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 in the heat treatment step to form the corresponding polyimide.

The temperature of the heat treatment is preferably 250°C or lower, more preferably 120 to 250°C, and further preferably 200°C or lower or 150 to 200°C.
Within the above range, damage to substrates and devices can be minimized, devices can be produced with high yield, and energy saving in the process can be realized.

The heat treatment time is preferably 5 hours or less, more preferably 30 minutes to 3 hours. By being within the above range, the cross-linking reaction or the dehydration ring-closing reaction can proceed sufficiently.
The atmosphere of the heat treatment may be the air or an inert atmosphere such as nitrogen, but the nitrogen atmosphere is preferable from the viewpoint of preventing the pattern resin film from being oxidized.

Devices used for the heat treatment include quartz tube furnaces, hot plates, rapid thermal annealing, vertical diffusion furnaces, infrared curing furnaces, electron beam curing furnaces, microwave curing furnaces, and the like.

[Interlayer insulating film, cover coat layer, surface protective film, electronic component]
The cured film of the present invention can be used as a passivation film, buffer coat film, interlayer insulating film, cover coat layer, surface protective film, or the like.
Using one or more selected from the group consisting of the passivation film, buffer coat film, interlayer insulating film, cover coat layer, surface protective film, etc., highly reliable semiconductor devices, multilayer wiring boards, various electronic devices, etc. Electronic parts and the like can be manufactured.

An example of the manufacturing process of the semiconductor device, which is the 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 multilayer 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 circuit elements is covered with a protective film 2 such as a silicon oxide film except for predetermined portions of the circuit elements, and a first conductor layer 3 is formed on the exposed circuit elements. It is formed. After that, an interlayer insulating film 4 is formed on the semiconductor substrate 1 .

Next, a photosensitive resin layer 5 made of chlorinated rubber, phenol novolac, or the like is formed on the interlayer insulating film 4, and a window 6A is provided by a known photolithography technique so that a predetermined portion of the interlayer insulating film 4 is exposed. be done.

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

Further, using a known photolithography technique, the second conductor layer 7 is formed and electrically connected to the first conductor layer 3 .
In the case of forming a multilayer wiring structure having three or more layers, the above steps can be repeated to form each layer.

Next, using the photosensitive resin composition described above, the windows 6C are opened by pattern exposure, and the surface protection film 8 is formed. The surface protective film 8 protects the second conductor layer 7 from external stress, α-rays, etc., and the resulting semiconductor device has excellent reliability.
In the above examples, it is also possible to form the interlayer insulating film using the photosensitive resin composition of the present invention.

The present invention will be specifically described below based on examples and comparative examples. It should be noted that 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′-diphenylethertetracarboxylic dianhydride (ODPA) and 4.12 g of 2,2′-dimethylbiphenyl-4,4′-diamine (DMAP) were added to N-methylpyrrolidone. The solution was dissolved in 30 g of (NMP), stirred at 30° C. for 4 hours, and then stirred overnight at room temperature to obtain a polyamic acid. 9.45 g of trifluoroacetic anhydride was added thereto under water cooling, stirred at 45° C. for 3 hours, and 7.08 g of 2-hydroxyethyl methacrylate (HEMA) was added. This reaction liquid was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyimide precursor (hereinafter referred to as polymer I).
A gel permeation chromatography (GPC) method was used to determine the number average molecular weight under the following conditions by standard polystyrene conversion. Polymer I had a number average molecular weight of 40,000.
The number average molecular weight was measured using a solution in which 1 mL of a solvent [tetrahydrofuran (THF)/dimethylformamide (DMF) = 1/1 (volume ratio)] was added to 0.5 mg of polymer I.
Measuring device: Detector L4000UV manufactured by Hitachi, Ltd.
Pump: L6000 manufactured by Hitachi, Ltd.
Shimadzu Corporation C-R4A Chromatopac
Measurement conditions: Column Gelpack GL-S300MDT-5 x 2 Eluent: THF/DMF = 1/1 (volume ratio)
LiBr (0.03 mol/L), _H3PO4 ( _0.06 mol/L)
Flow rate: 1.0 mL/min, detector: UV270 nm

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

Examples 1 to 5 and Comparative Example 1
[Preparation and Evaluation of Photosensitive Resin Composition]
(Preparation of photosensitive resin composition)
The photosensitive resin compositions of Examples 1 to 5 and Comparative Example 1 were prepared using the components and blending amounts shown in Table 1. The blending amounts in Table 1 are parts by mass of components (B) to (E) and solvent for 100 parts by mass of polymer I.
The components used are as follows.

((A) component: polyimide precursor having a polymerizable unsaturated bond)
Polymer I: Polymer I obtained in Synthesis Example 1

(Component (B): Polymerizable compound having an aliphatic cyclic skeleton)
B1: "A-DCP" (manufactured by Shin-Nakamura Chemical Co., Ltd., tricyclodecanedimethanol diacrylate, compound represented by the following formula)

Ｃ２：「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））

((C) component: thermal base generator)
C1: "U-CAT SA1" (manufactured by San-Apro Co., Ltd., 1,8-diazabicyclo[5.4.0]undec-7-ene phenol salt, 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))

C2: "U-CAT SA810" (manufactured by San-Apro Co., Ltd., bis(1,8-diazabicyclo[5.4.0]undec-7-ene) orthophthalate, compound represented by the following formula, base generation temperature : 176 ° C., generated base: 1,8-diazabicyclo[5.4.0]undec-7-ene, boiling point of base: 240 ° C. (1 atm))

((D) component: photopolymerization initiator)
D1: "IRUGCURE OXE 02" (manufactured by BASF Japan Ltd., ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime) )
D2: "PDO" (1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime manufactured by Lambuson)

((E) component: thermal polymerization initiator)
E1: "Percumyl D" (manufactured by NOF Co., Ltd., bis (1-phenyl-1-methylethyl) peroxide, a compound represented by the following formula)

(solvent)
NMP: N-methylpyrrolidone

(Evaluation of sensitivity)
The sensitivity of the obtained photosensitive resin composition was evaluated as follows. Table 1 shows the results.
The obtained photosensitive resin composition is spin-coated on a silicon wafer using a coating device "Act8" (manufactured by Tokyo Electron Co., Ltd.), dried at 100°C for 2 minutes, and then dried at 110°C for 2 minutes. A photosensitive resin film having a dry film thickness of 13 μm was formed. The development time was set to twice the time required for the resulting photosensitive resin film to be immersed in cyclopentanone and dissolved.
A photosensitive resin film was prepared in the same manner as described above, and an i-line stepper “FPA-3000iW” (manufactured by Canon Inc.) was applied to the obtained photosensitive resin film with an i-line of 100 to 600 mJ/ ^cm2 at 50 mJ. Exposure was performed by irradiating a predetermined pattern with an irradiation dose in units of 1/cm ² . The exposed resin film was puddle-developed using cyclopentanone for the above-described development time by "Act8", and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a patterned resin film. The remaining film ratio was calculated by dividing the obtained film thickness of the patterned resin film by the film thickness of the photosensitive resin film before exposure and converting the result into a percentage. The sensitivity was evaluated as the amount of exposure with which a patterned resin film having a residual film rate of 80% or more was formed.

[Production and Evaluation of Patterned Cured Film]
(Production of pattern cured film)
(Evaluation of sensitivity) The patterned resin film obtained in the same manner as in (Evaluation of sensitivity) is heated at 175 ° C. for 2 hours in a nitrogen atmosphere using a vertical diffusion furnace “μ-TF” (manufactured by Koyo Thermo Systems Co., Ltd.). A cured film (film thickness after curing: 10 μm) was obtained.

(Evaluation of chemical resistance)
The obtained pattern cured film was immersed in stripping solution "Dynastrip 7700" (manufactured by Dynaloy Co., Ltd.) heated to 70°C for 30 minutes. The pattern cured film was then 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 stripping solution) - (film thickness of pattern cured film after drying)" by the film thickness before immersion in stripping solution. The film thickness change rate was calculated by converting it into a percentage, and evaluated as follows. Table 1 shows the results.
○: Film thickness change rate is less than 4% △: Film thickness change rate is 4 to 10%
×: film thickness change rate is more than 10%

(Evaluation of flux resistance)
A water-soluble flux “WS-600” (manufactured by Arendt Japan Co., Ltd.) was applied to the patterned cured film obtained in (Production of patterned cured film) and heated on a hot plate at 245° C. for 1 minute. After cooling, the substrate was washed with water heated to 60° C. to remove the flux, and dried. Measure the thickness of the patterned cured film after drying, and calculate the absolute value of (thickness of the patterned cured film before flux immersion - patterned cured film thickness after drying) with the thickness of the patterned cured film before flux immersion. The film thickness change rate was calculated by dividing it into a percentage and evaluated as follows. Table 1 shows the results. "-" indicates that evaluation was not performed.
○: Film thickness change rate is less than 5% ×: Film thickness change rate is 5% or more

In addition, the pattern cured film after drying was observed with an optical microscope to evaluate pattern damage as follows. Table 1 shows the results.
◯: Neither cracks, wrinkles, nor pattern shape changes were observed, and the pattern surface was not roughened or had relatively little surface roughness.
x: At least one of cracks, wrinkles, pattern shape change, and pattern surface severe roughness was observed.

(Production of cured film 1)
The photosensitive resin composition obtained in (Preparation of photosensitive resin composition) is spin-coated onto a Cu-plated wafer using a coating device "Act8" (manufactured by Tokyo Electron Ltd.) and dried at 100 ° C. for 2 minutes. After that, it was dried at 110° C. for 2 minutes to form a photosensitive resin film. The resulting photosensitive resin film was exposed at 500 mJ/cm ² using a proximity exposure machine "Mask Aligner MA8" (manufactured by SUSS MICROTECH). The resin film after exposure was cured under the same conditions as in (Production of patterned cured film) to obtain a cured film.

(Initial adhesiveness evaluation)
An epoxy resin layer at the tip of an aluminum stud was fixed on the surface of the obtained cured film and heated in an oven at 120° C. for 1 hour to bond the epoxy resin layer and the cured film. Thereafter, the stud was pulled using a thin film adhesion strength measuring device "Romulus" (manufactured by QUAD Group), the peeling mode during peeling was observed, and the initial adhesiveness was evaluated as follows. Table 1 shows the results. "-" indicates that evaluation was not performed.
○: Cohesive failure occurred (there was no peeling between the cured film and the Cu-plated wafer)
×: Peeled off between the cured film and the Cu-plated wafer

(Adhesion evaluation after PCT treatment)
In addition, the cured film obtained in the same manner as described above was placed in a saturated pressure cooker (manufactured by Hirayama Seisakusho Co., Ltd.) and treated for 300 hours at a temperature of 121 ° C. and a relative humidity of 100% (PCT treatment). . After the PCT treatment, the cured film was taken out and evaluated for adhesiveness in the same manner as described above. Table 1 shows the results. "-" indicates that evaluation was not performed.
When cohesive failure occurs, it indicates that the adhesive strength between the cured film and the Cu-plated wafer is stronger than the cohesive failure strength of the cured film.

(Production of cured film 2)
The photosensitive resin composition obtained in (Preparation of photosensitive resin composition) is applied to a 6-inch silicon wafer with a thickness of 625 μm using a coating device “Act8” (manufactured by Tokyo Electron Co., Ltd.), and after curing It was spin-coated so that the film thickness was about 10 μm. The resulting photosensitive resin film was exposed at 500 mJ/cm ² using a proximity exposure machine "Mask Aligner MA8" (manufactured by SUSS MICROTECH). This was cured by heating at 175° C. for 2 hours in a nitrogen atmosphere using a vertical diffusion furnace manufactured by Koyo Thermo Systems Co., Ltd. to obtain a cured film.

(Evaluation of breaking elongation)
Next, the cured film was peeled off using a 4.9% hydrofluoric acid aqueous solution, washed with water, and dried. The elongation at break of the resulting cured film was measured as follows.
The absolute value of (length of cured film at break - length of cured film before measurement) is divided by the length of cured film before measurement and expressed as a percentage, and the average value of 5 measurements is the elongation at break (% ) and evaluated as follows. Table 1 shows the results.
○: Elongation at break of 35% or more ×: Elongation at break of less than 35%

From Table 1, it can be seen that the photosensitive resin compositions of Examples 1 to 5 have high sensitivity and can form cured films excellent in chemical resistance, flux resistance, adhesion and elongation at break.

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

Although several embodiments and/or examples of the present invention have been described above in detail, those of ordinary skill in the art may modify these exemplary embodiments and/or examples without departing substantially from the novel teachings and advantages of the present invention. It is easy to make many modifications to the examples. Accordingly, many of these variations are included within the scope of the present invention.
The documents mentioned in this specification and the contents of the applications from which this application has priority under the Paris Convention are incorporated in their entirety.

Claims (13)

(A) a polyimide precursor having a structural unit represented by the following formula (1);
(B) a polymerizable compound having an aliphatic cyclic skeleton;
(C) a compound represented by the following formula (21) or (22);
(D) a photoinitiator;
including
The component (C) contains a phenol-derived structure or an orthophthalic acid-derived structure as the following anion, and a 1,5-diazabicyclo[4.3.0]non-5-ene-derived structure or 1,8-diazabicyclo[4.3.0]non-5-ene-derived structure as the following cation. 5.4.0] A photosensitive resin composition comprising an undec-7-ene-derived structure .

(In formula (1), X ¹ is a tetravalent aromatic group. Y ¹ is a divalent aromatic group. R ¹ and R ² are each independently a hydrogen atom, and the following formula (2) 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 positions to each other, and -COOR ² groups and -CO- groups are in ortho positions to each other.)

(In formula (2), R ³ to R ⁵ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. m is an integer of 1 to 10. * is a bond. be.)

(In formulas (21) and (22), R ²¹ to R ²⁹ are each independently a hydrogen atom, a monovalent organic group or a divalent organic group. 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, and X ^n- is a compound represented by any of the following formulas (23) to (26) It is an anion excluding n hydrogen atoms, where n is an integer from 1 to 4.)

(In formulas (23) to (26), R ³¹ to R ³³ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group 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, eh each independently represents 1 is an integer between ~4.) The photosensitive resin composition according to claim 1, wherein the component (B) contains a compound represented by any one of the following formulas (11) to (14).

(In formulas (11) to (14), R ¹¹ to R ¹⁴ are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following formula (15). a is 1 is an integer of up to 10, at least one R ¹¹ is a group represented by the following formula (15), b is an integer of 1 to 12, and at least one R ¹² is represented by the following formula (15) c is an integer of 1 to 16, at least one R ¹³ is a group represented by the following formula (15), d is an integer of 1 to 16, and at least one R ¹⁴ is It is a group represented by the following formula (15).

(In formula (15), R ¹⁵ to R ¹⁷ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. l is an integer of 0 to 10. * is a bond. be.) The photosensitive resin composition according to claim 2, wherein the component (B) is a compound represented by the formula (13). The photosensitive resin composition according to any one of claims 1 to 3, which is a compound represented by the formula (21). 5. The photosensitive resin composition according to any one of claims 1 to 4, wherein X ^n- is an anion obtained by removing n hydrogen atoms from the compound represented by formula (23) or (26). 6. The photosensitive resin composition according to any one of claims 1 to 5, wherein R ²¹ and R ²² are bonded together to form a ring, and R ²³ and R ²⁴ are bonded together to form a ring. . 4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the component (C) contains a 1,8-diazabicyclo[5.4.0]undec-7-ene-derived structure as the cation. A step of applying the photosensitive resin composition according to any one of claims 1 to 7 on 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;
a step of developing the resin film after the pattern exposure using an organic solvent to obtain a patterned resin film;
a step of heat-treating the pattern resin film;
A method for producing a patterned cured film comprising: 9. The method for producing a pattern cured film according to claim 8, wherein the heat treatment temperature is 200[deg.] C. or lower. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 7. The cured film according to claim 10, which is a pattern cured film. An interlayer insulating film, a cover coat layer, or a surface protective film produced using the cured film according to claim 10 or 11. An electronic component comprising the interlayer insulating film, cover coat layer or surface protective film according to claim 12 .

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