JP2020122875A - Photosensitive resin composition, method for producing pattern cured product, cured product, interlayer insulation film, cover coat layer, surface protective film and electronic component - Google Patents

Abstract

To provide a photosensitive resin composition that can form a cured product having excellent moisture resistance as well as excellent elongation, even when cured at a low temperature of 200°C or lower, and a method for producing a pattern cured product, a cured product, an interlayer insulation film, a cover coat layer, a surface protective film and an electronic component each of which employs the photosensitive resin composition.SOLUTION: A photosensitive resin composition contains (A) a polyimide precursor having a specific structural unit, (B) a polymerizable monomer, (C) a photopolymerization initiator, (D) alcohol having an aliphatic cyclic skeleton, and (E) a solvent.SELECTED DRAWING: None

Description

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

Conventionally, polyimide or polybenzoxazole having excellent heat resistance, electrical characteristics, and mechanical characteristics are used for the surface protective film and the interlayer insulating film of the semiconductor element. In recent years, a photosensitive resin composition in which a photosensitive property is imparted to these resins themselves has been used, and when this is used, the manufacturing process of a patterned cured film can be simplified and the complicated manufacturing process can be shortened (for example, Patent Document 1). 1).

In recent years, the miniaturization of transistors, which has supported the high performance of computers, is facing the limit of scaling law, and a stacked device structure in which semiconductor elements are three-dimensionally stacked for higher performance and higher speed is attracting attention. Have been collected. Among the stacked device structures, a multi-die fanout wafer level package is a package manufactured by encapsulating a plurality of dies in a single package, and has been proposed in the past. It is attracting attention because it can be expected to achieve lower cost and higher performance than the existing fan-out wafer level package (manufactured by encapsulating one die in one package).

In manufacturing a multi-die fan-out wafer-level package, low-temperature curability is strongly required from the viewpoint of protecting high-performance dies and encapsulating materials with low heat resistance and improving yield (for example, patents Reference 2). Examples of conventional resin compositions used for the above applications include those disclosed in Patent Document 3.

JP, 2009-265520, A International Publication No. 2008/111470 JP, 2016-199662, A

However, with the conventional resin composition, a cured film satisfying both moisture resistance and extensibility cannot be obtained. If the moisture resistance is low, the reliability of the semiconductor device and the display device may be affected when the surface protective film and the interlayer insulating film are formed.

An object of the present invention is to use a photosensitive resin composition capable of forming a cured product having excellent moisture resistance and excellent elongation even at low temperature curing of 200° C. or less, and the use of the photosensitive resin composition. Another object of the present invention is to provide 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.

（式（１）中、Ｘ^１は１以上の芳香族基を有する４価の基であり、−ＣＯＯＲ^１基と−ＣＯ−基とは互いにオルト位置にあり、−ＣＯＯＲ^２基と−ＣＯＮＨ−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。）
２．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重合性モノマーを含む１に記載の感光性樹脂組成物。
３．前記重合性の不飽和二重結合を含む基の数が２以上である２に記載の感光性樹脂組成物。
４．前記（Ｄ）成分が、下記式（４１）〜（４４）で表される化合物からなる群から選択される１以上の化合物を含む１〜３のいずれかに記載の感光性樹脂組成物。

（式（４１）〜（４４）中、Ｒ^４１〜Ｒ^４４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（４５）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^４１は下記式（４５）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^４２は下記式（４５）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^４３は下記式（４５）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^４４は下記式（４５）で表される基である。
式（４３）においてＲ^４３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（４４）においてＲ^４４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（４５）中、ｌは１〜１０の整数である。）
５．前記式（４１）〜（４４）で表される化合物が、前記式（４５）で表される基を２つ有する４に記載の感光性樹脂組成物。
６．前記（Ｄ）成分が、前記式（４３）で表される化合物を含む４又は５に記載の感光性樹脂組成物。
７．前記（Ｄ）成分の含有量が、前記（Ａ）成分１００質量部に対して、１〜５０質量部である１〜６のいずれかに記載の感光性樹脂組成物。
８．前記（Ｄ）成分の含有量が、前記（Ｂ）成分の含有量に対して、０．１〜５倍である１〜７のいずれかに記載の感光性樹脂組成物。
９．さらに、（Ｆ）熱重合開始剤を含む１〜８のいずれかに記載の感光性樹脂組成物。
１０．１〜９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。
１１．前記加熱処理の温度が２００℃以下である１０に記載のパターン硬化物の製造方法。
１２．１〜１１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。
１３．パターン硬化物である１２に記載の硬化物。
１４．１２又は１３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。
１５．１４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 composition and the like are provided.
1. (A) a polyimide precursor having a structural unit represented by the following formula (1),
(B) polymerizable monomer,
(C) a photopolymerization initiator,
A photosensitive resin composition containing (D) an alcohol having an aliphatic cyclic skeleton, and (E) a solvent.

(In the formula (1), X ¹ is a tetravalent group having one or more aromatic groups, the —COOR ¹ group and the —CO— group are in the ortho positions to each other, and the —COOR ² group and the —CONH— group are present. Y ¹ is a divalent aromatic group, and 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 formula (2).)

(In the 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.)
2. 2. The photosensitive resin composition according to 1, wherein the component (B) contains a polymerizable monomer having a group containing a polymerizable unsaturated double bond.
3. 3. The photosensitive resin composition according to 2, wherein the number of groups containing the polymerizable unsaturated double bond is 2 or more.
4. The photosensitive resin composition according to any one of 1 to 3, wherein the component (D) contains one or more compounds selected from the group consisting of compounds represented by the following formulas (41) to (44).

(In formulas (41) to (44), R ^{41 to} R ⁴⁴ are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following formula (45).
a is an integer of 1 to 10 and at least one R ⁴¹ is a group represented by the following formula (45).
b is an integer of 1 to 12, and at least one R ⁴² is a group represented by the following formula (45).
c is an integer of 1 to 16, and at least one R ⁴³ is a group represented by the following formula (45).
d is an integer of 1 to 16 and at least one R ⁴⁴ is a group represented by the following formula (45).
In the formula (43), R ⁴³ can be bonded to all the substitution positions of the aliphatic cyclic skeleton, and in the formula (44), R ⁴⁴ can be bonded to all the substitution positions of the aliphatic cyclic skeleton. )

In formula (45), l is an integer of 1-10. )
5. 5. The photosensitive resin composition according to 4, wherein the compound represented by the formulas (41) to (44) has two groups represented by the formula (45).
6. 6. The photosensitive resin composition according to 4 or 5, wherein the component (D) contains the compound represented by the formula (43).
7. Content of the said (D) component is 1-50 mass parts with respect to 100 mass parts of said (A) components, The photosensitive resin composition in any one of 1-6.
8. 8. The photosensitive resin composition according to any one of 1 to 7, wherein the content of the component (D) is 0.1 to 5 times the content of the component (B).
9. Furthermore, the photosensitive resin composition in any one of 1-8 containing (F) thermal-polymerization initiator.
10. A step of applying the photosensitive resin composition according to any one of 10 to 9 to a substrate and drying the composition to form a photosensitive resin film,
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 pattern resin film,
A method for producing a patterned cured film, comprising the step of heat-treating the patterned resin film.
11. 11. The method for producing a patterned cured product according to 10, wherein the temperature of the heat treatment is 200° C. or lower.
A cured product obtained by curing the photosensitive resin composition according to any of 12.1 to 11.
13. The cured product according to 12, which is a pattern cured product.
14. An interlayer insulating film, a cover coat layer or a surface protective film produced by using the cured product according to 12 or 13.
An electronic component including the interlayer insulating film, the cover coat layer, or the surface protective film according to 15.14.

EFFECTS OF THE INVENTION According to the present invention, a photosensitive resin composition capable of forming a cured product having good moisture resistance and excellent elongation even if it is cured at a low temperature of 200° C. or less, and the photosensitive resin composition is used. It is possible to provide 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.

It is a manufacturing-process figure of the electronic component which concerns on one Embodiment of this invention.

Hereinafter, embodiments of the photosensitive resin composition of the present invention, a method for producing a pattern cured 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. The present invention is not limited to the embodiments described below.

In the present specification, “A or B” may include either A or B, or may include both. Further, in the present specification, the term “process” is used not only as an independent process but also in the case where the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. included.
The numerical range indicated by "-" indicates the range including the numerical values before and after "-" as the minimum value and the maximum value, respectively. In addition, in the present specification, the content of each component in the composition is the sum of the plurality of substances present in the composition unless there is a plurality of substances corresponding to each component in the composition, unless otherwise specified. Means quantity. Furthermore, unless otherwise specified, the exemplified materials may be used alone or in combination of two or more kinds.
In the present specification, the “(meth)acrylic group” means “acrylic group” and “methacrylic group”.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention includes (A) a polyimide precursor having a structural unit represented by the formula (1) (hereinafter, also referred to as “component (A)”), and (B) a polymerizable monomer (hereinafter, referred to as “monomer”). , (Also referred to as “(B) component”), (C) photopolymerization initiator (hereinafter, also referred to as “(C) component”), (D) alcohol having an aliphatic cyclic skeleton (hereinafter, “(D)”). And (E) solvent (hereinafter also referred to as “(E) component”). 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.

The photosensitive resin composition of the present invention can form a cured product having excellent moisture resistance even when it is cured at a low temperature of 200° C. or lower by containing the above components. Further, even at a low temperature of 200° C. or lower, a cured product having excellent mechanical properties (especially elongation) can be formed.
Hereinafter, each component will be described.

（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−ＣＯ−基とは互いにオルト位置にあり、−ＣＯＯＲ^２基と−ＣＯＮＨ−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（好ましくは２〜５の整数、より好ましくは２又は３）である。） (Component (A): Polyimide Precursor Having Structural Unit Represented by Formula (1))
Since the photosensitive resin composition of the present invention contains the component (A), it has a high i-line transmittance and can form a good cured product even when it is cured at a low temperature of 200° C. or lower. The component (A) is not particularly limited as long as it is a polyimide precursor having a structural unit represented by the formula (1).

(In the formula (1), X ¹ is a tetravalent group having one or more aromatic groups, the —COOR ¹ group and the —CO— group are in the ortho position to each other, and the —COOR ² group and the —CONH group are present. -Group is 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 are aliphatic hydrocarbon groups, and at least one of R ¹ and R ² is a group represented by the formula (2).)

(In the 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). , And more preferably 2 or 3).)

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

In the tetravalent group having one or more (preferably 1 to 3, more preferably 1 or 2) aromatic groups of X ¹ of the formula (1), the aromatic group is an aromatic hydrocarbon group (having a carbon number of For example, it may be 6 to 20) or an aromatic heterocyclic group (the number of atoms is, for example, 5 to 20). Aromatic hydrocarbon groups are preferred.

The aromatic hydrocarbon group represented by X ^{1 in} the formula (1) is a divalent to tetravalent (divalent, trivalent or tetravalent) group formed from a benzene ring and a divalent to tetravalent group formed from naphthalene. And a divalent to tetravalent group formed from perylene.

（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 group having one or more aromatic groups represented by X ¹ of the formula (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 with the benzene ring to which they are bonded. 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—, methylene group, bis(trifluoromethyl)methylene group, or difluoromethylene group, and more preferably —O—.
Z ³ is preferably -O-.

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

（式（２１）中、Ｒ^２１〜Ｒ^２８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 (23).

(In the formula (21), R ^{21 to} R ²⁸ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group or a monovalent organic group having a halogen atom.)

As the monovalent aliphatic hydrocarbon group of R ^{21 to} R ²⁸ (preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), a methyl group is preferable.

The monovalent organic group having a halogen atom (preferably a fluorine atom) of R ^{21 to} R ²⁸ is a monovalent aliphatic hydrocarbon group having a halogen atom (preferably having 1 to 10 carbon atoms, more preferably having 1 carbon atom). To 6) are preferable, and a trifluoromethyl group is more preferable.

In the formula (21), for example, R ²² and R ²³ may be a monovalent aliphatic hydrocarbon group (for example, a methyl group), and R ²¹ and R ^{24 to} R ²⁸ may be hydrogen atoms.

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

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

Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms (preferably 1 or 2) represented by R ^{3 to} R ^{5 in} the formula (2) include a methyl group, an ethyl group, an n-propyl group and a 2-propyl group. To be A methyl group is preferred.

（式（２２）中、Ｘ^１は式（１）で定義した通りである。式（２３）中、Ｙ^１は式（１）で定義した通りである。式（２４）中、Ｒ^３〜Ｒ^５及びｍは式（２）で定義した通りである。） The polyimide precursor having a structural unit represented by the formula (11) includes, for example, a tetracarboxylic dianhydride represented by the following formula (22) and a diamino compound represented by the following formula (23): A polyamic acid is produced by reacting in an organic solvent such as N-methyl-2-pyrrolidone (hereinafter referred to as “NMP”), and a compound represented by the following formula (24) is added and reacted in an organic solvent. Can be produced by introducing an ester group wholly or partly.

(In Formula (22), X ¹ is as defined in Formula (1). In Formula (23), Y ¹ is as defined in Formula (1). In Formula (24), R ³ to R ⁵ and m are as defined in formula (2).)

The tetracarboxylic dianhydride represented by the formula (22) and the diamino compound represented by the formula (23) may be one type alone or two or more types.

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

（式（３１）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^３１基と−ＣＯ−基とは互いにオルト位置にあり、−ＣＯＯＲ^３２基と−ＣＯＮＨ−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^３１及びＲ^３２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。） The component (A) may have a structural unit other than the structural unit represented by the formula (1). Examples of the structural unit other than the structural unit represented by the formula (1) include a structural unit represented by the following formula (31).

(In the formula (31), X ² is a tetravalent group having one or more aromatic groups, the —COOR ³¹ group and the —CO— group are in the ortho position to each other, and the —COOR ³² group and the —CONH group are present. The — group is in an ortho position to each other, Y ² is a divalent aromatic group, and R ³¹ and R ³² 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 (31) include the same groups as the tetravalent groups having one or more aromatic groups represented by X ^{1 in} formula (1). Examples of the divalent aromatic group for Y ² include the same groups as the divalent aromatic group for Y ^{1 in} formula (1). Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms of R ³¹ and R ³² include the same groups as the aliphatic hydrocarbon group having 1 to 4 carbon atoms of R ¹ and R ² of the formula (1).

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

In the component (A), the ratio of the carboxy groups esterified with the group represented by the formula (2) to all carboxy groups and all carboxy esters in the polyimide precursor is 50 mol% or more. Preferably, 60 to 100 mol% is more preferable, and 70 to 90 mol% is more preferable. The upper limit is not particularly limited and may be 100 mol%.

The molecular weight of the component (A) is not particularly limited, but the weight average molecular weight is preferably 10,000 to 50,000, more preferably 15,000 to 45,000, and 18,000 to 40, More preferably, it is 000.
The weight average molecular weight of the component (A) can be measured, for example, by a gel permeation chromatography method, and can be determined by conversion using a standard polystyrene calibration curve.

(Component (B): polymerizable monomer)
The photosensitive resin composition of the present invention contains (B) a polymerizable monomer. The component (B) crosslinks with the component (A), or the components (B) polymerize with each other to form a crosslinked network. The component (B) preferably has a group containing a polymerizable unsaturated double bond, and in order to improve the crosslinking density, improve the photosensitivity, and suppress the swelling of the pattern after development, 2 to 4 (preferably 2) is used. Alternatively, it preferably has a group containing a polymerizable unsaturated double bond of 3). The group is preferably a (meth)acrylic group or an allyl group from the viewpoint of being polymerizable by a photopolymerization initiator.

Examples of the component (B) include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate , Pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethoxylated pentaerythritol tetraacrylate Acrylate, ethoxylated isocyanuric acid triacrylate, ethoxylated isocyanuric acid trimethacrylate, acryloyloxyethyl isocyanurate, methacryloyloxyethyl isocyanurate and the like can be mentioned. Among them, tetraethylene glycol dimethacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol Tetraacrylate is preferred.

The content of the component (B) is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the component (A). From the viewpoint of improving the hydrophobicity of the cured product, it is more preferably 3 to 45 parts by mass, further preferably 5 to 40 parts by mass.
When it is within the above range, a practical relief pattern is easily obtained, and the residue after development of the unexposed portion is easily suppressed.

(Component (C): photopolymerization initiator)
Examples of the component (C) include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, benzophenone derivatives such as fluorenone; 2,2′-diethoxyacetophenone, 2- Acetophenone derivatives such as hydroxy-2-methylpropiophenone and 1-hydroxycyclohexyl phenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and diethylthioxanthone; benzyl, benzyldimethylketal, benzyl-β-methoxy Benzyl derivatives such as ethyl acetal; benzoin derivatives such as benzoin and benzoin methyl ether; 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2- (O-Methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1 , 3-Diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime, ethanone, 1-[9-ethyl-6-(2- Methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), oxime esters such as compounds represented by the following formulas, and the like are preferable, but not limited thereto. .. Oxime esters are preferable in terms of photosensitivity.

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

(Component (D): alcohol having an aliphatic cyclic skeleton)
By containing the component (D), the photosensitive resin composition of the present invention can impart hydrophobicity to the obtained cured film and improve moisture resistance.

The component (D) is not particularly limited as long as it is an alcohol having an aliphatic cyclic skeleton (the carbon number forming the cyclic skeleton is, for example, 3 to 20, preferably 5 to 15). For example, the aliphatic cyclic skeleton (at least One, preferably two or three) and a compound containing a structure represented by the following formula (45).

（式（４１）〜（４４）中、Ｒ^４１〜Ｒ^４４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（４５）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^４１は下記式（４５）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^４２は下記式（４５）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^４３は下記式（４５）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^４４は下記式（４５）で表される基である。
式（４３）においてＲ^４３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（４４）においてＲ^４４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（４５）中、ｌは１〜１０の整数である。） Examples of the component (D) include compounds represented by the following formulas (41) to (44).

(In formulas (41) to (44), R ^{41 to} R ⁴⁴ are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following formula (45).
a is an integer of 1 to 10, and at least one (preferably two or three) R ⁴¹ is a group represented by the following formula (45).
b is an integer of 1 to 12, and at least one (preferably two or three) R ⁴² is a group represented by the following formula (45).
c is an integer of 1 to 16, and at least one (preferably two or three) R ⁴³ is a group represented by the following formula (45).
d is an integer of 1 to 16, and at least one (preferably two) R ⁴⁴ is a group represented by the following formula (45).
In formula (43), R ⁴³ can be bonded to all the substitution positions of the aliphatic cyclic skeleton, and in formula (44), R ⁴⁴ can be bonded to all the substitution positions of the aliphatic cyclic skeleton. )

In formula (45), l is an integer of 1-10. )

The aliphatic hydrocarbon group having 1 to 4 carbon atoms of R ^{41 to} R ⁴⁴ of formulas (41) to (44) is an aliphatic hydrocarbon group having 1 to 4 carbon atoms of R ¹ and R ² of formula (1). The same groups as the groups can be mentioned.

Among the compounds represented by the formulas (41) to (44), for example, the compound represented by the formula (43) can be used.

From the viewpoint of improving the hydrophobicity of the cured film, the amount of component (D) added is preferably 1 to 50 parts by weight, more preferably 3 to 45 parts by weight, and even more preferably 100 parts by weight of component (A). It is 3 to 40 parts by mass, and may be 3 to 30 parts by mass, 3 to 20 parts by mass, or 3 to 15 parts by mass. The amount of component (B) added is preferably 0.1 to 5 times, more preferably 0.3 to 3 times, and still more preferably 0.3 to 2 times.

(Component (E): solvent)
The photosensitive resin composition of the present invention contains (E) a solvent.
As the component (E), N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, cyclohexanone, cyclopentanone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, N-dimethylmorpholine and the like can be mentioned. Usually, there is no particular limitation as long as it can sufficiently dissolve other components.
Among these, N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, and N,N-dimethylformamide are preferred from the viewpoint of excellent solubility of each component and coating properties when forming a photosensitive resin film. , N,N-dimethylacetamide is preferably used.

（式中、Ｒ^５１〜Ｒ^５３は、それぞれ独立に、炭素数１〜１０のアルキル基である。） Further, as the component (E), a compound represented by the following formula (51) may be used.

(In the formula, R ^{51 to} R ⁵³ are each independently an alkyl group having 1 to 10 carbon atoms.)

The alkyl group having 1 to 10 carbon atoms (preferably 1 to 3, more preferably 1 or 3) represented by R ^{51 to} R ⁵³ in the formula (51) includes a methyl group, an ethyl group, an n-propyl group and an isopropyl group. , N-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like.
The compound represented by the formula (51) is preferably 3-methoxy-N,N-dimethylpropanamide (for example, trade name “KJCMPA-100” (manufactured by KJ Chemicals Corporation)).

Although the content of the component (E) is not particularly limited, it is generally 50 to 1000 parts by mass with respect to 100 parts by mass of the component (A).

(Component (F): thermal polymerization initiator)
The photosensitive resin composition of the present invention may further contain (F) a thermal polymerization initiator (hereinafter, also referred to as “(F) component”) from the viewpoint of accelerating the polymerization reaction.
The component (F) is not decomposed by heating (drying) for removing the solvent during film formation, but is decomposed by heating during curing to generate radicals, and the components (B), the components (A) and ( Compounds that accelerate the polymerization reaction of component B) are preferred.
The component (F) preferably has a decomposition point of 110° C. or higher and 200° C. or lower, and more preferably 110° C. or higher and 175° C. or lower from the viewpoint of promoting the polymerization reaction at lower temperatures.

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, di- Dialkyl peroxides such as -t-butyl peroxide, diacyl peroxides such as dilauroyl peroxide, dibenzoyl peroxide, peroxy compounds such as di(4-t-butylcyclohexyl)peroxydicarbonate and di(2-ethylhexyl)peroxydicarbonate. Dicarbonate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropylmonocarbonate, t-butylperoxybenzoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexa Examples thereof include peroxyesters such as noate and bis(1-phenyl-1-methylethyl)peroxide. Commercially available products include trade names “Park Mill D”, “Park Mill P”, “Park Mill H” (above, manufactured by NOF CORPORATION) and the like.

When the component (F) is contained, the content of the component (F) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (A), and is 0 to secure good flux resistance. 2 to 20 parts by mass is more preferable, and 0.3 to 10 parts by mass is further preferable from the viewpoint of suppressing deterioration of solubility due to decomposition during drying.

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

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

（式（６１）中、Ｒ^６１及びＲ^６２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。） Preferred silane coupling agents include compounds having a urea bond (-NH-CO-NH-). This makes it possible to further enhance the adhesiveness to the substrate even when the curing is performed at a low temperature of 200° C. or lower.
The compound represented by the following formula (61) is more preferable because it exhibits excellent adhesiveness when cured at a low temperature.

(In the formula (61), R ⁶¹ and R ⁶² 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 the formula (61) include ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, and 3-ureidopropyltrimethoxysilane. , 3-ureidopropyltriethoxysilane, 4-ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane and the like can be mentioned, with preference given to 3-ureidopropyltriethoxysilane.

A silane coupling agent having a hydroxy 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 a urea bond in the molecule can further improve the adhesion of the cured product to the substrate during low temperature curing.

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, phenylsilanetriol, 1,4-bis(trihydroxysilyl)benzene, 1,4-bis(methyldihydroxysilyl)benzene, 1,4-bis(ethyldihydroxysilyl)benzene, 1,4-bis(propyldihydroxysilyl)benzene, 1,4-bis(butyldihydroxysilyl)benzene, 1,4-bis(dimethylhydroxysilyl)benzene, 1,4-bis(diethylhydroxysilyl)benzene, 1, Examples thereof include 4-bis(dipropylhydroxysilyl)benzene, 1,4-bis(dibutylhydroxysilyl)benzene, and a compound represented by the following formula (62). Among them, the compound represented by the formula (62) is particularly preferable in order to further improve the adhesiveness to the substrate.

（式（６２）中、Ｒ^６３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^６４及びＲ^６５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 the formula (62), R ⁶³ is a monovalent organic group having a hydroxy group or a glycidyl group, and R ⁶⁴ and R ⁶⁵ are each independently an alkyl group having 1 to 5 carbon atoms. o is 1 Is an integer of 10 and p is an integer of 1 to 3.)

Examples of the compound represented by the formula (62) include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, and 3-hydroxypropyltrimethoxysilane. Hydroxypropyltriethoxysilane, 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2- Examples include glycidoxyethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybutyltriethoxysilane, and the like. To be

The silane coupling agent having a hydroxy group or a glycidyl group preferably further contains a group having a nitrogen atom, and more preferably a silane coupling agent having an amino group or an amide bond.
Further, as a silane coupling agent having an amino group, bis(2-hydroxymethyl)-3-aminopropyltriethoxysilane, bis(2-hydroxymethyl)-3-aminopropyltrimethoxysilane, bis(2-glycid Examples include xymethyl)-3-aminopropyltriethoxysilane and bis(2-hydroxymethyl)-3-aminopropyltrimethoxysilane.

Examples of the silane coupling agent having an amide bond include compounds represented by the following formula (63).
^{_{R 66 - (CH 2) q}} -CO-NH- (CH 2) r -Si (OR 67) 3 (63)
(In formula (63), R ⁶⁶ is a hydroxy group or a glycidyl group, q and r are each independently an integer of 1 to 3, and R ⁶⁷ 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 0.3 to 10 parts by mass, and more preferably 1 to 100 parts by mass of the component (A). More preferably, it is from 10 to 10 parts by mass.

(Surfactant or leveling agent)
By containing a surfactant or a leveling agent, coating properties (for example, suppression of striation (unevenness of 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, and the like, and as a commercially available product, a trade name “Megafuck F171 , "F173", "R-08" (above, manufactured by DIC Corporation), trade names "Florard FC430", "FC431" (above, manufactured by Sumitomo 3M Co., Ltd.), trade names "organosiloxane polymer KP341", " KBM303", "KBM403", "KBM803" (above, Shin-Etsu Chemical Co., Ltd. make) etc. are mentioned.

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

(anti-rust)
By containing a rust preventive agent, it is possible to suppress corrosion of copper and copper alloys and prevent discoloration.
Examples of the rust preventive agent include triazole derivatives and tetrazole derivatives.

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 100 parts by mass of the component (A). 3 parts by mass is more preferable.

(Polymerization inhibitor)
By containing the polymerization inhibitor, good storage stability can be secured.
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-toluquinone, tannic acid, parabenzylaminophenol, and nitrosamines.

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

The photosensitive resin composition of the present invention essentially comprises the components (A) to (E), and optionally the component (F), a coupling agent, a surfactant, a leveling agent, a rust inhibitor, and a polymerization inhibitor. In addition, inevitable impurities may be contained in 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 Alternatively, 100% by mass may be the components (A) to (E) or the components (A) to (F).

[Cured product]
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 film or a patterned cured film. The 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, a step of applying the above-mentioned photosensitive resin composition onto a substrate and drying to form a photosensitive resin film, and pattern-exposing the photosensitive resin film to form the resin film. It includes a step of obtaining, a step of developing the resin film after pattern exposure with an organic solvent to obtain a pattern resin film, and a step of heat-treating the pattern resin film. Thereby, a patterned cured film can be obtained.

The method for producing a cured product having no pattern includes, for example, the step of forming the above-mentioned photosensitive resin film and the step of heat treatment. Further, a step of exposing may be provided.

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

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

Drying can be performed using a hot plate, oven, or the like.
The drying temperature is preferably 90 to 150°C, and more preferably 90 to 120°C from the viewpoint of ensuring the dissolution contrast.
The drying time is preferably 30 seconds to 5 minutes.
You may dry twice or more.
This makes it possible to obtain a photosensitive resin film in which the above-mentioned photosensitive resin composition is formed into a film.

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

In pattern exposure, for example, a predetermined pattern is exposed through a photomask.
Examples of the actinic ray to be applied include i-rays, ultraviolet rays such as broadband (BB), visible rays, and radiations, but i-rays are preferable.
As the 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. Generally, when a negative photosensitive resin composition is used, the unexposed portion is removed with a developing solution.
As the organic solvent used as the developing solution, as the developing solution, a good solvent for the photosensitive resin film may be used alone, or a good solvent and a poor solvent may be appropriately mixed and used.
Examples of the good solvent include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, gamma butyrolactone, α-acetyl-gamma butyrolactone and cyclopenta. Non, cyclohexanone, etc. are mentioned.
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 addition amount is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the developing solution.

The development time can be set to, for example, twice as long as the time until the photosensitive resin film is immersed and completely 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 further preferably 20 seconds to 5 minutes from the viewpoint of productivity.

After development, you may wash 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 alone or in an appropriate mixture, or may be used in combination stepwise. Good.

A patterned cured product can be obtained by heating the patterned resin film.
The polyimide precursor of the component (A) undergoes a ring-closing reaction in the 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, further preferably 200°C or lower, or 140 to 200°C.
Within the above range, damage to the substrate and the device can be suppressed to be small, the device can be produced with a high yield, and the energy saving of the process can be realized.

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

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

[Interlayer insulation film, cover coat layer, surface protection film, electronic parts]
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 or a surface protective film.
Using one or more selected from the group consisting of the passivation film, the buffer coat film, the interlayer insulating film, the cover coat layer, and the surface protective film, the semiconductor device, the multilayer wiring board, various electronic devices, and the laminate having high reliability can be obtained. It is possible to manufacture electronic parts such as devices (multi-die fan-out wafer level package etc.).

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

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

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

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

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

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

Synthesis example 1 (synthesis of A1)
3,3′,4,4′-Diphenyl ether tetracarboxylic dianhydride (ODPA) 7.07 g, 2-hydroxyethyl methacrylate (HEMA) 0.831 g and a catalytic amount of 1,4-diazabicyclo[2.2. 2. ] Octane was dissolved in 30 g of N-methyl-2-pyrrolidone (NMP), stirred at 45°C for 1 hour, and then cooled to 25°C. After adding a solution of 4.12 g of 2,2′-dimethylbiphenyl-4,4′-diamine (DMAP) dissolved in NMP, the mixture was stirred at 30° C. for 4 hours. Then, the mixture was stirred overnight at room temperature to obtain a reaction solution.

9.45 g of trifluoroacetic anhydride was added to this reaction solution, and the mixture was stirred at 45° C. for 3 hours, 7.08 g of HEMA and 0.01 g of benzoquinone were added, and the mixture was stirred at 45° C. for 20 hours. This reaction liquid was added dropwise to distilled water, the precipitate was collected by filtration, and dried under reduced pressure to obtain a polyimide precursor A1.
Using a gel permeation chromatograph (GPC) method, the weight average molecular weight was determined under the following conditions by standard polystyrene conversion. The weight average molecular weight of A1 was 25,575.

It was measured using a solution of 1 mL of a solvent [tetrahydrofuran (THF)/dimethylformamide (DMF)=1/1 (volume ratio)] against 0.5 mg of A1.
Measuring device: Detector L4000UV manufactured by Hitachi, Ltd.
Pump: L6000 made by Hitachi, Ltd.
Shimadzu C-R4A Chromatopac
Measurement conditions: Column Gelpack GL-S300MDT-5×2 eluent: THF/DMF=1/1 (volume ratio)
_{LiBr (0.03mol / L), H} 3 PO 4 (0.06mol / L)
Flow rate: 1.0 mL/min, detector: UV270 nm

Further, the esterification rate of A1 (reaction rate of carboxy group of ODPA with HEMA) was calculated by performing NMR measurement under the following conditions. The esterification rate was 80 mol% with respect to all carboxy groups and all carboxy esters (the remaining 20 mol% were carboxy groups).
Measuring instrument: Bruker BioSpin AV400M
Magnetic field strength: 400MHz
Reference substance: Tetramethylsilane (TMS)
Solvent: Dimethyl sulfoxide (DMSO)

Examples 1 and 2 and Comparative Examples 1 and 2
[Preparation of photosensitive resin composition]
Photosensitive resin compositions of Examples 1 and 2 and Comparative Examples 1 and 2 were prepared with the components and blending amounts shown in Table 1. The blending amounts in Table 1 are parts by mass of each component with respect to 100 parts by mass of A1.

Component (A): Polyimide precursor A1: having a structural unit represented by formula (1): Polyimide precursor A1

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：Ａ−ＤＣＰ（新中村化学工業株式会社製、トリシクロデカンジメタノールジアクリレート、下記式で表される化合物）

Component (B): Polymerizable monomer B1: TEGDMA (manufactured by Shin-Nakamura Chemical Co., Ltd., tetraethylene glycol dimethacrylate, compound represented by the following formula)

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

B3: A-DCP (Shin-Nakamura Chemical Co., Ltd., tricyclodecane dimethanol diacrylate, a compound represented by the following formula)

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

Component (D): Alcohol having an aliphatic cyclic skeleton D1: Tricyclo[5.2.1.0(2,6)]decanedimethanol (manufactured by Tokyo Chemical Industry Co., Ltd., compound represented by the following formula D1)

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

[Production of cured pattern]
The obtained photosensitive resin composition was spin-coated on a silicon wafer using a coating device Act8 (manufactured by Tokyo Electron Ltd.), dried at 100° C. for 2 minutes, and then dried at 110° C. for 2 minutes to form a dried film. A photosensitive resin film having a thickness of 10 to 15 μm was formed.
The developing time was set to twice the time taken until the resulting photosensitive resin film was immersed in cyclopentanone and completely dissolved.
In addition, a photosensitive resin film was prepared in the same manner as above, and a broad band (BB) exposure was performed on the obtained photosensitive resin film using a mask aligner MA-8 (manufactured by SUSS Microtec Co., Ltd.) in a predetermined pattern. Exposure was performed by irradiating (a strip-shaped pattern having a width of 10 mm).
The exposed resin film was paddle-developed to cyclopentanone using Act8 for the above development time, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a patterned resin film.
The obtained patterned resin film was heated at 175° C. for 2 hours in a nitrogen atmosphere using a vertical diffusion furnace μ-TF (manufactured by Koyo Thermo System Co., Ltd.) to obtain a pattern cured product (film thickness after curing 10 μm). Obtained.

[Evaluation of PCT resistance]
<Tensile test before PCT>
The pattern-cured product obtained in [Production of pattern-cured product] was immersed in a 4.9 mass% hydrofluoric acid aqueous solution to separate the cured product having a width of 10 mm from the wafer.
The peeled cured product having a width of 10 mm was subjected to a tensile test using Autograph AGS-100NX (manufactured by Shimadzu Corporation). The distance between chucks was 20 mm, the pulling speed was 5 mm/min, the measurement temperature was 18 to 25° C., the measurement was performed for each cured product of each Example and Comparative Example, and a graph of tensile elongation and tensile stress was obtained. In the obtained graph of tensile elongation and tensile stress, the maximum point in the range of tensile elongation of 15% or less was determined. This was measured 6 times, and the average value 1 was obtained.

<Tensile test after PCT>
The pattern cured product obtained in [Production of pattern cured product] was treated with a PCT (pressure cooker test) device HASTEST (manufactured by Hirayama Seisakusho Co., Ltd., PC-R8D) at 121° C., 100% RH (Relative Humidity), It was treated at 2 atm for 100 hours.
The patterned cured product was taken out from the PCT apparatus, peeled off and subjected to a tensile test in the same manner as the tensile test before PCT, and an average value of 2 was obtained.
The absolute value of the value obtained by subtracting the average value 2 from the average value 1 is divided by the average value 1 to obtain a percentage value of less than 5% is A, and 5% or more and less than 10% is B, and 10%. The above case was designated as C. The results are shown in Table 1.

[Evaluation of growth rate]
The pattern-cured product obtained in [Production of pattern-cured product] was immersed in a 4.9 mass% hydrofluoric acid aqueous solution to separate the 10-mm-wide cured product from the wafer. A tensile test was performed on the peeled cured product having a width of 10 mm by using Autograph AGS-100NX. The distance between chucks was 20 mm, the pulling speed was 5 mm/min, the measurement temperature was 18 to 25° C., the measurement was performed 6 times, and the results were averaged to obtain the elongation percentage.
When the elongation rate was 45% or more, it was designated as A, when 25% or more and less than 45% was designated as B, and when it was less than 25%, it was designated as C. The results are shown in Table 1.

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

1 Semiconductor Substrate 2 Protective Film 3 First Conductor Layer 4 Interlayer Insulating Film 5 Photosensitive Resin Layer 6A, 6B, 6C Window 7 Second Conductor Layer 8 Surface Protective Film

Claims (15)

(A) a polyimide precursor having a structural unit represented by the following formula (1),
(B) polymerizable monomer,
(C) a photopolymerization initiator,
A photosensitive resin composition containing (D) an alcohol having an aliphatic cyclic skeleton, and (E) a solvent.

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

(In the 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 photosensitive resin composition according to claim 1, wherein the component (B) contains a polymerizable monomer having a group containing a polymerizable unsaturated double bond. The photosensitive resin composition according to claim 2, wherein the number of groups containing the polymerizable unsaturated double bond is 2 or more. The photosensitive resin composition according to claim 1, wherein the component (D) contains one or more compounds selected from the group consisting of compounds represented by the following formulas (41) to (44). ..

(In formulas (41) to (44), R ^{41 to} R ⁴⁴ are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following formula (45).
a is an integer of 1 to 10 and at least one R ⁴¹ is a group represented by the following formula (45).
b is an integer of 1 to 12, and at least one R ⁴² is a group represented by the following formula (45).
c is an integer of 1 to 16, and at least one R ⁴³ is a group represented by the following formula (45).
d is an integer of 1 to 16 and at least one R ⁴⁴ is a group represented by the following formula (45).
In formula (43), R ⁴³ can be bonded to all the substitution positions of the aliphatic cyclic skeleton, and in formula (44), R ⁴⁴ can be bonded to all the substitution positions of the aliphatic cyclic skeleton. )

In formula (45), l is an integer of 1-10. ) The photosensitive resin composition according to claim 4, wherein the compounds represented by the formulas (41) to (44) have two groups represented by the formula (45). The photosensitive resin composition according to claim 4 or 5, wherein the component (D) contains a compound represented by the formula (43). Content of the said (D) component is 1-50 mass parts with respect to 100 mass parts of said (A) components, The photosensitive resin composition in any one of Claims 1-6. The photosensitive resin composition according to claim 1, wherein the content of the component (D) is 0.1 to 5 times the content of the component (B). The photosensitive resin composition according to claim 1, further comprising (F) a thermal polymerization initiator. A step of applying the photosensitive resin composition according to any one of claims 1 to 9 onto a substrate and drying it to form a photosensitive resin film;
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 pattern resin film,
A method for producing a patterned cured film, comprising the step of heat-treating the patterned resin film. The method for producing a patterned cured film according to claim 10, wherein the temperature of the heat treatment is 200° C. or lower. A cured product obtained by curing the photosensitive resin composition according to claim 1. The cured product according to claim 12, which is a patterned cured product. An interlayer insulating film, a cover coat layer, or a surface protective film produced using the cured product according to claim 12. An electronic component comprising the interlayer insulating film, the cover coat layer or the surface protective film according to claim 14.

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