JP7405088B2 - Photosensitive resin composition, method for producing patterned cured product, cured product, 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 patterned cured product, a cured product, 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 protection films and interlayer insulating films of semiconductor devices. In recent years, photosensitive resin compositions in which these resins themselves have been given photosensitivity properties have been used, and by using these, the manufacturing process of patterned cured products can be simplified and the complicated manufacturing process can be shortened (for example, as disclosed in Patent Document (see 1).

By the way, in recent years, the miniaturization of transistors, which has supported the high performance of computers, has reached the limit of the scaling law, and in order to further improve performance and speed, a stacked device structure in which semiconductor elements are stacked three-dimensionally is being developed. is attracting attention.

Among stacked device structures, multi-die fanout wafer level packaging (Multi-die Fanout Wafer Level Packaging) is a package manufactured by sealing multiple dies in one package, and has not been proposed in the past. It is attracting a lot of attention because it is expected to be lower cost and have higher performance than conventional fan-out wafer-level packages (manufactured by sealing one die in one package).

In the fabrication of multi-die fan-out wafer-level packages, low-temperature curing properties are strongly required from the viewpoint of protecting high-performance die, protecting encapsulants with low heat resistance, and improving yield (for example, patented (See Reference 2).

Further, as a resin composition, a resin composition containing a polyimide precursor is disclosed (for example, see Patent Document 3).

JP2009-265520A International Publication No. 2008/111470 Japanese Patent Application Publication No. 2016-199662

The purpose of the present invention is to provide a photosensitive resin composition with excellent storage stability, which can form a cured product with excellent mechanical properties even when cured at a low temperature of 230°C or lower, a method for producing a patterned cured product, a cured product, and an interlayer The purpose of the present invention is to provide insulating films, cover coat layers, surface protective films, and electronic components.

（式（１）中、Ｘ_１は１以上の芳香族基を有する４価の基であって、－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。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の少なくとも一方が前記式（２）で表される基である。）

（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り、ｍは１～１０の整数である。）
３．前記（Ｄ）成分が、Ｎ－フェニルジエタノールアミン、Ｎ－メチルアニリン、Ｎ－エチルアニリン、Ｎ，Ｎ－ジメチルアニリン、Ｎ－フェニルエタノールアミン、４－フェニルモルフォリン及び２，２′－（４－メチルフェニルイミノ)ジエタノールからなる群から選択される１以上である１又は２に記載の感光性樹脂組成物。
４．前記（Ｄ）成分が、下記式（１７）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（１７）中、Ｒ_３１Ａ～Ｒ_３３Ａは、それぞれ独立に、水素原子、１価の脂肪族炭化水素基、ヒドロキシ基を有する１価の脂肪族炭化水素基、又は１価の芳香族基であり、Ｒ_３１Ａ～Ｒ_３３Ａの少なくとも１つが１価の芳香族基である。Ｒ_３１Ａ～Ｒ_３３Ａは隣接する基同士で環を形成してもよい。）
５．前記（Ｃ）成分が（Ｃ１）下記式（１５）で表される化合物及び（Ｃ２）下記式（１６）で表される化合物を含む１～４のいずれかに記載の感光性樹脂組成物。

（式（１５）中、Ｒ_１１Ａは炭素数１～１２のアルキル基であり、ａ１は０～５の整数である。Ｒ_１２Ａは水素原子又は炭素数１～１２のアルキル基である。Ｒ_１３Ａ及びＲ_１４Ａは、それぞれ独立に水素原子、炭素数１～１２のアルキル基、フェニル基又はトリル基を示す。ａ１が２以上の整数の場合、Ｒ_１１Ａはそれぞれ同一でもよく、異なっていてもよい。）

（式（１６）中、Ｒ_２１Ａは炭素数１～１２のアルキル基であり、Ｒ_２２Ａ及びＲ_２３Ａは、それぞれ独立に水素原子、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、ｃ１は０～５の整数である。ｃ１が２以上の整数の場合、Ｒ_２１Ａはそれぞれ同一でもよく、異なっていてもよい。）
６．前記（Ｂ）成分が、脂肪族環状骨格を有する重合性モノマーを含む１～５のいずれかに記載の感光性樹脂組成物。
７．前記（Ｂ）成分が、重合性の不飽和二重結合を含む基を有する１～６のいずれかに記載の感光性樹脂組成物。
８．前記（Ｂ）成分が、２以上の重合性の不飽和二重結合を含む基を有する重合性モノマーである７に記載の感光性樹脂組成物。
９．前記（Ｂ）成分が、下記式（３）で表される重合性モノマーを含む１～７のいずれかに記載の感光性樹脂組成物。

（式（３）中、Ｒ_６及びＲ_７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（４）で表される基である。ｎ１は０又は１であり、ｎ２は０～２の整数であり、ｎ１＋ｎ２は１以上である。ｎ１個のＲ_６及びｎ２個のＲ_７の少なくとも１つは、下記式（４）で表される基である。）

（式（４）中、Ｒ_９～Ｒ_１１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り、ｌは０～１０の整数である。）
１０．ｎ１＋ｎ２が、２又は３である９に記載の感光性樹脂組成物。
１１．前記（Ｂ）成分が、下記式（５）で表される重合性モノマーを含む１～１０のいずれかに記載の感光性樹脂組成物。

１２．さらに、（Ｆ）熱重合開始剤を含む１～１１のいずれかに記載の感光性樹脂組成物。
１３．さらに、酸化防止剤を含む１～１２のいずれかに記載の感光性樹脂組成物。
１４．１～１３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物の製造方法。
１５．前記加熱処理の温度が２３０℃以下である１４に記載のパターン硬化物の製造方法。
１６．１～１３のいずれかに記載の感光性樹脂組成物を硬化した硬化物。
１７．パターン硬化物である１６に記載の硬化物。
１８．１６又は１７に記載の硬化物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。
１９．１８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。According to the present invention, the following photosensitive resin compositions and the like are provided.
1. (A) a polyimide precursor having a polymerizable unsaturated bond,
(B) a polymerizable monomer,
(C) photopolymerization initiator,
(D) A cyclization catalyst, and (E) a photosensitive resin composition containing a solvent.
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 group having one or more aromatic groups, -COOR ₁ group and -CONH- group are in the ortho position to each other, -COOR ₂ group and -CO - groups are in the ortho position to each other.Y ₁ is a divalent aromatic group.R ₁ and R ₂ are each independently a hydrogen atom, a group represented by the following formula (2), or a carbon number 1 to 4 aliphatic hydrocarbon groups, and at least one of R ₁ and R ₂ is a group represented by the above formula (2).)

(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, and m is an integer of 1 to 10.)
3. The component (D) is N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, and 2,2'-(4-methyl 3. The photosensitive resin composition according to 1 or 2, which is one or more selected from the group consisting of phenylimino)diethanol.
4. 3. The photosensitive resin composition according to 1 or 2, wherein the component (D) contains a compound represented by the following formula (17).

(In formula (17), R _31A to R _33A are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxy group, or a monovalent aromatic group) and at least one of R _31A to R _33A is a monovalent aromatic group. _{R 31A} to R _33A may form a ring with adjacent groups.)
5. 5. The photosensitive resin composition according to any one of 1 to 4, wherein the component (C) comprises (C1) a compound represented by the following formula (15) and (C2) a compound represented by the following formula (16).

(In formula (15), R _11A is an alkyl group having 1 to 12 carbon atoms, and a1 is an integer of 0 to 5. R _12A is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. R _13A and R _14A each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group. When a1 is an integer of 2 or more, R _11A may be the same or different. .)

(In formula (16), R _21A is an alkyl group having 1 to 12 carbon atoms, and R _22A and R _23A are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and an alkyl group having 1 to 12 carbon atoms. group, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group, and c1 is an integer of 0 to 5. When c1 is an integer of 2 or more, R _21A may be the same or different. Also good.)
6. 6. The photosensitive resin composition according to any one of 1 to 5, wherein the component (B) contains a polymerizable monomer having an aliphatic cyclic skeleton.
7. 7. The photosensitive resin composition according to any one of 1 to 6, wherein the component (B) has a group containing a polymerizable unsaturated double bond.
8. 8. The photosensitive resin composition according to 7, wherein the component (B) is a polymerizable monomer having a group containing two or more polymerizable unsaturated double bonds.
9. 8. The photosensitive resin composition according to any one of 1 to 7, wherein the component (B) contains a polymerizable monomer represented by the following formula (3).

(In formula (3), R ₆ and R ₇ are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following formula (4). n1 is 0 or 1; , n2 is an integer of 0 to 2, and n1+n2 is 1 or more.At least one of n1 R ₆ and n2 R ₇ is a group represented by the following formula (4).)

(In formula (4), R ₉ to R ₁₁ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and l is an integer of 0 to 10.)
10. 10. The photosensitive resin composition according to 9, wherein n1+n2 is 2 or 3.
11. The photosensitive resin composition according to any one of 1 to 10, wherein the component (B) contains a polymerizable monomer represented by the following formula (5).

12. The photosensitive resin composition according to any one of 1 to 11, further comprising (F) a thermal polymerization initiator.
13. 13. The photosensitive resin composition according to any one of 1 to 12, further comprising an antioxidant.
14. Applying the photosensitive resin composition according to any one of 1 to 13 on a substrate and drying it to form a photosensitive resin film;
pattern-exposing the photosensitive resin film to obtain a resin film;
Developing the resin film after the pattern exposure using an organic solvent to obtain a pattern resin film;
A method for producing a patterned cured product, comprising the step of heat-treating the patterned resin film.
15. 15. The method for producing a patterned cured product according to 14, wherein the temperature of the heat treatment is 230° C. or lower.
16. A cured product obtained by curing the photosensitive resin composition according to any one of 1 to 13.
17. 17. The cured product according to 16, which is a pattern cured product.
18. An interlayer insulating film, a cover coat layer, or a surface protective film produced using the cured product according to 16 or 17.
19. An electronic component comprising an interlayer insulating film, a cover coat layer, or a surface protective film according to 18.

According to the present invention, a photosensitive resin composition with excellent storage stability that can form a cured product with excellent mechanical properties even when cured at a low temperature of 230°C or lower, a method for producing a patterned cured product, a cured product, and an interlayer Insulating films, cover coat layers, surface protection films, and electronic components can be provided.

FIG. 3 is a manufacturing process diagram of an electronic component according to an embodiment of the present invention.

Below, embodiments of the photosensitive resin composition of the present invention, a method for producing a patterned cured product using the same, a cured product, an interlayer insulating film, a cover coat layer, a surface protective film, and an electronic component will be described in detail. Note that the present invention is not limited to the following embodiments.

In this specification, "A or B" may include either A or B, or may include both. In addition, in this specification, the term "process" does not only refer to an independent process, but also refers to a process that cannot be clearly distinguished from other processes, as long as the intended effect of the process is achieved. included.
A numerical range indicated using "~" indicates a range that includes the numerical values written before and after "~" as the minimum and maximum values, respectively. In addition, in this specification, if there are multiple substances corresponding to each component in the composition, unless otherwise specified, the content of each component in the composition refers to the total content of the multiple substances present in the composition. means quantity. Furthermore, unless otherwise specified, the exemplified materials may be used alone or in combination of two or more.
The "(meth)acrylic group" in this specification means an "acrylic group" and a "methacrylic group."

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)"), (B) a polymerizable monomer (also referred to as a "crosslinking agent"). ) (hereinafter also referred to as "component (B)"), (C) photopolymerization initiator (hereinafter also referred to as "component (C)"), (D) cyclization catalyst (hereinafter also referred to as "(D ), and (E) a solvent (hereinafter also referred to as "component (E)").

Thereby, a cured product with excellent mechanical properties can be formed even when cured at a low temperature of 230° C. or lower.
Moreover, storage stability can be improved.
Further, as an optional effect, a cured product with an excellent cyclization rate can be formed even when curing at a low temperature of 230° C. or lower.
As an optional effect, sensitivity can be improved.

The photosensitive resin composition of the present invention is preferably a negative photosensitive resin composition. The photosensitive resin composition of the present invention is preferably a material for electronic parts.

Component (A) is not particularly limited, but is preferably a polyimide precursor that has high transmittance when i-line is used as a light source during patterning and exhibits high cured product properties even when cured at a low temperature of 230° C. or lower.

Examples of the polymerizable unsaturated bond include a carbon-carbon double bond.

Component (A) is preferably a polyimide precursor having a structural unit represented by the following formula (1). As a result, the i-line transmittance is high, and a good cured product can be formed even when cured at a low temperature of 230° C. or lower.
The content of the structural unit represented by formula (1) is preferably 50 mol% or more, more preferably 80 mol% or more, and 90 mol% or more of the total structural units of component (A). More preferred. The upper limit is not particularly limited and may be 100 mol%.

（式（１）中、Ｘ_１は１以上の芳香族基を有する４価の基であって、－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。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の少なくとも一方が前記式（２）で表される基である。）

(In formula (1), X ₁ is a tetravalent group having one or more aromatic groups, -COOR ₁ group and -CONH- group are in the ortho position to each other, -COOR ₂ group and -CO - groups are in the ortho position to each other.Y ₁ is a divalent aromatic group.R ₁ and R ₂ are each independently a hydrogen atom, a group represented by the following formula (2), or a carbon number 1 to 4 aliphatic hydrocarbon groups, and at least one of R ₁ and R ₂ is a group represented by the above formula (2).)

（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り、ｍは１～１０の整数（好ましくは２～５の整数、より好ましくは２又は３）である。）

(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, and m is an integer of 1 to 10 (preferably an integer of 2 to 5). , more preferably 2 or 3).

In the tetravalent group having one or more (preferably 1 to 3, more preferably 1 or 2) aromatic groups in X ₁ of formula (1), the aromatic group may be an aromatic hydrocarbon group, and the aromatic group may be an aromatic hydrocarbon group. It may also be a group heterocyclic group. Aromatic hydrocarbon groups are preferred.

The aromatic hydrocarbon group represented by X ₁ in formula (1) includes a divalent to tetravalent (divalent, trivalent or tetravalent) group formed from a benzene ring, a divalent to tetravalent group formed from naphthalene. , divalent to tetravalent groups formed from perylene, and the like.

（式（６）中、Ｘ及びＹ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価の基又は単結合を示す。Ｚはエーテル基（－Ｏ－）又はスルフィド基（－Ｓ－）である（－Ｏ－が好ましい）。）Examples of the tetravalent group having one or more aromatic groups represented by X ₁ in formula (1) include, but are not limited to, the following tetravalent group in formula (6).

(In formula (6), X and Y each independently represent a divalent group or a single bond that is not conjugated with the benzene ring to which they are bonded. Z is an ether group (-O-) or a sulfide group (-S -) (-O- is preferred).

In formula (6), the divalent groups of X and Y that are not conjugated with the benzene ring to which they are bonded are -O-, -S-, a methylene group, a bis(trifluoromethyl)methylene group, or a difluoromethylene group. is preferable, and -O- is more preferable.

The divalent aromatic group of Y ₁ in formula (1) may be a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group. A divalent aromatic hydrocarbon group is preferred.

（式（７）中、Ｒ_１２～Ｒ_１９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 represented by Y ₁ in formula (1) include, but are not limited to, a group represented by formula (7) below.

(In formula (7), R ₁₂ to R ₁₉ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group, or a monovalent organic group having a halogen atom.)

Examples of the monovalent aliphatic hydrocarbon group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms) for R ₁₂ to R ₁₉ in formula (7) include a methyl group and the like. For example, R ₁₂ and R ₁₅ to R ₁₉ may be hydrogen atoms, and R ₁₃ and R ₁₄ may be monovalent aliphatic hydrocarbon groups.

The monovalent organic group having a halogen atom (preferably a fluorine atom) represented by R ₁₂ to R ₁₉ in formula (7) is a monovalent aliphatic hydrocarbon group having a halogen atom (preferably having 1 to 10 carbon atoms, or more). Preferably, the carbon number is 1 to 6), such as a trifluoromethyl group.

Examples of the aliphatic hydrocarbon group 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- Examples include butyl group.

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

Examples of the aliphatic hydrocarbon group 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, 2-propyl group, etc. It will be done. Methyl group is preferred.

A polyimide precursor having a structural unit represented by the formula (1) can be obtained by combining, for example, a tetracarboxylic dianhydride represented by the following formula (8) and a diamino compound represented by the following formula (9) with N - By reacting in an organic solvent such as methyl-2-pyrrolidone to obtain a polyamic acid, adding a compound represented by the following formula (10), and reacting in an organic solvent to partially introduce an ester group. Obtainable.
The tetracarboxylic dianhydride represented by formula (8) and the diamino compound represented by formula (9) may be used alone or in combination of two or more.

（式（８）中、Ｘ_１は式（１）のＸ_１に対応する基である。）

(In formula (8), X ₁ is a group corresponding to X ₁ in formula (1).)

（式（９）中、Ｙ_１は式（１）で定義した通りである。）

(In formula (9), _Y1 is as defined in formula (1).)

（式（１０）中、Ｒは上述の式（２）で表される基である。）

(In formula (10), R is a group represented by the above formula (2).)

（式（１１）中、Ｘ_２は１以上の芳香族基を有する４価の基であって、－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。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。）Component (A) may have a structural unit other than the structural unit represented by formula (1).
Examples of structural units other than the structural unit represented by formula (1) include the structural unit represented by formula (11).

(In _{the formula} ( ₁₁ ), - groups are in the ortho position to each other. Y ₂ is a divalent aromatic group. R ₅₁ and R ₅₂ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. )

Examples of the tetravalent group having one or more aromatic groups represented by X ₂ in formula (11) include those similar to the tetravalent group having one or more aromatic groups represented by X ₁ in formula (1).
Examples of the divalent aromatic group of Y ₂ in formula (11) include the same divalent aromatic group as Y ₁ of formula (1).
Examples of the aliphatic hydrocarbon groups having 1 to 4 carbon atoms for R ₅₁ and R ₅₂ in formula (11) include the same aliphatic hydrocarbon groups having 1 to 4 carbon atoms as R ₁ and R ₂ .

Structural units other than the structural unit represented by formula (1) may be used alone or in combination of two or more.

The content of structural units other than the structural unit represented by formula (1) is preferably less than 50 mol % based on all the structural units of component (A).

In component (A), the proportion of carboxyl groups esterified with the group represented by formula (2) is preferably 50 mol% or more, and 60 to 100 mol%, based on all the carboxy groups and all the carboxy esters. More preferably mol%, and even more preferably 70 to 90 mol%.

There is no particular restriction on the molecular weight of component (A), but it is preferably a number average molecular weight of 10,000 to 200,000.
The number average molecular weight can be measured, for example, by gel permeation chromatography, and can be determined by conversion using a standard polystyrene calibration curve.

Component (B) may have a group containing (preferably two or more) polymerizable unsaturated double bonds (preferably a (meth)acrylic group since it is polymerizable with a photopolymerization initiator). preferable. Component (B) is preferably a polymerizable monomer having a group containing two or more polymerizable unsaturated double bonds. In order to improve the crosslinking density and photosensitivity and to suppress swelling of the pattern after development, it is preferable to have a group containing 2 to 3 polymerizable unsaturated double bonds.

Moreover, the component (B) may contain a polymerizable monomer having a functional group other than the group containing a polymerizable unsaturated double bond. Examples of the functional group include cyclic ether groups such as epoxy groups and oxetane groups.

Component (B) preferably contains a polymerizable monomer having an aliphatic cyclic skeleton (preferably having 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms). Thereby, hydrophobicity can be imparted to the cured product that can be formed, and deterioration in adhesiveness between the cured product and the substrate under high temperature and high humidity conditions can be suppressed.

（式（３）中、Ｒ_６及びＲ_７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（４）で表される基である。ｎ１は０又は１であり、ｎ２は０～２の整数であり、ｎ１＋ｎ２は１以上（好ましくは２又は３）である。ｎ１個のＲ_６及びｎ２個のＲ_７の少なくとも１つ（好ましくは２又は３）は、下記式（４）で表される基である。）It is preferable that the component (B) contains a polymerizable monomer represented by the following formula (3).

(In formula (3), R ₆ and R ₇ are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following formula (4). n1 is 0 or 1; , n2 is an integer of 0 to 2, and n1+n2 is 1 or more (preferably 2 or 3). At least one of n1 R ₆ and n2 R ₇ (preferably 2 or 3) is the following: It is a group represented by formula (4).)

When there are two R _7s , the two R _7s may be the same or different.

（式（４）中、Ｒ_９～Ｒ_１１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り、ｌは０～１０の整数（好ましくは０、１又は２）である。）

(In formula (4), R ₉ to R ₁₁ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and l is an integer of 0 to 10 (preferably 0, 1 or 2 ).)

It is more preferable that the component (B) contains a polymerizable monomer represented by the following formula (5).

Further, as component (B), for example, the following polymerizable monomers may be used.

式（１２）中、Ｒ_２１～Ｒ_２４は、それぞれ独立に、炭素数１～４の脂肪族炭化水素基又は上記式（４）で表される基である。ｎ３は１～３の整数（好ましくは２又は３）である。ｎ４は１～３の整数（好ましくは２又は３）である。ｎ５は０又は１であり、ｎ６は０又は１である。ｎ５＋ｎ６は１以上（好ましくは２）である。

In formula (12), R ₂₁ to R ₂₄ are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the above formula (4). n3 is an integer from 1 to 3 (preferably 2 or 3). n4 is an integer from 1 to 3 (preferably 2 or 3). n5 is 0 or 1, and n6 is 0 or 1. n5+n6 is 1 or more (preferably 2).

When two or more R _21s exist, the two or more R _21s may be the same or different.
When two or more R _22s exist, the two or more R _22s may be the same or different.

At least one (preferably 2 or 3) of n3 R ₂₁ is a group represented by the above formula (4).
At least one (preferably 2 or 3) of n4 R ₂₂ is a group represented by the above formula (4).
At least one (preferably 2) of n5 _R23s and n6 _R24s is a group represented by the above formula (4).

The aliphatic hydrocarbon groups having 1 to 4 carbon atoms in R ₆ and R ₇ in formula (3) and R ₂₁ to R ₂₄ in formula (12) include 1 to 4 carbon atoms in R ₁ and R ₂ in formula (1); Examples include those similar to the aliphatic hydrocarbon groups in ~4.

The aliphatic hydrocarbon groups having 1 to 3 carbon atoms represented by R ₉ to R ₁₁ in formula (4) are the same as the aliphatic hydrocarbon groups having 1 to 3 carbon atoms represented by R ₃ to R ₅ in formula (2). Things can be mentioned.

Component (B) may contain a polymerizable monomer other than the polymerizable monomer having an aliphatic cyclic skeleton. Thereby, a cured product with good mechanical properties can be obtained.

Examples of polymerizable monomers other than polymerizable monomers having an aliphatic cyclic skeleton include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and tetraethylene glycol dimethacrylate. , 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, Methylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, dipentaerythritol hexaacrylate, di Pentaerythritol hexamethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated isocyanuric acid triacrylate, ethoxylated isocyanuric acid trimethacrylate, acryloyloxyethyl isocyanurate, methacryloyloxyethyl isocyanurate, ethylene oxide (EO) modified bisphenol A diacrylate (e.g. Examples of commercially available products include FA324A (manufactured by Hitachi Chemical Co., Ltd.).

Component (B) may be used alone or in combination of two or more.

From the viewpoint of obtaining good mechanical properties and photosensitive properties, component (B) preferably contains a polymerizable monomer having an aliphatic cyclic skeleton and a polymerizable monomer other than the polymerizable monomer having an aliphatic cyclic skeleton.
When containing a polymerizable monomer other than the polymerizable monomer having an aliphatic cyclic skeleton and the polymerizable monomer having an aliphatic cyclic skeleton, the content of the polymerizable monomer having an aliphatic cyclic skeleton is 100 parts by mass of component (A). On the other hand, 1 to 40 parts by mass is preferable. From the viewpoint of improving the hydrophobicity of the cured product, the amount is more preferably 5 to 35 parts by mass. The content of polymerizable monomers other than the polymerizable monomer having an aliphatic cyclic skeleton is preferably 1 to 20 parts by weight based on 100 parts by weight of component (A). From the viewpoint of improving the hydrophobicity of the cured product, the amount is more preferably 5 to 15 parts by mass.

The content of component (B) is preferably 1 to 50 parts by mass per 100 parts by mass of component (A). From the viewpoint of improving the hydrophobicity of the cured product, the amount is more preferably 3 to 50 parts by weight, and even more preferably 5 to 40 parts by weight.
When it is within the above range, it is easy to obtain a practical relief pattern, and it is easy to suppress residues after development in unexposed areas.

Component (C) includes, for example, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, benzophenone derivatives such as fluorenone,
Acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone,
Thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone,
Benzyl, benzyl dimethyl ketal, benzyl derivatives such as benzyl-β-methoxyethyl acetal,
Benzoin, benzoin derivatives such as benzoin methyl ether, 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl) Oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, 1,3-diphenylpropanetrione -2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H- Preferred examples include oxime esters such as carbazol-3-yl]-,1-(O-acetyloxime) and compounds represented by the following formula, but are not limited thereto.

Oxime esters are particularly preferred from the viewpoint of photosensitivity.

Component (C) preferably contains (C1) a compound represented by the following formula (15) (hereinafter also referred to as "component (C1)").
The component (C1) preferably has higher sensitivity to actinic rays than the component (C2) described later, and is preferably a highly sensitive photosensitizer.

式（１５）中、Ｒ_１１Ａは炭素数１～１２のアルキル基であり、ａ１は０～５の整数である。Ｒ_１２Ａは水素原子又は炭素数１～１２のアルキル基である。Ｒ_１３Ａ及びＲ_１４Ａは、それぞれ独立に水素原子、炭素数１～１２（好ましくは炭素数１～４）のアルキル基、フェニル基又はトリル基を示す。ａ１が２以上の整数の場合、Ｒ_１１Ａはそれぞれ同一でもよく、異なっていてもよい。

In formula (15), R _11A is an alkyl group having 1 to 12 carbon atoms, and a1 is an integer of 0 to 5. R _12A is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. R _13A and R _14A each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms), a phenyl group, or a tolyl group. When a1 is an integer of 2 or more, R _11A may be the same or different.

R _11A is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group. a1 is preferably 1. R _12A is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an ethyl group. R _13A and R _14A are preferably each independently an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

Examples of the compound represented by formula (15) include a compound represented by formula (15A) below, which is available as "IRGACURE OXE 02" manufactured by BASF Japan Co., Ltd.

Further, the component (C) preferably contains (C2) a compound represented by the following formula (16) (hereinafter also referred to as "component (C2)").
Component (C2) preferably has lower sensitivity to actinic rays than component (C1), and is preferably a photosensitizer with standard sensitivity.

式（１６）中、Ｒ_２１Ａは炭素数１～１２のアルキル基であり、Ｒ_２２Ａ及びＲ_２３Ａは、それぞれ独立に水素原子、炭素数１～１２のアルキル基（好ましくは炭素数１～４）、炭素数１～１２のアルコキシ基（好ましくは炭素数１～４）、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、ｃ１は０～５の整数である。ｃ１が２以上の整数の場合、Ｒ_２１Ａはそれぞれ同一でもよく、異なっていてもよい。

In formula (16), R _21A is an alkyl group having 1 to 12 carbon atoms, and R _22A and R _23A are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms). , an alkoxy group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms), a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group, and c1 is an integer of 0 to 5. When c1 is an integer of 2 or more, R _21A may be the same or different.

c1 is preferably 0. R _22A is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group. R _23A is preferably an alkoxy group having 1 to 12 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and even more preferably a methoxy group or an ethoxy group.

Examples of the compound represented by the formula (16) include a compound represented by the following formula (16A), which is available as "G-1820 (PDO)" manufactured by Lambson.

Component (C) may be used alone or in combination of two or more.

Component (C) preferably includes one or more selected from the group consisting of component (C1) and component (C2).
Moreover, it is preferable that the (C) component includes a (C1) component and a (C2) component.

The content of component (C) is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 10 parts by mass, per 100 parts by mass of component (A). 5 parts by mass.
Within the above range, photocrosslinking tends to be uniform in the film thickness direction, making it easier to obtain a practical relief pattern.

When containing component (C1), the content of component (C1) is usually 0.05 to 5.0 parts by mass, preferably 0.07 to 2.0 parts by mass, per 100 parts by mass of component (A). The amount is 5 parts by weight, more preferably 0.09 to 1.0 parts by weight.

When component (C2) is contained, the content of component (C2) is usually 0.5 to 15.0 parts by mass, preferably 1.0 to 15.0 parts by mass, per 100 parts by mass of component (A). It is 0 parts by mass.

When containing component (C1) and component (C2), the content of component (C1) is 0.05 to 5.0 parts by mass per 100 parts by mass of component (A), and the component (C2) The content is preferably 0.5 to 15.0 parts by weight per 100 parts by weight of component (A).

When containing component (C1) and component (C2), the mass ratio of the content of component (C1) and component (C2) is preferably 1:2 to 1:15, more preferably 1:3 to It is 1:10.

The photosensitive resin composition of the present invention contains (D) a cyclization catalyst.
Component (D) is 2-(methylphenylamino)ethanol, 2-(ethylanilino)ethanol, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N-dimethylaniline, N-phenylethanolamine, It is preferably one or more selected from the group consisting of 4-phenylmorpholine and 2,2'-(4-methylphenylimino)diethanol, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N- , N-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, and 2,2'-(4-methylphenylimino)diethanol.

（式（１７）中、Ｒ_３１Ａ～Ｒ_３３Ａは、それぞれ独立に、水素原子、１価の脂肪族炭化水素基、ヒドロキシ基を有する１価の脂肪族炭化水素基、又は１価の芳香族基であり、Ｒ_３１Ａ～Ｒ_３３Ａの少なくとも１つ（好ましくは１つ）が１価の芳香族基である。Ｒ_３１Ａ～Ｒ_３３Ａは隣接する基同士で環（例えば、置換基（例えば、メチル基、フェニル基）を有してもよい５員環又は６員環）を形成してもよい。）It is preferable that component (D) contains a compound represented by the following formula (17).

(In formula (17), R _31A to R _33A are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxy group, or a monovalent aromatic group) and at least one (preferably one) of _{R 31A to R 33A is} a monovalent aromatic group. , phenyl group) may be formed.

Preferably, at least one of R _31A to R _33A is a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxy group, or a monovalent aromatic group.

Examples of the monovalent aliphatic hydrocarbon group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms) represented by R _31A to R _33A in formula (17) include a methyl group and an ethyl group.
As the monovalent aliphatic hydrocarbon group having a hydroxy group of R _31A to _{R 33A} in formula (17), one or more (preferably 1 _to 3 ) to which a hydroxy group is bonded. Specific examples include methylol group and hydroxyethyl group. Hydroxyethyl group is preferred.

The monovalent aromatic group R _31A to R _33A in formula (17) may be a monovalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms); It may also be a valent aromatic heterocyclic group. Monovalent aromatic hydrocarbon groups are preferred.
Examples of the monovalent aromatic hydrocarbon group include a phenyl group and a naphthyl group.
The monovalent aromatic groups R _31A to R _33A in formula (17) may have a substituent. Examples of substituents include monovalent aliphatic hydrocarbon groups represented by R _31A to R _33A of the above formula (17), and monovalent aliphatic groups having a hydroxy group represented by R _31A to R _33A of the above formula (17). Examples include those similar to hydrocarbon groups.

Component (D) may be used alone or in combination of two or more.
The content of component (D) is preferably 0.1 to 20 parts by mass based on 100 parts by mass of component (A) from the viewpoint of imidization rate and sensitivity improvement. From the viewpoint of storage stability, the amount is more preferably 0.3 to 15 parts by weight, and even more preferably 0.5 to 10 parts by weight.

The photosensitive resin composition of the present invention contains (E) a solvent.
Component (E) includes N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethylpropionate, 3-methylmethoxypropionate, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, cyclohexanone, cyclopentanone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, N-dimethylmorpholine, etc. Generally, there are no particular limitations as long as the other components can be sufficiently dissolved.
Among these, N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, and N,N-dimethylformamide are selected from the viewpoints of excellent solubility of each component and coating properties when forming a photosensitive resin film. , N,N-dimethylacetamide is preferably used.

（式中、Ｒ_４１～Ｒ_４３は、それぞれ独立に、炭素数１～１０のアルキル基である。）Moreover, as the component (E), a compound represented by the following formula (21) may be used.

(In the formula, R ₄₁ to R ₄₃ are each independently an alkyl group having 1 to 10 carbon atoms.)

In formula (21), the alkyl group having 1 to 10 carbon atoms (preferably 1 to 3, more preferably 1 or 3) in R ₄₁ to R ₄₃ includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group. , n-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, etc.
The compound represented by formula (21) is preferably 3-methoxy-N,N-dimethylpropanamide (eg, trade name "KJCMPA-100" (manufactured by KJ Chemicals Co., Ltd.)).

Component (E) may be used alone or in combination of two or more.
The content of component (E) is not particularly limited, but is generally 50 to 1,000 parts by mass per 100 parts by mass of component (A).

The photosensitive resin composition of the present invention may further contain (F) a thermal polymerization initiator (hereinafter also referred to as "component (F)") from the viewpoint of promoting the polymerization reaction.
Component (F) does not decompose by heating (drying) to remove the solvent during film formation, but decomposes by heating during curing to generate radicals, and component (B) or component (A) Compounds that promote the polymerization reaction of component (B) are preferred.
Component (F) is preferably a compound with a decomposition point of 110°C or more and 200°C or less, and more preferably a compound with a decomposition point of 110°C or more and 175°C or less from the viewpoint of promoting the polymerization reaction at a lower temperature.

Specific examples include ketone peroxides such as methyl ethyl ketone peroxide, 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, 1, Peroxyketals such as 1-di(t-butylperoxy)cyclohexane, hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, dicumyl peroxide, dicumyl peroxide, -Dialkyl peroxides such as t-butyl peroxide, diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide, peroxides such as di(4-t-butylcyclohexyl) peroxydicarbonate and di(2-ethylhexyl) peroxydicarbonate Dicarbonate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxybenzoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate Examples include peroxy esters such as noate, bis(1-phenyl-1-methylethyl) peroxide, and the like. Examples of commercially available products include the trade names "Percmil D", "Percmil P", and "Percmil H" (all manufactured by NOF Corporation).

When containing component (F), the content of component (F) is preferably 0.1 to 20 parts by mass per 100 parts by mass of component (A), and in order to ensure good flux resistance, the content of component (F) is preferably 0.1 to 20 parts by mass. The amount is more preferably 0.2 to 20 parts by weight, and even more preferably 0.3 to 10 parts by weight from the viewpoint of suppressing a decrease in solubility due to decomposition during drying.

The photosensitive resin composition of the present invention may further contain an antioxidant. By containing an antioxidant, oxygen radicals and peroxide radicals generated during high-temperature storage or reflow treatment can be captured, and a decrease in adhesiveness (adhesion) can be further suppressed. Further, oxidation of the electrode during an insulation reliability test can be suppressed, and diffusion from the electrode to the resin film or patterned resin film can be suppressed.

As antioxidants, N,N'-bis[2-[2-(3,5-di-tert-butyl-4-hydroxyphenyl)ethylcarbonyloxy]ethyl]oxamide, N,N'-bis-3 -(3,5-di-tert-butyl-4'-hydroxyphenyl)propionylhexamethylenediamine, 1,3,5-tris(3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl)-1 , 3,5-triazine-2,4,6(1H,3H,5H)-trione,
2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate , 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3- methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3, 5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), isooctyl-3-( 3,5-di-t-butyl-4-hydroxyphenyl)propionate, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine- 2,4,6-(1H,3H,5H)-trione, 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6 -t-butylphenol),
Tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4 -hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H )-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H )-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H )-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H, 3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H, 5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H, 5H)-trion,
Pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4) -hydroxyphenyl)propionate], 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-( 1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4 ,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3 ,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1 , 3,5-triazine-2,4,6-(1H,3H,5H)-trione,
1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)- trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid.

The antioxidants may be used alone or in combination of two or more.

When containing an antioxidant, the content of the antioxidant is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of component (A). Preferably it is 0.1 to 5 parts by mass.

The photosensitive resin composition of the present invention may further contain a coupling agent (adhesive aid), a surfactant or a leveling agent, a rust preventive agent, a polymerization inhibitor, and the like.

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

（式（１３）中、Ｒ_３１及びＲ_３２は、それぞれ独立に炭素数１～５のアルキル基である。ａは１～１０の整数であり、ｂは１～３の整数である。）Preferred silane coupling agents include compounds having a urea bond (-NH-CO-NH-). Thereby, even when curing is performed at a low temperature of 230° C. or lower, the adhesion to the substrate can be further improved.
A compound represented by the following formula (13) is more preferred because it exhibits excellent adhesive properties when cured at low temperatures.

(In formula (13), R ₃₁ and R ₃₂ are each independently an alkyl group having 1 to 5 carbon atoms. a is an integer of 1 to 10, and b is an integer of 1 to 3.)

Specific examples of the compound represented by formula (13) include ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, and 3-ureidopropyltrimethoxysilane. , 3-ureidopropyltriethoxysilane, 4-ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane, etc., with 3-ureidopropyltriethoxysilane being preferred.

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 together, the adhesion of the cured product 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, 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, phenylsilane triol, 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 include 4-bis(dipropylhydroxysilyl)benzene, 1,4-bis(dibutylhydroxysilyl)benzene, and a compound represented by the following formula (14). Among these, the compound represented by formula (14) is particularly preferred in order to further improve adhesiveness with the substrate.

（式（１４）中、Ｒ_３３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_３４及びＲ_３５は、それぞれ独立に炭素数１～５のアルキル基である。ｃは１～１０の整数であり、ｄは１～３の整数である。）

(In formula (14), R ₃₃ is a monovalent organic group having a hydroxy group or a glycidyl group, R ₃₄ and R ₃₅ are each independently an alkyl group having 1 to 5 carbon atoms, and c is 1 to 5. is an integer of 10, and d is an integer of 1 to 3.)

Examples of the compound represented by formula (14) include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3- Hydroxypropyltriethoxysilane, 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2- Examples include glycidoxyethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybutyltriethoxysilane, etc. It will be done.

The silane coupling agent having a hydroxy group or a glycidyl group preferably further contains a group having a nitrogen atom, and further preferably has an amino group or an amide bond.
Furthermore, examples of silane coupling agents having an amino group include bis(2-hydroxymethyl)-3-aminopropyltriethoxysilane, bis(2-hydroxymethyl)-3-aminopropyltrimethoxysilane, and bis(2-glycid). Examples include oxymethyl)-3-aminopropyltriethoxysilane, bis(2-hydroxymethyl)-3-aminopropyltrimethoxysilane, and the like.

Furthermore, as a silane coupling agent having an amide bond, R ₃₆ -(CH ₂ ) _e -CO-NH-(CH ₂ ) _f -Si(OR ₃₇ ) ₃ (R ₃₆ is a hydroxy group or a glycidyl group, e and f are each independently an integer of 1 to 3, and R ₃₇ is a methyl group, an ethyl group, or a propyl group.

The silane coupling agents may be used alone or in combination of two or more.

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

By including a surfactant or a leveling agent, coating properties (for example, suppression of striations (unevenness in film thickness)) and developability can be improved.

Examples of the surfactant or leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, etc. Commercially available products include the product name "Megafac F171". ", "F173", "R-08" (manufactured by DIC Corporation), product name "Florado FC430", "FC431" (manufactured by Sumitomo 3M Corporation), product name "Organosiloxane Polymer KP341", " KBM303," "KBM403," and "KBM803" (all manufactured by Shin-Etsu Chemical Co., Ltd.).

The surfactant and the leveling agent may be used alone or in combination of two or more.

When a surfactant or leveling agent is included, the content of the surfactant or leveling agent is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of component (A). It is preferably 0.05 to 3 parts by mass, and more preferably 0.05 to 3 parts by mass.

By containing a rust preventive agent, corrosion of copper and copper alloys can be suppressed and discoloration can be prevented.
Examples of the rust preventive include triazole derivatives and tetrazole derivatives.
The rust inhibitors may be used alone or in combination of two or more.

When using a rust preventive agent, the content of the rust preventive agent 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, based on 100 parts by mass of component (A). 3 parts by mass is more preferred.

By containing a polymerization inhibitor, good storage stability can be ensured.
Examples of the polymerization inhibitor include radical polymerization inhibitors and radical polymerization inhibitors.

Examples of the polymerization inhibitor include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N-phenyl-2- Examples include naphthylamine, cuperone, 2,5-torquinone, tannic acid, parabenzylaminophenol, and nitrosamines.

The polymerization inhibitors may be used alone or in combination of two or more.

When containing a polymerization inhibitor, the content of the polymerization inhibitor is 0 to 100 parts by mass of component (A) from the viewpoint of storage stability of the photosensitive resin composition and heat resistance of the obtained cured product. The amount is preferably from 0.01 to 30 parts by weight, more preferably from 0.01 to 10 parts by weight, and even more preferably from 0.05 to 5 parts by weight.

The photosensitive resin composition of the present invention essentially consists of components (A) to (E), and optionally component (F), a coupling agent, a surfactant, a leveling agent, a rust preventive, and a polymerization inhibitor. Other unavoidable impurities may be included 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, or 100% by mass of the photosensitive resin composition of the present invention,
(A) to (E) components,
Even if it consists of components (A) to (F), or components (A) to (E), and optionally component (F), a coupling agent, a surfactant, a leveling agent, a rust preventive agent, and a polymerization inhibitor. good.

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

The method for producing a patterned cured product of the present invention includes a step of coating the above-described photosensitive resin composition on a substrate and drying it to form a photosensitive resin film, and exposing the photosensitive resin film in a pattern to form a resin film. The patterned resin film is developed using an organic solvent to obtain a patterned resin film, and the patterned resin film is heat-treated.
Thereby, a patterned cured product can be obtained.

A method for manufacturing a cured product without a pattern includes, for example, the step of forming the above-mentioned photosensitive resin film and the step of heat treatment. Furthermore, a step of exposing may be included.

Examples of the substrate include semiconductor substrates such as glass substrates and Si substrates (silicon wafers), metal oxide insulator substrates such as TiO ₂ substrates and SiO ₂ substrates, silicon nitride substrates, copper substrates, and copper alloy substrates.

There are no particular restrictions on the coating method, but a spinner or the like can be used.

Drying can be performed using a hot plate, oven, or the like.
The drying temperature is preferably 90 to 150°C, more preferably 90 to 120°C from the viewpoint of ensuring dissolution contrast.
The drying time is preferably 30 seconds to 5 minutes.
Drying may be performed two or more times.
Thereby, a photosensitive resin film formed from the above-described photosensitive resin composition can be obtained.

The thickness of the photosensitive resin film is preferably 5 to 100 μm, more preferably 6 to 50 μm, and even more preferably 7 to 30 μm.

In the pattern exposure, for example, a predetermined pattern is exposed through a photomask.
The active light to be irradiated includes i-line, ultraviolet rays such as broadband (BB), visible light, radiation, etc., but i-line is preferable.
As the exposure device, a parallel exposure device, a projection exposure device, a stepper, a scanner exposure device, etc. can be used.

By developing, a patterned resin film (patterned resin film) can be obtained. Generally, when a negative photosensitive resin composition is used, unexposed areas are removed with a developer.
The organic solvent used as the developer may be a good solvent for the photosensitive resin film alone, or a suitable mixture of a good solvent and a poor solvent.
Good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, α-acetyl-γ-butyrolactone, Examples include cyclopentanone and cyclohexanone.
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 added is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the developer.

The development time can be, for example, twice the time required for the photosensitive resin film to be completely dissolved after being immersed.
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 even more preferably 20 seconds to 5 minutes from the viewpoint of productivity.

After development, cleaning may be performed with a rinse solution.
As the rinsing liquid, distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. may be used alone or in appropriate mixtures, or may be used in stepwise combinations. good.

A patterned cured product can be obtained by heat-treating the patterned resin film.
The polyimide precursor of component (A) undergoes a dehydration ring-closing reaction through a heat treatment step, and usually becomes 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 230°C or lower or 180 to 230°C.
By being within the above range, damage to the substrate and devices can be suppressed to a minimum, making it possible to produce devices with a high yield, and realizing energy saving in the process.

The heat treatment time is preferably 5 hours or less, more preferably 30 minutes to 3 hours.
By being within the above range, the crosslinking reaction or dehydration ring closure reaction can proceed sufficiently.
The atmosphere for the heat treatment may be air 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.

The cured product 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 protection film, etc.
By using one or more selected from the group consisting of the above-mentioned passivation film, buffer coat film, interlayer insulating film, cover coat layer, surface protection film, etc., highly reliable semiconductor devices, multilayer wiring boards, various electronic devices, and laminated It is possible to manufacture electronic components such as devices (multi-die fan-out wafer level packages, etc.).

An example of the 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 with 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 a predetermined portion of the circuit elements, and a first conductor layer 3 is formed on the exposed circuit elements. It is formed. Thereafter, an interlayer insulating film 4 is formed on the semiconductor substrate 1.

Next, a photosensitive resin layer 5 made of chloride rubber, phenol novolac, or the like is formed on the interlayer insulating film 4, and a window 6A is formed using a known photolithographic technique to expose a predetermined portion of the interlayer insulating film 4. provided.

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

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

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

The present invention will be described in more detail below based on Examples and Comparative Examples. Note that the present invention is not limited to the following examples.

Synthesis example 1 (synthesis of A1)
N-methyl- It was dissolved in 30 g of 2-pyrrolidone (NMP) and stirred at 30° C. for 4 hours and then at room temperature overnight to obtain 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 solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyimide precursor A1.
Using gel permeation chromatography (GPC), the number average molecular weight was determined in terms of standard polystyrene under the following conditions. The number average molecular weight of A1 was 40,000.

The measurement was performed using a solution of 1 mL of solvent [tetrahydrofuran (THF)/dimethylformamide (DMF) = 1/1 (volume ratio)] for 0.5 mg of A1.

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 (0.03mol/L), _H3PO4 ( _0.06mol /L)
Flow rate: 1.0mL/min, detector: UV270nm

Further, the esterification rate of A1 (the reaction rate of the carboxy group of ODPA with HEMA) was calculated by performing NMR measurement under the following conditions. The esterification rate was 80 mol% based on the total carboxyl groups of the polyamic acid (the remaining 20 mol% was carboxyl groups).

Measuring equipment: Bruker Biospin AV400M
Magnetic field strength: 400MHz
Reference material: Tetramethylsilane (TMS)
Solvent: dimethyl sulfoxide (DMSO)

Examples 1 to 3 and Comparative Examples 1 to 5
(Preparation of photosensitive resin composition)
Photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 5 were prepared using the components and blending amounts shown in Table 1. The blending amounts in Table 1 are parts by mass of each component relative to 100 parts by mass of A1.

The components used are as follows. As component (A), A1 obtained in Synthesis Example 1 was used.

Ｂ２：ＡＴＭ-４Ｅ(新中村化学工業株式会社製、エトキシ化ペンタエリスリトールテトラアクリレート、下記式で表される化合物（ｎ１１＋ｎ１２＋ｎ１３＋ｎ１４は４である)）

Ｂ３：ＦＡ－３２４Ａ（日立化成株式会社製、ＥＯ変性ビスフェノールＡジアクリレート、下記式Ｂ３で表される化合物）

(B) Component: Polymerizable monomer B1: A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd., tricyclodecane dimethanol diacrylate, compound represented by the following formula B1)

B2: ATM-4E (manufactured by Shin Nakamura Chemical Industry Co., Ltd., ethoxylated pentaerythritol tetraacrylate, compound represented by the following formula (n11 + n12 + n13 + n14 is 4))

B3: FA-324A (manufactured by Hitachi Chemical Co., Ltd., EO-modified bisphenol A diacrylate, compound represented by the following formula B3)

Component (C): Photoinitiator C1: IRUGCURE OXE 02 (manufactured by BASF Japan Co., Ltd., ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1 -(O-acetyloxime))
C2: G-1820 (PDO) (manufactured by Lambson Co., Ltd., 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime)

(D) Component: Cyclization catalyst D1:2HE (manufactured by Morin Chemical Industry Co., Ltd., N-phenyldiethanolamine)

Ｄ３：Ｕ－ＣＡＴ ＳＡ１（サンアプロ株式会社製、下記式Ｄ３で表される化合物）

Ｄ４：４－ヒドロキシピリジン(D') Component D2: U-CAT SA810 (manufactured by San-Apro Co., Ltd., compound represented by the following formula D2)

D3: U-CAT SA1 (manufactured by San-Apro Co., Ltd., compound represented by the following formula D3)

D4: 4-hydroxypyridine

(E) Component: Solvent E1: KJCMPA-100 (manufactured by KJ Chemicals Co., Ltd., compound represented by the following formula E1)

(F) Component: Thermal polymerization initiator F1: Percyl D (manufactured by NOF Corporation, bis(1-phenyl-1-methylethyl) peroxide, compound represented by the following formula F1)

(Evaluation of sensitivity)
The obtained photosensitive resin composition was spin-coated onto a silicon wafer using a coating device Act8 (manufactured by Tokyo Electron Ltd.), dried at 105°C for 120 seconds, and then dried at 115°C for 120 seconds to form a dry film. A photosensitive resin film having a thickness of 13 μm was formed.
The development time was set to be twice the time required for the obtained photosensitive resin film to be completely dissolved by immersing it in cyclopentanone.
In addition, a photosensitive resin film was prepared in the same manner as above, and an i-line of 100 to 1100 mJ/cm ² was applied to the obtained photosensitive resin film using an i-line stepper FPA-3000iW (manufactured by Canon Inc.). Exposure was performed by irradiating a predetermined pattern with an irradiation dose of 100 mJ/cm2 in steps of ² .
The exposed resin film was developed with cyclopentanone using Act 8 for the above development time, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a patterned resin film.

The lower limit of the exposure amount at which the thickness of the patterned resin film obtained was 80% or more of the thickness of the photosensitive resin film before exposure was defined as the sensitivity. The results are shown in Table 1.

(Manufacture of patterned cured product 1)
The patterned resin film obtained in the sensitivity evaluation was heated at 200°C for 2 hours in a nitrogen atmosphere using a vertical diffusion furnace μ-TF (manufactured by Koyo Thermo Systems Co., Ltd.) to form a patterned cured product (cured film). A thickness of 10 μm) was obtained.

(Manufacture of patterned cured product 2)
The patterned resin film obtained in the sensitivity evaluation was heated at 400° C. for 1 hour in a nitrogen atmosphere using a vertical diffusion furnace μ-TF to obtain a patterned cured product.

(Evaluation of cyclization rate)
The IR (infrared spectroscopy) spectrum of the patterned resin film obtained in the sensitivity evaluation was measured using FT-IR IRAffinity-1S (manufactured by Shimadzu Corporation) under the following conditions. Let this value be IR1.
The measurement conditions for the IR spectrum were a transmission method, a measurement range of 400 to 4000 cm ⁻¹ , and 16 integrations.
A silicon wafer was used as the substrate for the measurement of the IR spectrum. First, a substrate to which no photosensitive resin composition was applied was measured and used as a background. Next, the resin film portion of the patterned resin film was measured using the above background to obtain an IR spectrum.

Further, the IR was measured in the same manner as above for the patterned cured product obtained in Production 1 of patterned cured product. Let this value be IR2.
Regarding the patterned cured product obtained in Production of Patterned Cured Product 2, IR was measured in the same manner as above. Let this value be IR3.

The cyclization rate was determined by dividing the value obtained by subtracting IR1 from IR2 by the value obtained by subtracting IR1 from IR3 and converting the result into a percentage. 65% or more was rated A, and less than 65% was rated B. The results are shown in Table 1.

(Evaluation of storage stability)
Within 24 hours after preparation, the photosensitive resin composition described above was spin-coated onto a Si substrate at a rotation speed that gave a film thickness of 13 μm after drying, and then coated on a hot plate at 105°C for 120 seconds at 115°C. The film was dried by heating for 120 seconds to form a photosensitive resin film. The silicon wafer was exposed by scratching a part of the film, and the height from the exposed silicon wafer surface to the film surface was measured using a contact profiler Dektak150 (manufactured by Bruker). , the same applies above and the same applies below). This is defined as a film thickness of 1.
After the above photosensitive resin composition was adjusted, it was allowed to stand at room temperature (25° C.) for 14 days. After standing still, spin coating was performed on the Si substrate at the same rotation speed as when forming the photosensitive resin film for film thickness 1 measurement, and heated on a hot plate at 105°C for 120 seconds and at 115°C for 120 seconds. It was dried to form a photosensitive resin film. The film thickness was measured in the same manner as above. This is assumed to have a film thickness of 2.
The absolute value obtained by subtracting the film thickness 1 from the film thickness 2 was divided by the film thickness 1, and the case where the percentage value was 5% or less was designated as A. Cases exceeding 5% were rated B. The results are shown in Table 1.

(Manufacture of patterned cured product 3)
The above-described photosensitive resin composition was spin-coated onto a Si substrate, and heated and dried on a hot plate at 105°C for 120 seconds and at 115°C for 120 seconds to form a photosensitive resin film with a thickness of 12.0 to 13.0 μm. Formed.
The obtained photosensitive resin film was exposed to broadband (BB) light using Mask Aligner MA-8 (manufactured by SUSS Microtech), and the exposed resin film was developed with cyclopentanone to form a 10 mm wide film. A strip-shaped patterned resin film was obtained.
The resulting patterned resin film was cured for 2 hours at 200° C. in a nitrogen atmosphere using a vertical diffusion furnace μ-TF to obtain a patterned cured product with a thickness of 10 μm.

(Evaluation of growth rate)
The patterned cured product obtained in Production of Patterned Cured Product 3 was immersed in a 4.9% by mass hydrofluoric acid aqueous solution, and a 10 mm wide cured product was peeled from the wafer.
A tensile test was performed on the peeled cured product with a width of 10 mm using Autograph AGS-X 100N (manufactured by Shimadzu Corporation). The distance between the chucks was 20 mm, the tensile speed was 5 mm/min, and the measurement temperature was 18 to 25° C., and each cured product of each example and comparative example was measured three times, and the average elongation rate was determined.
When the average elongation rate was over 50%, it was designated as A, when it was over 45% and not more than 50%, it was designated as B, and when it was 45% or less, it was designated as C. Table 1 shows the results before PCT (pressure cooker test).

Further, the patterned cured product obtained in the above-mentioned pattern cured product production 3 was tested at 121°C, 100RH (Relative Humidity)%, 2atm using a PCT test device HASTEST (manufactured by Hirayama Seisakusho Co., Ltd., PC-R8D). Processed for 100 hours.
The pattern cured product was taken out from the PCT testing apparatus, and the pattern cured product was peeled off in the same manner as above, a tensile test was performed, and the average elongation rate was determined.
When the average elongation rate was over 50%, it was designated as A, when it was over 45% and not more than 50%, it was designated as B, and when it was 45% or less, it was designated as C. Table 1 shows the results after PCT. "-" indicates that no measurement was performed.

The photosensitive resin composition of the present invention can be used for an interlayer insulating film, a cover coat layer, a surface protective film, etc., and the interlayer insulating film, cover coat layer, or surface protective film of the present invention can be used for electronic components, etc. I can do it.

Although some embodiments and/or examples of the present invention have been described in detail above, those skilled in the art will appreciate that these exemplary embodiments and/or It is easy to make many changes to the embodiment. Accordingly, many of these modifications are within the scope of this invention.
The documents mentioned in this specification and the content of the application that is the basis of the priority right under the Paris Convention of this application are all incorporated by reference.

Claims (19)

(A) a polyimide precursor having a polymerizable unsaturated bond,
(B) a polymerizable monomer,
(C1) A compound represented by the following formula (15) ,
(C2) a compound represented by the following formula (16),
(D) A cyclization catalyst, and (E) a photosensitive resin composition containing a solvent.

(In formula (15), R _11A is an alkyl group having 1 to 12 carbon atoms, and a1 is an integer of 0 to 5. R _12A is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. R _13A and R _14A each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group. When a1 is an integer of 2 or more, R _11A may be the same or different. .)

(In formula (16), R _21A is an alkyl group having 1 to 12 carbon atoms, and R _22A and R _23A are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and an alkyl group having 1 to 12 carbon atoms. group, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group, and c1 is an integer of 0 to 5. When c1 is an integer of 2 or more, R _21A may be the same or different. Also good.) 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 formula (1), X ₁ is a tetravalent group having one or more aromatic groups, -COOR ₁ group and -CONH- group are in the ortho position to each other, -COOR ₂ group and -CO - groups are in the ortho position to each other.Y ₁ is a divalent aromatic group.R ₁ and R ₂ are each independently a hydrogen atom, a group represented by the following formula (2), or a carbon number 1 to 4 aliphatic hydrocarbon groups, and at least one of R ₁ and R ₂ is a group represented by the above formula (2).)

(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, and m is an integer of 1 to 10.) The component (D) is N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, and 2,2'-(4-methyl The photosensitive resin composition according to claim 1 or 2, wherein the photosensitive resin composition is one or more selected from the group consisting of phenylimino)diethanol. The photosensitive resin composition according to claim 1 or 2, wherein the component (D) contains a compound represented by the following formula (17).

(In formula (17), R _31A to R _33A are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxy group, or a monovalent aromatic group) and at least one of R _31A to R _33A is a monovalent aromatic group. _{R 31A} to R _33A may form a ring with adjacent groups.) The photosensitive resin composition according to any one of claims 1 to 4, wherein R _11A is an alkyl group having 1 to 4 carbon atoms . The photosensitive resin composition according to any one of claims 1 to 5, wherein the component (B) contains a polymerizable monomer having an aliphatic cyclic skeleton. The photosensitive resin composition according to any one of claims 1 to 6, wherein the component (B) has a group containing a polymerizable unsaturated double bond. 8. The photosensitive resin composition according to claim 7, wherein the component (B) is a polymerizable monomer having a group containing two or more polymerizable unsaturated double bonds. The photosensitive resin composition according to any one of claims 1 to 7, wherein the component (B) contains a polymerizable monomer represented by the following formula (3).

(In formula (3), R ₆ and R ₇ are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following formula (4). n1 is 0 or 1; , n2 is an integer of 0 to 2, and n1+n2 is 1 or more.At least one of n1 R ₆ and n2 R ₇ is a group represented by the following formula (4).)

(In formula (4), R ₉ to R ₁₁ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and l is an integer of 0 to 10.) The photosensitive resin composition according to claim 9, wherein n1+n2 is 2 or 3. The photosensitive resin composition according to any one of claims 1 to 10, wherein the component (B) contains a polymerizable monomer represented by the following formula (5).

The photosensitive resin composition according to any one of claims 1 to 11, further comprising (F) a thermal polymerization initiator. The photosensitive resin composition according to any one of claims 1 to 12, further comprising an antioxidant. Coating the photosensitive resin composition according to any one of claims 1 to 13 on a substrate and drying it to form a photosensitive resin film;
pattern-exposing the photosensitive resin film to obtain a resin film;
Developing the resin film after the pattern exposure using an organic solvent to obtain a pattern resin film;
A method for producing a patterned cured product, comprising the step of heat-treating the patterned resin film. The method for producing a patterned cured product according to claim 14, wherein the temperature of the heat treatment is 230°C or less. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 13. The cured product according to claim 16, which is a pattern cured product. An interlayer insulating film, a cover coat layer, or a surface protective film produced using the cured product according to claim 16 or 17. An electronic component comprising the interlayer insulating film, cover coat layer, or surface protection film according to claim 18.

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