JP2019152791A - Photosensitive resin composition, patterned cured film production method, cured film, interlayer insulating film, cover coat layer, surface protective film, and electronic component - Google Patents

Abstract

To provide a photosensitive resin composition capable of forming a cured product having high adhesion after storage in a high-temperature condition even if the curing temperature is 200°C or less, a production method of 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.SOLUTION: The photosensitive resin composition comprises (A) a polyimide precursor having a polymerizable unsaturated bond, (B) a polymerizable monomer, (C) a photoinitiator, and (D) a compound represented by a specific formula.SELECTED DRAWING: None

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 having both excellent heat resistance, electrical characteristics, mechanical characteristics, and the like have been used for the surface protective film and interlayer insulating film of semiconductor elements. In recent years, photosensitive resin compositions in which photosensitive properties are imparted to these resins themselves have been used, and using this can simplify the manufacturing process of the pattern cured product and shorten complicated manufacturing processes (for example, patent documents). 1).

Further, in order to achieve a reduction in size and weight of a semiconductor package, a semiconductor packaging technique called a wafer level chip size package has been developed in which terminals on the surface of a semiconductor element are rewired using a laminate of polyimide and copper. .
In the production of a wafer level chip size package, low temperature curability is strongly required from the viewpoint of protecting a high-performance die and a sealing material having low heat resistance and improving yield (for example, see Patent Document 2). . Further, from the viewpoint of heat resistance reliability of the package, it is required that polyimide and copper wiring do not peel when exposed to high temperature conditions in the atmosphere, and that copper does not change color (for example, Non-Patent Document 1). reference). Specifically, in the step of forming a semiconductor device having bump electrodes, a high temperature reflow treatment is performed after applying flux to the electrode pad portion of the copper wiring, but the photosensitive resin composition when exposed to the reflow temperature Adhesion between copper and copper wiring is required, and various attempts have been made.

  Patent Document 3 discloses a positive photosensitive resin composition containing a triazole compound having a specific structure. Patent Document 4 discloses a photosensitive resin composition containing a pyridine compound having a specific structure.

JP 2009-265520 A International Publication No. 2008/111470 JP 2014-178471 A International Publication No. 2016/152656

“Vacuum”, Japan Vacuum Association, Vol. 39, p. 103-110

However, the conventional resin composition cannot obtain a cured film having sufficient adhesiveness.
An object of the present invention is to provide a photosensitive resin composition capable of forming a cured product having high adhesiveness after storage under a high temperature condition even when the curing temperature is 200 ° C. or less, and a method for producing a patterned cured product using the same It is to provide a cured product, an interlayer insulating film, a cover coat layer, a surface protective film, and an electronic component.

The present inventors searched for the cause of the decrease in adhesiveness using a conventional photosensitive resin composition. As a result of the high-temperature storage, oxygen permeates the cured product and copper is oxidized. It was found that the adhesion between copper and copper deteriorated.
As a result of intensive studies in view of the above, the present inventors have found that the curing temperature is 200 ° C. or lower by using a compound having a specific structure represented by the formula (1) in the photosensitive resin composition. In addition, the present inventors have found that a cured film showing high adhesion can be obtained after storage under high temperature conditions, and completed the present invention.

（式（１）中、Ｒ^１は窒素原子又はＣＲ^６であり、Ｒ^２は窒素原子又はＣＲ^７である。
Ｒ^３〜Ｒ^７は、それぞれ独立に、水素原子、水酸基、カルボキシ基、アミノ基、アゾ結合含有基、脂肪族炭化水素基、アルコキシ基、ヒドロキシアルキル基、芳香族基、又は下記式（２）で表される基である。
Ｒ^３及びＲ^４の少なくとも一方は、水酸基、アミノ基、脂肪族炭化水素基、芳香族基又は下記式（２）で表される基である。
Ｒ^３とＲ^６は、互いに結合して環を形成してもよい。Ｒ^４とＲ^７は、互いに結合して環を形成してもよい。

式（２）中、Ｒ^８は酸素原子又はＮＨであり、Ｒ^９は水素原子、カルボキシ基、脂肪族炭化水素基、アルコキシ基、ヒドロキシアルキル基、又は芳香族基である。）
２．前記（Ａ）成分が、下記式（１１）で表される構造単位を有するポリイミド前駆体である１に記載の感光性樹脂組成物。

（式（１１）中、Ｘ^１は４価の芳香族基である。Ｙ^１は２価の芳香族基である。Ｒ^１１及びＲ^１２は、それぞれ独立に、水素原子、下記式（１２）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^１１及びＲ^１２の少なくとも一方は下記式（１２）で表される基である。−ＣＯＯＲ^１１基と−ＣＯＮＨ−基とは、互いにオルト位置にあり、−ＣＯＯＲ^１２基と−ＣＯ−基とは、互いにオルト位置にある。）

（式（１２）中、Ｒ^１３〜Ｒ^１５は、それぞれ独立に、水素原子又は炭素数１〜３の脂肪族炭化水素基である。ｍは１〜１０の整数である。）
３．前記式（１）において、Ｒ^１がＣＲ^６であり、Ｒ^２がＣＲ^７である１又は２に記載の感光性樹脂組成物。
４．前記式（１）において、
Ｒ^１及びＲ^２が窒素原子であるか、
Ｒ^１がＣＲ^６であり、かつＲ^２が窒素原子であるか、又は
Ｒ^１が窒素原子であり、かつＲ^２がＣＲ^７である
１又は２に記載の感光性樹脂組成物。
５．前記式（１）において、Ｒ^１がＣＲ^６であり、Ｒ^２がＣＲ^７であり、Ｒ^３〜Ｒ^５が、水素原子、水酸基又はアミノ基である１又は２に記載の感光性樹脂組成物。
６．１〜５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。
７．前記加熱処理の温度が２００℃以下である６に記載のパターン硬化膜の製造方法。
８．１〜５のいずれかに記載の感光性樹脂組成物を硬化した硬化膜。
９．パターン硬化膜である８に記載の硬化膜。
１０．９に記載の硬化膜を用いて作製された層間絶縁膜、カバーコート層又は表面保護膜。
１１．１０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 polymerizable unsaturated bond;
(B) a polymerizable monomer;
(C) a photopolymerization initiator;
(D) a compound represented by the following formula (1);
A photosensitive resin composition comprising:

(In formula (1), R ¹ is a nitrogen atom or CR ⁶ , and R ² is a nitrogen atom or CR ⁷ .
R ^{3 to} R ⁷ are each independently a hydrogen atom, a hydroxyl group, a carboxy group, an amino group, an azo bond-containing group, an aliphatic hydrocarbon group, an alkoxy group, a hydroxyalkyl group, an aromatic group, or the following formula (2) It is group represented by these.
At least one of R ³ and R ⁴ is a hydroxyl group, an amino group, an aliphatic hydrocarbon group, an aromatic group, or a group represented by the following formula (2).
R ³ and R ⁶ may combine with each other to form a ring. R ⁴ and R ⁷ may be bonded to each other to form a ring.

In Formula (2), R ⁸ is an oxygen atom or NH, and R ⁹ is a hydrogen atom, a carboxy group, an aliphatic hydrocarbon group, an alkoxy group, a hydroxyalkyl group, or an aromatic group. )
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 (11).

(In formula (11), X ¹ is a tetravalent aromatic group. Y ¹ is a divalent aromatic group. R ¹¹ and R ¹² are each independently a hydrogen atom, the following formula (12): Or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and at least one of R ¹¹ and R ¹² is a group represented by the following formula (12): —COOR ¹¹ group and —CONH— Group is in the ortho position to each other, and the —COOR ¹² group and the —CO— group are in the ortho position to each other.)

(In Formula (12), R < ¹³ > -R < ¹⁵ > is a hydrogen atom or a C1-C3 aliphatic hydrocarbon group each independently. M is an integer of 1-10.)
3. 3. The photosensitive resin composition according to 1 or 2, wherein in the formula (1), R ¹ is CR ⁶ and R ² is CR ⁷ .
4). In the formula (1),
Whether R ¹ and R ² are nitrogen atoms,
The photosensitive resin composition according to 1 or 2, wherein R ¹ is CR ⁶ and R ² is a nitrogen atom, or R ¹ is a nitrogen atom and R ² is CR ⁷ .
5. The photosensitive resin composition according to 1 or 2, wherein, in the formula (1), R ¹ is CR ⁶ , R ² is CR ⁷ , and R ^{3 to} R ⁵ are a hydrogen atom, a hydroxyl group, or an amino group. .
A step of applying the photosensitive resin composition according to any one of 6.1 to 5 onto a substrate and drying to form a photosensitive resin film;
Pattern exposure of the photosensitive resin film to obtain a resin film;
The step of developing the resin film after the pattern exposure using an organic solvent to obtain a pattern resin film;
Heat-treating the pattern resin film;
The manufacturing method of the pattern cured film containing this.
7). The manufacturing method of the pattern cured film of 6 whose temperature of the said heat processing is 200 degrees C or less.
The cured film which hardened the photosensitive resin composition in any one of 8.1-5.
9. The cured film according to 8, which is a pattern cured film.
An interlayer insulating film, a cover coat layer or a surface protective film produced using the cured film described in 10.9.
11. An electronic component comprising the interlayer insulating film, cover coat layer or surface protective film according to 11.10.

  ADVANTAGE OF THE INVENTION According to this invention, even if hardening temperature is 200 degrees C or less, the photosensitive resin composition which can form the hardened | cured material which has high adhesiveness after storage on high temperature conditions, and the manufacturing method of a pattern hardened | cured material using the same , Cured products, interlayer insulating films, cover coat layers, surface protective films, and electronic components can be provided.

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

  Below, the photosensitive resin composition of this invention, the manufacturing method of a pattern cured material using the same, cured | curing material, an interlayer insulation film, a cover coat layer, a surface protective film, and embodiment of an electronic component are described in detail. The present invention is not limited to the following embodiments.

  In this specification, “A or B” may include either one of A and B, or may include both. In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. . In the present specification, a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. In the present specification, the content of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. means. In this specification, unless otherwise indicated, exemplary materials may be used independently and may be used in combination of 2 or more type. The “(meth) acryl group” in the present specification means “acryl group” and “methacryl group”.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention comprises (A) a polyimide precursor having a polymerizable unsaturated bond (hereinafter also referred to as “(A) component”), (B) a polymerizable monomer (hereinafter referred to as “(B ) Component ”), (C) photopolymerization initiator (hereinafter also referred to as“ (C) component ”), and (D) a compound represented by formula (1) (hereinafter referred to as“ (D) component ”. "). The photosensitive resin composition of the present invention is preferably a negative photosensitive resin composition.

Since the photosensitive resin composition of this invention has said component, even if hardening temperature is 200 degrees C or less, the hardened | cured material which has high adhesiveness can be formed even after storage on high temperature conditions. Specifically, for example, high adhesiveness can be maintained even after a high temperature storage test (HTS test) performed in the examples of the present application or after repeatedly performing heat treatment a plurality of times. Furthermore, the photosensitive resin composition of the present invention has excellent photosensitive properties.
Hereinafter, each component will be described.

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

（式（１１）中、Ｘ^１は４価の芳香族基である。Ｙ^１は２価の芳香族基である。Ｒ^１１及びＲ^１２は、それぞれ独立に、水素原子、下記式（１２）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^１１及びＲ^１２の少なくとも一方は下記式（１２）で表される基である。−ＣＯＯＲ^１１基と−ＣＯＮＨ−基とは、互いにオルト位置にあり、−ＣＯＯＲ^１２基と−ＣＯ−基とは、互いにオルト位置にある。）

（式（１２）中、Ｒ^１３〜Ｒ^１５は、それぞれ独立に、水素原子又は炭素数１〜３の脂肪族炭化水素基である。ｍは１〜１０の整数（好ましくは２〜１０の整数、より好ましくは２〜５の整数、さらに好ましくは２又は３）である。） The component (A) is preferably a polyimide precursor having a structural unit represented by the following formula (11). Thereby, even if it is a case where the transmittance | permeability of i line | wire is high and it hardens | cures at the low temperature of 200 degrees C or less, the cured film which has a favorable physical property can be formed.

(In formula (11), X ¹ is a tetravalent aromatic group. Y ¹ is a divalent aromatic group. R ¹¹ and R ¹² are each independently a hydrogen atom, the following formula (12): Or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and at least one of R ¹¹ and R ¹² is a group represented by the following formula (12): —COOR ¹¹ group and —CONH— Group is in the ortho position to each other, and the —COOR ¹² group and the —CO— group are in the ortho position to each other.)

(In Formula (12), R < ¹³ > -R < ¹⁵ > is a hydrogen atom or a C1-C3 aliphatic hydrocarbon group each independently. M is an integer of 1-10 (preferably an integer of 2-10). More preferably, it is an integer of 2 to 5, more preferably 2 or 3).

The tetravalent aromatic group of X ^{1 in} the formula (11) may be a tetravalent aromatic hydrocarbon group (having 6 to 20 carbon atoms, for example), or a tetravalent aromatic heterocyclic group (number of atoms). May be, for example, 5-20). X ¹ is preferably a tetravalent aromatic hydrocarbon group.

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

(In the formula, Z ¹ and Z ² are each independently a divalent group or a single bond that is not conjugated to the benzene ring to which each is 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—, a methylene group, a bis (trifluoromethyl) methylene group, or a difluoromethylene group, and more preferably —O—.
Z ³ is preferably —O—.

The divalent aromatic group of Y ^{1 in} the formula (11) may be a divalent aromatic hydrocarbon group (having 6 to 20 carbon atoms, for example), or a divalent aromatic heterocyclic group (number of atoms). May be, for example, 5-20). Y ¹ is preferably a divalent aromatic hydrocarbon group.

（式（１３）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 a group represented by the following formula (13), but are not limited thereto.

(In formula (13), 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.)

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

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

In the formula (13), 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 a hydrogen atom.

Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms (preferably 1 or 2) of R ¹¹ and R ^{12 in} the formula (11) include methyl group, ethyl group, n-propyl group, 2-propyl group, n- A butyl group etc. are mentioned.

In formula (11), at least one of R ¹¹ and R ¹² is a group represented by formula (12), and preferably both R ¹¹ and R ¹² are groups represented by formula (12).

Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms (preferably 1 or 2) of R ^{13 to} R ^{15 in} the formula (12) include a methyl group, an ethyl group, an n-propyl group, and a 2-propyl group. It is done. A methyl group is preferred.

（式（１４）中、Ｘ^１は式（１１）のＸ^１に対応する基である。式（１５）中、Ｙ^１は式（１１）で定義した通りである。式（１６）中、Ｒ^１３〜Ｒ^１５及びｍは式（１２）で定義した通りである。） The polyimide precursor having the structural unit represented by the formula (11) includes, for example, a tetracarboxylic dianhydride represented by the following formula (14) and a diamino compound represented by the following formula (15). A polyamic acid is produced by reaction in an organic solvent such as N-methylpyrrolidone, a compound represented by the following formula (16) is added, and the reaction is carried out in an organic solvent to introduce an ester group in whole or in part. Can be manufactured.

(In the formula (14) in, ^{X 1} is a group corresponding to ^{X 1} of the formula (11). Formula in (15), ^{Y 1} is as defined in formula (11). Equation (16), R ^{13 to} R ¹⁵ and m are as defined in Formula (12).)

  The tetracarboxylic dianhydride represented by the formula (14) and the diamino compound represented by the formula (15) may be used alone or in combination of two or more.

  The content of the structural unit represented by the formula (11) is preferably 50% by mole or more, more preferably 80% by mole or more, and 90% by mole or more with respect to all the structural units of the component (A). Further preferred. An upper limit is not specifically limited, 100 mol% may be sufficient.

（式（１７）中、Ｘ^１２は４価の芳香族基である。Ｙ^１２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。−ＣＯＯＲ^３１基と−ＣＯＮＨ−基とは、互いにオルト位置にあり、−ＣＯＯＲ^３２基と−ＣＯ−基とは、互いにオルト位置にある。） (A) A component may have structural units other than the structural unit represented by Formula (11). Examples of the structural unit other than the structural unit represented by the formula (11) include a structural unit represented by the following formula (17).

(In formula (17), X ¹² is a tetravalent aromatic group. Y ¹² is a divalent aromatic group. R ³¹ and R ³² are each independently a hydrogen atom or a carbon number of 1 to 4. (The —COOR ³¹ group and the —CONH— group are in the ortho position with each other, and the —COOR ³² group and the —CO— group are in the ortho position with each other.)

Examples of the tetravalent aromatic group of X ^{12 in} formula (17) include the same groups as the tetravalent aromatic group of X ^{1 in} formula (11). Examples of the divalent aromatic group for Y ¹² include the same groups as the divalent aromatic group for Y ^{1 in} formula (11). 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 ¹¹ and R ¹² in formula (11).

The content of structural units other than the structural unit represented by formula (11) is preferably less than 50 mol% with respect to all structural units of the component (A).
Structural units other than the structural unit represented by formula (11) may be used alone or in combination of two or more.

  In the component (A), the ratio of the carboxy group esterified with the group represented by the formula (12) with respect 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.

Although there is no restriction | limiting in particular in the molecular weight of (A) component, It is preferable that it is 10,000-200,000 in a number average molecular weight.
The number average molecular weight is determined by measuring with gel permeation chromatography (GPC) and converting using a standard polystyrene calibration curve. Specific measurement conditions and the like are as described in the examples.

((B) component: polymerizable monomer)
The photosensitive resin composition of the present invention contains (B) a polymerizable monomer. Thereby, it can bridge | crosslink with (A) component or (B) component can superpose | polymerize and can form a crosslinked network, and can improve the heat resistance and mechanical characteristics of the hardened | cured material (cured film) formed. .

  The component (B) preferably has a group containing a polymerizable unsaturated double bond. In order to improve the crosslinking density, improve the photosensitivity, and suppress the swelling of the pattern after development, It preferably has a group containing an unsaturated double bond. The group is preferably a (meth) acryl group from the viewpoint that it can be polymerized by a photopolymerization initiator.

（式（２１）中、Ｒ^４１〜Ｒ^４３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。） Examples of the component (B) include, but are not limited to, compounds having a group represented by the following formula (21).

(In the formula (21), R ^{41 to} R ⁴³ 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). ).)

Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms of the formula (21) include the same aliphatic hydrocarbon group having 1 to 3 carbon atoms ^R 13 ^{to R 15} of formula (12).

  As the component (B), specifically, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol di Acrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane Trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pen Erythritol trimethacrylate, pentaerythritol tetramethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated isocyanuric acid triacrylate, ethoxylated isocyanuric Examples include acid trimethacrylate, acryloyloxyethyl isocyanurate, and methacryloyloxyethyl isocyanurate.

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), more preferably 5 to 50 parts by mass from the viewpoint of improving the hydrophobicity of the cured product. Preferably it is 5-40 mass parts.
When it is within the above range, a practical relief pattern is likely to be obtained, and the post-development residue in the unexposed area is easily suppressed.

((C) component: photopolymerization initiator)
Examples of the photopolymerization initiator of component (C) include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; 2,2′-di Acetophenone derivatives such as ethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone; benzyl, benzyldimethyl ketal, Benzyl derivatives such as benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin and benzoin methyl ether; 1-phenyl-1,2-butanedione-2- (o-methoxycal Bonyl) 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- (0-acetyloxime), oximes such as compounds represented by the following formula Preferred examples include esters, but are not limited thereto. From the viewpoint of photosensitivity, oxime esters are preferred.

As for content of (C) component, 0.1-20 mass parts is preferable with respect to 100 mass parts of (A) component, More preferably, it is 0.1-10 mass parts, More preferably, it is 0.1-0.1 mass parts. 8 parts by mass.
In the above range, photocrosslinking tends to be uniform in the film thickness direction, and a practical relief pattern can be easily obtained.

（式（１）中、Ｒ^１は窒素原子又はＣＲ^６であり、Ｒ^２は窒素原子又はＣＲ^７である。
Ｒ^３〜Ｒ^７は、それぞれ独立に、水素原子、水酸基、カルボキシ基、アミノ基、アゾ結合含有基、脂肪族炭化水素基、アルコキシ基、ヒドロキシアルキル基、芳香族基、又は下記式（２）で表される基である。
Ｒ^３及びＲ^４の少なくとも一方は、水酸基、アミノ基、脂肪族炭化水素基、芳香族基又は下記式（２）で表される基である。
Ｒ^３とＲ^６は、互いに結合して環を形成してもよい。Ｒ^４とＲ^７は、互いに結合して環を形成してもよい。

式（２）中、Ｒ^８は酸素原子又はＮＨであり、Ｒ^９は水素原子、カルボキシ基、脂肪族炭化水素基、アルコキシ基、ヒドロキシアルキル基、又は芳香族基である。） ((D) component: compound represented by formula (1))
The photosensitive resin composition of this invention contains the nitrogen-containing heterocyclic compound represented by following formula (1). Thereby, the hardened | cured material excellent in adhesiveness can be formed even after the preservation | save on high temperature conditions.

(In formula (1), R ¹ is a nitrogen atom or CR ⁶ , and R ² is a nitrogen atom or CR ⁷ .
R ^{3 to} R ⁷ are each independently a hydrogen atom, a hydroxyl group, a carboxy group, an amino group, an azo bond-containing group, an aliphatic hydrocarbon group, an alkoxy group, a hydroxyalkyl group, an aromatic group, or the following formula (2) It is group represented by these.
At least one of R ³ and R ⁴ is a hydroxyl group, an amino group, an aliphatic hydrocarbon group, an aromatic group, or a group represented by the following formula (2).
R ³ and R ⁶ may combine with each other to form a ring. R ⁴ and R ⁷ may be bonded to each other to form a ring.

In Formula (2), R ⁸ is an oxygen atom or NH, and R ⁹ is a hydrogen atom, a carboxy group, an aliphatic hydrocarbon group, an alkoxy group, a hydroxyalkyl group, or an aromatic group. )

R ¹ and R ² may be such that R ¹ is CR ⁶ and R ² may be CR ⁷ ; R ¹ and R ² may be nitrogen atoms; or R ¹ is CR ⁶ R ² may be a nitrogen atom, or R ¹ may be a nitrogen atom and R ² may be CR ⁷ .

It is preferable that R ¹ is CR ⁶ and R ² is CR ⁷ because it is possible to form a cured product that can suppress discoloration before and after storage under high temperature conditions.

Also, R ¹ may be CR ⁶ , R ² may be CR ⁷ , and R ^{3 to} R ⁵ may be a hydrogen atom, a hydroxyl group, or an amino group.

R ⁵ is preferably a hydrogen atom, an amino group, or an aliphatic hydrocarbon group.
R ⁶ and R ⁷ are preferably a hydrogen atom, an azo bond-containing group (for example, —N═NH), or an aliphatic hydrocarbon group (for example, ethenyl group).
R ⁹ is preferably a hydrogen atom.

Examples of the case where R ³ and R ⁶ (or R ⁴ and R ⁷ ) are bonded to each other to form a ring include, for example, R ³ is an amino group, and R ⁶ is an azo bond-containing group (for example, —N═ NH), or when R ³ is an aromatic group (for example, pyridinyl group) and R ⁶ is an aliphatic hydrocarbon group (for example, ethenyl group).

Examples of the azo bond-containing group of the formulas (1) and (2) include -N = NH.
Examples of the aliphatic hydrocarbon group (preferably having 1 to 10 carbon atoms) of the formulas (1) and (2) include an alkyl group (preferably 1 to 10 carbon atoms) and an alkenyl group (preferably 2 to 8 carbon atoms). Examples of the alkyl group include a methyl group, an ethyl group, and a cyclohexyl group. Examples of the alkenyl group include an ethenyl group and an allyl group.
Examples of the alkoxy group (preferably having 1 to 8 carbon atoms) of the formulas (1) and (2) include a methoxy group and an ethoxy group.
Examples of the hydroxyalkyl group (preferably having 1 to 8 carbon atoms) of the formulas (1) and (2) include a methylol group.
Examples of the aromatic group of the formulas (1) and (2) include an aryl group (preferably having 6 to 10 carbon atoms) and a heteroaryl group (preferably having 5 to 10 atoms). And examples of the heteroaryl group include a pyridinyl group.

  (D) As for content of a component, 0.1-25 mass parts is preferable with respect to 100 mass parts of (A) component, More preferably, it is 0.1-10 mass parts, More preferably, it is 0.1-0.1 mass parts. 5 parts by mass. Moreover, it is good also as 0.8-25 mass parts or 1.0-25 mass parts with respect to 100 mass parts of (A) component. In the case of 0.1 parts by mass or more, it is easy to suppress a decrease in adhesion with copper, and in the case of 25 parts by mass or less, generation of a residue after development is suppressed, and good photosensitive characteristics are easily obtained.

(Rust inhibitor)
Although the above component (D) is usually used as a rust inhibitor, the photosensitive resin composition of the present invention may contain a rust inhibitor other than the component (D).
By including other rust preventives, copper corrosion and discoloration can be further suppressed.
Examples of the rust inhibitor include triazole derivatives and tetrazole derivatives (for example, 5-aminotetrazole and the like).
When using the said rust preventive agent, 0.01-10 mass parts is preferable with respect to 100 mass parts of (A) component, as for content of a rust preventive agent, 0.1-5 mass parts is more preferable, 0.5 -3 mass parts is more preferable.

((E) component: solvent)
The photosensitive resin composition of the present invention preferably contains a solvent.
As the solvent, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, 3-methoxy-N, N-dimethylpropanamide (for example, “KJCMPA-100” manufactured by KJ Chemicals Co., Ltd.) And organic solvents such as N-dimethylmorpholine.
Although content of a solvent is not specifically limited, Generally, it is 50-1000 mass parts with respect to 100 mass parts of (A) component.

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

(Coupling agent)
In general, the coupling agent is crosslinked by reacting with the component (A) in the heat treatment after development, or the coupling agent itself is polymerized in the heat treatment step. Thereby, the adhesiveness of the cured film obtained and a board | substrate can be improved more.

（式（３１）中、Ｒ^５１及びＲ^５２は、それぞれ独立に、炭素数１〜５のアルキル基である。ｊは１〜１０の整数であり、ｋは１〜３の整数である。） A silane coupling agent is preferable as the coupling agent.
A preferable silane coupling agent includes a compound having a urea bond (—NH—CO—NH—). Thereby, also when it hardens | cures under the low temperature of 200 degrees C or less, adhesiveness with a board | substrate can further be improved.
A compound represented by the following formula (31) is more preferable in that it exhibits excellent adhesion when cured at low temperature.

(In Formula (31), R ⁵¹ and R ⁵² 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 (31) include ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, and 3-ureidopropyltrimethoxysilane. , 3-ureidopropyltriethoxysilane, 4-ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane, and the like, preferably 3-ureidopropyltriethoxysilane.

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

（式（３２）中、Ｒ^５３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^５４及びＲ^５５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。） 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, Sobutylethylphenylsilanol, 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, , 4-bis (butyldihydroxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) Benzene, 1,4-bis (dipropyl hydroxy silyl) benzene, 1,4-bis (dibutyl hydroxy silyl) benzene, and compounds represented by the following formula (32) below. Especially, in order to improve adhesiveness with a board | substrate more, the compound represented by Formula (32) is preferable.

(In formula (32), R ⁵³ is a monovalent organic group having a hydroxy group or a glycidyl group, and R ⁵⁴ and R ⁵⁵ are each independently an alkyl group having 1 to 5 carbon atoms. -10 is an integer, and p is an integer of 1-3.)

  Examples of the compound represented by the formula (32) include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3- Hydroxypropyltriethoxysilane, 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2- Glycidoxyethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybutyl Silane and the like.

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

Examples of the silane coupling agent having an amide bond include a compound represented by the following formula (33).
^{_{R 56 - (CH 2) q}} -CO-NH- (CH 2) r -Si (OR 57) 3 (33)
(In Formula (33), R ⁵⁶ is a hydroxy group or a glycidyl group, q and r are each independently an integer of 1 to 3, and R ⁵⁷ is a methyl group, an ethyl group, or a propyl group.)

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

(Surfactant or leveling agent)
By including the surfactant or the leveling agent, coating properties (for example, suppression of striation (film thickness unevenness)) 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. "F171", "F173", "R-08" (above, manufactured by DIC Corporation), trade names "Florard FC430", "FC431" (above, manufactured by 3M Japan), trade names "organosiloxane polymer KP341", “KBM303”, “KBM403”, “KBM803” (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

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

(Polymerization inhibitor)
By containing a polymerization inhibitor, good storage stability can be ensured.
Examples of the polymerization inhibitor include 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, nitrosamines and the like.

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

The photosensitive resin composition of the present invention is essentially a component (A) to (D), and a rust inhibitor other than the component (D), a coupling agent, a surfactant, and a leveling agent, except for the solvent. And one or more components selected from the group consisting of polymerization inhibitors, and may contain other inevitable impurities as long as the effects of the present invention are not impaired.
Of the photosensitive resin composition 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. Or 100% by weight, excluding solvents,
Components (A) to (D),
Rust preventives other than (A) to (D) and (D) component, or rust preventives other than (A) to (C) and (D), and coupling agents, surfactants, and leveling. It may consist of one or more components selected from the group consisting of an agent and a polymerization inhibitor.

[Curing film]
The cured film of the present invention can be obtained by curing the above-described photosensitive resin composition. The cured film of the present invention may be used as a pattern cured film or a cured film having no pattern. As for the film thickness of the cured film of this invention, 5-20 micrometers is preferable.

[Method for producing patterned cured film]
In the method for producing a patterned cured film of the present invention, the above-described photosensitive resin composition is applied on a substrate and dried to form a photosensitive resin film, and the photosensitive resin film is subjected to pattern exposure to form a resin film. A step of obtaining the pattern resin film by developing the resin film after pattern exposure using an organic solvent, and a step of heat-treating the pattern resin film. Thereby, a pattern cured film can be obtained.

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

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

  Although there is no restriction | limiting in particular in the application method, It can carry out using a spinner etc.

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

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

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

By developing, a patterned resin film (pattern resin film) can be obtained. Generally, when a negative photosensitive resin composition is used, an unexposed portion is removed with a developer.
As the organic solvent used as the developer, a good solvent for the photosensitive resin film can be used alone, or a good solvent and a poor solvent can be mixed as appropriate.
Good solvents include N-methylpyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, gamma butyrolactone, α-acetyl-gammabutyrolactone, cyclopentanone, cyclohexanone Etc.
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 developer.

The development time can be set to, for example, twice the time until the photosensitive resin film is immersed and dissolved.
The development time varies depending on the component (A) to be 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.

You may wash | clean with a rinse solution after image development.
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 combination as appropriate, or may be used in a stepwise combination. Good.

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

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

The heat treatment time is preferably 5 hours or less, more preferably 30 minutes to 3 hours. By being within the above range, the crosslinking reaction or dehydration ring-closing reaction can sufficiently proceed.
The atmosphere for the heat treatment may be in the air or in an inert atmosphere such as nitrogen, but a nitrogen atmosphere is preferable from the viewpoint of preventing 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 insulating film, cover coat layer, surface protective film, electronic components]
The cured film of the present invention can be used as a passivation film, a buffer coat film, an interlayer insulating film, a cover coat layer, a surface protective film, or the like.
Using one or more selected from the group consisting of the above passivation film, buffer coat film, interlayer insulating film, cover coat layer, surface protective film, etc., a highly reliable semiconductor device, multilayer wiring board, various electronic devices, etc. Electronic parts and the like can be manufactured.

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 as an electronic component according to an embodiment of the present invention.
In FIG. 1, a semiconductor substrate 1 such as a Si substrate having a circuit element is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element, and a first conductor layer 3 is formed on the exposed circuit element. It is formed. Thereafter, an interlayer insulating film 4 is formed on the semiconductor substrate 1.

  Next, a photosensitive resin layer 5 such as chlorinated rubber or phenol novolac 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 photolithography technique. It is done.

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

Further, the second conductor layer 7 is formed by using a known photolithography technique, and electrical connection with the first conductor layer 3 is performed.
When a multilayer wiring structure having three or more layers is formed, each of the layers can be formed by repeating the above-described steps.

Next, using the above-described photosensitive resin composition, the window 6C is opened by pattern exposure, and the surface protective film 8 is formed. The surface protective 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 using the photosensitive resin composition of the present invention.

  Hereinafter, based on an Example and a comparative example, this invention is demonstrated concretely. In addition, this invention is not limited to the following Example.

Synthesis Example 1 (Synthesis of Polymer A1)
7.07 g of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (ODPA) and 4.12 g of 2,2′-dimethylbiphenyl-4,4′-diamine (DMAP) were added to N-methyl- It melt | dissolved in 2-pyrrolidone (NMP) 30g, and it stirred at 30 degreeC for 4 hours, after that, it stirred at room temperature overnight, and obtained the polyamic acid. 9.45g of trifluoroacetic anhydride was added there under water cooling, and it stirred at 45 degreeC for 3 hours, and 7.08g of 2-hydroxyethyl methacrylate (HEMA) was added. The reaction solution was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyimide precursor (hereinafter referred to as polymer A1).

Using gel permeation chromatography (GPC), the number average molecular weight of the polymer A1 was determined under the following conditions by standard polystyrene conversion. The number average molecular weight of the polymer A1 was 40,000. The number average molecular weight was measured using a solution of 1 mL of a solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1/1 (volume ratio)] to 0.5 mg of the polymer A1.
Measuring device: Detector L4000UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
C-R4A Chromatopac made by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5 × 2 eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.03 mol / L), H ₃ PO ₄ (0.06 mol / L)
Flow rate: 1.0 mL / min, detector: UV 270 nm

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

Examples 1-14 and Comparative Examples 1-7
[Preparation of photosensitive resin composition]
Photosensitive resin compositions of Examples 1 to 14 and Comparative Examples 1 to 7 were prepared using the components and blending amounts shown in Table 1. The compounding quantity of Table 1 is a mass part of each component with respect to 100 mass parts (A) component.
Each component used is as follows.

((A) component: polyimide precursor having a polymerizable unsaturated bond)
Polymer A1: Polymer A1 obtained in Synthesis Example 1

((B) component: polymerizable monomer)
B1: “TEGDMA” (manufactured by Shin-Nakamura Chemical Co., Ltd., tetraethylene glycol dimethacrylate)

((C) component: photopolymerization initiator)
C1: “G-1820 (PDO)” (Lambson, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime)

((D) component: compound represented by formula (1))
D1: 2-methylpyridine (manufactured by Tokyo Chemical Industry Co., Ltd.)
D2: 2-hydroxypyridine (manufactured by Tokyo Chemical Industry Co., Ltd.)
D3: 2-aminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.)
D4: 2-aminopyrimidine (manufactured by Tokyo Chemical Industry Co., Ltd.)
D5: 8-azaadenine (manufactured by Tokyo Chemical Industry Co., Ltd.)
D6: 2-pyridinemethanol (manufactured by Tokyo Chemical Industry Co., Ltd.)
D7: 2-aminomethylpyridine (manufactured by Tokyo Chemical Industry Co., Ltd.)
D8: o-phenanthroline (manufactured by Tokyo Chemical Industry Co., Ltd.)
D9: 2,4-diamino-6-methyl-1,3,5-triazine (manufactured by Tokyo Chemical Industry Co., Ltd.)

((D ′) component)
D'1: 3-aminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.)
D'2: 4-aminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.)
D'3: 2-hydroxyquinoxaline (manufactured by Tokyo Chemical Industry Co., Ltd.)
D'4: Phthalazone (manufactured by Tokyo Chemical Industry Co., Ltd.)
D′ 5: 5-aminotetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
The component (D ′) means a component different from the component (D) used in the present invention.

((E) component: solvent)
E1: γ-butyrolactone (manufactured by Wako Pure Chemical Industries, Ltd.)
E2: Compound represented by the following formula ("KJCMPA-100" manufactured by KJ Chemicals Co., Ltd.)

[Production and evaluation of cured film]
(Manufacture of cured film)
The obtained photosensitive resin composition was spin-coated on a Cu-plated wafer (Si wafer on which Cu plating having a thickness of 10 μm was formed) using a coating apparatus “Act8” (manufactured by Tokyo Electron Limited), and 100 ° C. And dried at 110 ° C. for 2 minutes to form a photosensitive resin film.
The obtained photosensitive resin film was exposed to 500 mJ / cm ² using a proximity exposure machine “MA8” (manufactured by SUSS Microtec Co., Ltd.). The exposed 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 cured film. The film thickness of the cured film was 10 μm.

(Heat treatment 1: HTS test)
The obtained Cu plated wafer with cured product was placed in a clean oven “DT-41” (manufactured by Yamato Scientific Co., Ltd.), stored at 175 ° C. for 100 hours, and then taken out.

(Heat treatment 2)
The Cu-plated wafer with a cured product obtained in (Production of cured film) was heated to a temperature of 260 ° C. at a heating rate of 80 ° C./min in an air atmosphere using a reflow furnace apparatus, and then heated at 260 ° C. for 30 seconds. Heat treatment was performed. Thereafter, when the heating was stopped and the temperature became 50 ° C. or lower, the wafer was taken out. The process from this temperature rise to removal was defined as one cycle, and the process was performed for 10 cycles.

(Copper adhesion test)
For each of the Cu-plated wafer with a cured product after (heat treatment 1) and the Cu-plated wafer with a cured product after (heat treatment 2), according to the cross-cut method of JIS K 5600-5-6 standard, the substrate (copper ) And the cured film was evaluated based on the following criteria. The results are shown in Table 1.
“A”: the number of lattices of the cured film adhered to the substrate is 100 “B”: the number of lattices of the cured film adhered to the substrate is 80 to 99 “C”: adhered to the substrate “D” when the number of lattices of the cured film is 50 to 79: “D” when the number of lattices of the cured film adhered to the substrate is 20 to 49 “E”: The number of lattices of the cured film adhered to the substrate is 19 or less Things

(Evaluation of appearance (color))
The color of the Cu-plated wafer with a cured product after (heat treatment 1) was visually confirmed. The results are shown in Table 1. The name of the color is “Japanese Color Dictionary” [online], [December 10, 2017 search], Internet <URL: https://www.colordic.org/w/>. (Heat treatment 1) The color of the Cu-plated wafer with a cured product before was “dark blue”. It shows that there is so little discoloration that the color of Cu plating wafer with hardened | cured material after (heat processing 1) is near amber.

  From Table 1, it can be seen that according to the photosensitive resin composition of the present invention, a cured product having high adhesiveness can be formed even after heat treatment. Moreover, it turns out that there is little discoloration before and behind heat processing among the (D) component used by this invention especially when D1-D3 and D6-D8 are used, and discoloration can be suppressed.

  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 the surface protective film of the present invention is used for an electronic component or the like. Can do.

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

Claims (11)

(A) a polyimide precursor having a polymerizable unsaturated bond;
(B) a polymerizable monomer;
(C) a photopolymerization initiator;
(D) a compound represented by the following formula (1);
A photosensitive resin composition comprising:

(In formula (1), R ¹ is a nitrogen atom or CR ⁶ , and R ² is a nitrogen atom or CR ⁷ .
R ^{3 to} R ⁷ are each independently a hydrogen atom, a hydroxyl group, a carboxy group, an amino group, an azo bond-containing group, an aliphatic hydrocarbon group, an alkoxy group, a hydroxyalkyl group, an aromatic group, or the following formula (2) It is group represented by these.
At least one of R ³ and R ⁴ is a hydroxyl group, an amino group, an aliphatic hydrocarbon group, an aromatic group, or a group represented by the following formula (2).
R ³ and R ⁶ may combine with each other to form a ring. R ⁴ and R ⁷ may be bonded to each other to form a ring.

In Formula (2), R ⁸ is an oxygen atom or NH, and R ⁹ is a hydrogen atom, a carboxy group, an aliphatic hydrocarbon group, an alkoxy group, a hydroxyalkyl group, or an aromatic group. ) 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 (11).

(In formula (11), X ¹ is a tetravalent aromatic group. Y ¹ is a divalent aromatic group. R ¹¹ and R ¹² are each independently a hydrogen atom, the following formula (12): Or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and at least one of R ¹¹ and R ¹² is a group represented by the following formula (12): —COOR ¹¹ group and —CONH— Group is in the ortho position to each other, and the —COOR ¹² group and the —CO— group are in the ortho position to each other.)

(In Formula (12), R < ¹³ > -R < ¹⁵ > is a hydrogen atom or a C1-C3 aliphatic hydrocarbon group each independently. M is an integer of 1-10.) The photosensitive resin composition according to claim 1 or 2, wherein, in the formula (1), R ¹ is CR ⁶ and R ² is CR ⁷ . In the formula (1),
Whether R ¹ and R ² are nitrogen atoms,
The photosensitive resin composition according to claim 1, wherein R ¹ is CR ⁶ and R ² is a nitrogen atom, or R ¹ is a nitrogen atom and R ² is CR ⁷ . The photosensitive resin according to claim 1 or 2, wherein, in the formula (1), R ¹ is CR ⁶ , R ² is CR ⁷ , and R ^{3 to} R ⁵ are a hydrogen atom, a hydroxyl group, or an amino group. Composition. Applying the photosensitive resin composition according to any one of claims 1 to 5 on a substrate and drying to form a photosensitive resin film;
Pattern exposure of the photosensitive resin film to obtain a resin film;
The step of developing the resin film after the pattern exposure using an organic solvent to obtain a pattern resin film;
Heat-treating the pattern resin film;
The manufacturing method of the pattern cured film containing this.   The manufacturing method of the pattern cured film of Claim 6 whose temperature of the said heat processing is 200 degrees C or less.   A cured film obtained by curing the photosensitive resin composition according to claim 1.   The cured film according to claim 8, which is a pattern cured film.   An interlayer insulating film, a cover coat layer or a surface protective film produced using the cured film according to claim 9.   An electronic component comprising the interlayer insulating film according to claim 10, a cover coat layer, or a surface protective film.

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