JP2020056934A - Method for producing pattern cured film, photosensitive resin composition, cured film, interlayer insulating film, cover coat layer, surface protective film and electronic component - Google Patents

Abstract

To provide a method for producing a pattern cured film that makes it possible to produce a pattern cured film having high chemical solution resistance even when cured at 200°C or lower, and a photosensitive resin composition, and also provide a cured film of the photosensitive resin composition, an interlayer insulation film or the like prepared using the cured film, and an electronic component including the interlayer insulation film or the like.SOLUTION: A method for producing a pattern cured film has a step of: applying a photosensitive resin composition containing (A) a polyimide precursor having a polymerizable unsaturated bond, (B) a polymerizable monomer, (C) a photopolymerization initiator, and (D) a heat radical generator, onto a substrate and drying it, to form a photosensitive resin film; subjecting the photosensitive resin film to pattern exposure, to obtain a resin film; developing the resin film after the pattern exposure, using an organic solvent, to obtain a pattern resin film; and heating the pattern resin film.SELECTED DRAWING: None

Description

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

  BACKGROUND ART Conventionally, polyimide and polybenzoxazole having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like have been used for a surface protective film and an interlayer insulating film of a semiconductor element. In recent years, photosensitive resin compositions in which photosensitive properties have been imparted to these resins themselves have been used, and the use of these resins can simplify the manufacturing process of a pattern cured film and shorten complicated manufacturing processes (for example, see Patent Document 1).

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

  Among the stacked device structures, a multi-die fanout wafer level package is a package in which a plurality of dies are collectively sealed in one package and manufactured. It has attracted a great deal of attention because it can be expected to have lower cost and higher performance than conventional fan-out wafer level packages (where one die is encapsulated in one package).

  In the production of a multi-die fan-out wafer-level package, low-temperature curability at, for example, 200 ° C. or lower is strongly required from the viewpoint of protecting a high-performance die and protecting a sealing material having low heat resistance and improving yield. (For example, see Patent Document 2). In addition, as the degree of integration, the function, and the chip size are reduced, multilayer wiring is required for the package, so that the cured film is required to have high chemical resistance to a chemical such as an organic solvent.

JP 2009-265520 A International Publication No. WO 2008/111470

  However, there is a problem that a cured film obtained by a curing reaction at 200 ° C. or lower has low chemical resistance.

  An object of the present invention is to provide a method for producing a pattern cured film capable of producing a pattern cured film having high chemical resistance even when cured at 200 ° C. or lower, and a photosensitive resin composition. Another object of the present invention is to provide a cured film of the photosensitive resin composition, an interlayer insulating film and the like manufactured using the cured film, and an electronic component including the interlayer insulating film and the like.

The present inventors considered the cause of the low chemical resistance of the cured film as follows. That is, generally, the polymerizable monomer (crosslinking agent) used in the photosensitive resin composition is expected to volatilize in a heat treatment step for curing after forming a pattern by a cross-linking reaction by exposure. In the case of curing at a low temperature of not more than ℃, the crosslinking agent may not be sufficiently volatilized and may remain in the film. If a crosslinking agent having a low degree of polymerization or an unreacted monomer remains in the film, the film becomes a fragile cured film in which a chemical solution easily infiltrates.
The present inventors believe that a dense higher-order structure can be obtained by effectively utilizing the remaining cross-linking agent and sufficiently cross-linking them, and by adding a thermal radical generator that promotes cross-linking in a curing reaction. The inventors have found that the object can be achieved, and have completed the present invention.

（式（１１）中、Ｘ^１は１以上の芳香族基を有する４価の基である。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。）
６．（Ａ）重合性の不飽和結合を有するポリイミド前駆体と、
（Ｂ）重合性モノマーと、
（Ｃ）光重合開始剤と、
（Ｄ）熱ラジカル発生剤と、
を含む感光性樹脂組成物。
７．前記（Ｄ）成分が、有機過酸化物である６に記載の感光性樹脂組成物。
８．前記（Ｄ）成分が、ジアルキルパーオキサイドである６又は７に記載の感光性樹脂組成物。
９．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６〜８のいずれかに記載の感光性樹脂組成物。

（式（１１）中、Ｘ^１は１以上の芳香族基を有する４価の基である。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。）
１０．６〜９のいずれかに記載の感光性樹脂組成物を硬化した硬化膜。
１１．パターン硬化膜である１０に記載の硬化膜。
１２．１０又は１１に記載の硬化膜を用いて作製された層間絶縁膜、カバーコート層又は表面保護膜。
１３．１２に記載の層間絶縁膜、カバーコート層又は表面保護膜を含む電子部品。 According to the present invention, the following method for producing a cured pattern film and the like are provided.
1. A photosensitive resin composition comprising (A) a polyimide precursor having a polymerizable unsaturated bond, (B) a polymerizable monomer, (C) a photopolymerization initiator, and (D) a thermal radical generator. Coating on a substrate and drying 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 patterned resin film,
Heating the pattern resin film,
A method for producing a cured pattern film comprising:
2. 2. The method for producing a cured pattern film according to 1, wherein the temperature of the heat treatment is 200 ° C. or lower.
3. 3. The method for producing a cured pattern film according to 1 or 2, wherein the component (D) is an organic peroxide.
4. 4. The method for producing a cured pattern film according to any one of 1 to 3, wherein the component (D) is a dialkyl peroxide.
5. The method for producing a cured pattern film according to any one of 1 to 4, wherein the component (A) is a polyimide precursor having a structural unit represented by the following formula (11).

(In the formula (11), X ¹ is a tetravalent group having one or more aromatic groups. Y ¹ is a divalent aromatic group. R ¹¹ and R ¹² are each independently a hydrogen atom And a group represented by 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). ^{(The 11} groups and the -CONH- groups are ortho to each other, and the -COOR ¹² groups and the -CO- groups are ortho to each other.)

(In the formula (12), R ^{13 to} R ¹⁵ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. M is an integer of 1 to 10.)
6. (A) a polyimide precursor having a polymerizable unsaturated bond;
(B) a polymerizable monomer;
(C) a photopolymerization initiator,
(D) a thermal radical generator;
A photosensitive resin composition containing:
7. 7. The photosensitive resin composition according to 6, wherein the component (D) is an organic peroxide.
8. The photosensitive resin composition according to 6 or 7, wherein the component (D) is a dialkyl peroxide.
9. The photosensitive resin composition according to any one of 6 to 8, wherein the component (A) is a polyimide precursor having a structural unit represented by the following formula (11).

(In the formula (11), X ¹ is a tetravalent group having one or more aromatic groups. Y ¹ is a divalent aromatic group. R ¹¹ and R ¹² are each independently a hydrogen atom And a group represented by 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). ^{(The 11} groups and the -CONH- groups are ortho to each other, and the -COOR ¹² groups and the -CO- groups are ortho to each other.)

(In the formula (12), R ^{13 to} R ¹⁵ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. M is an integer of 1 to 10.)
A cured film obtained by curing the photosensitive resin composition according to any one of 10.6 to 9.
11. The cured film according to 10, which is a pattern cured film.
12. An interlayer insulating film, a cover coat layer, or a surface protective film produced using the cured film according to 10 or 11.
13. An electronic component comprising the interlayer insulating film, the cover coat layer, or the surface protective film according to 13.12.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the pattern hardening film which can manufacture the pattern hardening film which has high chemical | medical solution resistance even if it hardens at 200 degrees C or less, and the photosensitive resin composition can be provided. Further, a cured film of the photosensitive resin composition, an interlayer insulating film or the like manufactured using the cured film, and an electronic component including the interlayer insulating film or the like can be provided.

It is a schematic diagram showing a manufacturing process of an electronic part concerning one embodiment of the present invention.

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

In the present specification, “A or B” may include either one of A and B, and may include both. In this specification, the term “step” is used not only for an independent step but also for the case where the intended action of the step is achieved even if it cannot be clearly distinguished from other steps. included.
The numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. Further, in the present specification, the content of each component in the composition, if there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, the total of the plurality of substances present in the composition Means quantity. Further, the exemplified materials may be used alone or in combination of two or more unless otherwise specified.
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 “component (A)”), (B) a polymerizable monomer (hereinafter, “(B) ) Component), (C) a photopolymerization initiator (hereinafter also referred to as “component (C)”), and (D) a thermal radical generator (hereinafter also referred to as “component (D)”). including. The photosensitive resin composition of the present invention is preferably a negative photosensitive resin composition.

Since the photosensitive resin composition of the present invention has the above-described components, a pattern cured film having high chemical resistance can be produced. Specifically, the pattern cured film obtained from the photosensitive resin composition of the present invention has a small rate of change in film thickness after being immersed in a chemical solution, and has a small swelling of the film due to penetration of the chemical solution. In addition, there is no crack or crack, and the appearance is excellent.
Further, in the photosensitive resin composition of the present invention, since the crosslinking reaction of the polymerizable monomer (crosslinking agent) (B) is promoted during the heat treatment step, the volatilization amount of the component is small. Therefore, film shrinkage (shrinkage) when a cured film is formed is small and the dimensional accuracy is excellent.
Hereinafter, each component will be described.

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

（式（１１）中、Ｘ^１は１以上の芳香族基を有する４価の基である。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). This makes it possible to form a cured film having high i-line transmittance and good physical properties even when curing is performed at a low temperature of 200 ° C. or less.

(In the formula (11), X ¹ is a tetravalent group having one or more aromatic groups. Y ¹ is a divalent aromatic group. R ¹¹ and R ¹² are each independently a hydrogen atom And a group represented by 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). ^{(The 11} groups and the -CONH- groups are ortho to each other, and the -COOR ¹² groups and the -CO- groups are ortho to each other.)

(In the formula (12), R ^{13 to} R ¹⁵ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. M is an integer of 1 to 10 (preferably an integer of 2 to 10) , More preferably an integer of 2 to 5, further preferably 2 or 3).

A tetravalent group having an aromatic group of one or more (preferably 1 to 3, more preferably 1 or 2) of X ^{1 in} the formula (11) is a tetravalent aromatic hydrocarbon group (for example, having 6 carbon atoms). To 20) or a tetravalent aromatic heterocyclic group (for example, having 5 to 20 atoms). X ¹ is preferably a tetravalent aromatic hydrocarbon group.

Examples of the aromatic hydrocarbon group for X ¹ include a divalent to tetravalent (divalent, trivalent or tetravalent) group formed from a benzene ring, a divalent to tetravalent group formed from naphthalene, and perylene. And divalent and tetravalent groups.

（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 for X ¹ include, for example, the following groups, but are not limited thereto.

(Wherein, Z ¹ and Z ² each independently represent a divalent group or a single bond that is not conjugated to a benzene ring to which they are bonded. Z ³ represents 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 represented by Y ^{1 in} the formula (11) may be a divalent aromatic hydrocarbon group (for example, having 6 to 20 carbon atoms), or may be a divalent aromatic heterocyclic group (having a number of atoms). May be, for example, 5 to 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, but are not limited to, groups represented by the following formula (13).

(In the 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.)

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

In the formula (13), for example, R ²² and R ²³ may be a monovalent aliphatic hydrocarbon group (eg, 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 (preferably 1 or 2) carbon atoms of R ¹¹ and R ^{12 in} the formula (11) include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, and an n- Butyl group and the like.

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

Examples of the aliphatic hydrocarbon group having 1 to 3 (preferably 1 or 2) carbon atoms represented by 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. Can be 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) is, 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 reacting in an organic solvent such as N-methylpyrrolidone, and a compound represented by the following formula (16) is added. 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 the 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 at least 50 mol%, more preferably at least 80 mol%, and preferably at least 90 mol%, based on all structural units of the component (A). More preferred. The upper limit is not particularly limited, and may be 100 mol%.

（式（１７）中、Ｘ^１２は１以上の芳香族基を有する４価の基である。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。） The component (A) may have a structural unit other than the structural unit represented by the 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 the formula (17), X ¹² is a tetravalent group having one or more aromatic groups. Y ¹² is a divalent aromatic group. R ³¹ and R ³² are each independently a hydrogen atom Or an aliphatic hydrocarbon group having 1 to 4. The -COOR ³¹ group and the -CONH- group are at the ortho position to each other, and the -COOR ³² group and the -CO- group are at the ortho position to each other. .)

The tetravalent group having one or more aromatic groups X ¹² of formula (17) include the same groups as tetravalent group having one or more aromatic groups of X ¹ of the 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 groups having 1 to 4 carbon atoms of R ¹¹ and R ^{12 in} the formula (11).

The content of the structural unit other than the structural unit represented by the formula (11) is preferably less than 50 mol% based on all the structural units of the component (A).
The structural units other than the structural unit represented by the 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) to all carboxy groups and all carboxy esters in the polyimide precursor is 50 mol% or more. Preferably, it is more preferably 60 to 100 mol%, and more preferably 70 to 90 mol%.

The molecular weight of the component (A) is not particularly limited, but is preferably 10,000 to 200,000 in number average molecular weight.
The number average molecular weight is measured by gel permeation chromatography (GPC), and is determined by conversion using a standard polystyrene calibration curve. Specific measurement conditions and the like are as described in Examples.

(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 to form a crosslinked network. This makes it possible to form a patterned resin film by a photoreaction, and in the subsequent heat treatment reaction, the crosslinking reaction is promoted by the component (D), so that a hardening having a dense high-order structure and high chemical resistance is achieved. A film (cured product) is obtained.

  The component (B) preferably has a group containing a polymerizable unsaturated double bond. The component (B) has a polymerizability of 2 to 4 for improving the crosslinking density, improving the photosensitivity, and suppressing 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 or an allyl group from the viewpoint of being polymerizable 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 as the aliphatic hydrocarbon group having 1 to 3 carbon atoms of R ^{13 to} R ¹⁵ of the formula (12).

（式（２２）中、Ｒ^４４及びＲ^４５は、それぞれ独立に、炭素数１〜４の脂肪族炭化水素基又は上記式（２１）で表される基である。ｎ１は０又は１であり、ｎ２は０〜２の整数であり、ｎ１＋ｎ２は１以上である。ｎ１個のＲ^４４及びｎ２個のＲ^４５の少なくとも１つは、上記式（２１）で表される基である。） As the component (B), a compound represented by the following formula (22) can be preferably used.

(In the formula (22), R ⁴⁴ and R ⁴⁵ are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the above formula (21). N1 is 0 or 1 , n2 is an integer of 0 to 2, n1 + n2 is at least one of .n1 one ^{R 44} and n2 amino ^{R 45} is 1 or more, a group represented by the formula (21).)

（式（２３）中、Ｒ^４６〜Ｒ^４８は、それぞれ独立に、上記式（２１）で表される基を含む炭素数１〜３０の有機基、又はアリル基を含む炭素数１〜３０の有機基である。）
Ｒ^４６〜Ｒ^４８は、それぞれ独立に、例えば、アリル基又は式（２１）で表される基である。 Further, as the component (B), a compound represented by the following formula (23) can be preferably used.

(In the formula (23), R ^{46 to} R ⁴⁸ each independently represent an organic group having 1 to 30 carbon atoms including a group represented by the above formula (21) or an organic group having 1 to 30 carbon atoms including an allyl group. It is an organic group.)
R ^{46 to} R ⁴⁸ are each independently, for example, an allyl group or a group represented by the formula (21).

  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 diacrylate 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, eth Pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, tetramethylol methane tetraacrylate, tetramethylol methane tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethoxylated pentaerythritol tetraacrylate, triallyl Examples include isocyanurate, ethoxylated isocyanuric acid triacrylate, ethoxylated isocyanuric acid trimethacrylate, acryloyloxyethyl isocyanurate, and methacryloyloxyethyl isocyanurate.

  The content of the component (B) is preferably from 1 to 50 parts by mass, more preferably from 5 to 50 parts by mass, and still more preferably from 5 to 40 parts by mass, per 100 parts by mass of the component (A). When it is within the above range, a practical relief pattern is easily obtained, and the post-development residue of the unexposed portion is easily suppressed.

(Component (C): photopolymerization initiator)
Examples of the photopolymerization initiator as the component (C) include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenylketone, dibenzylketone, and fluorenone; Acetophenone derivatives such as ethoxyacetophenone, 2-hydroxy-2-methylpropiophenone and 1-hydroxycyclohexylphenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and diethylthioxanthone; benzyl, benzyldimethylketal, 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 Oximes such as oxime, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and compounds represented by the following formula: Esters and the like are preferred, but are not limited thereto. Oxime esters are preferred in terms of light sensitivity.

  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 10 parts by mass, per 100 parts by mass of the component (A). 8 parts by mass. When it is in the above range, photocrosslinking tends to be uniform in the film thickness direction, and a practical relief pattern is easily obtained.

((D) component: thermal radical generator)
Since the photosensitive resin composition of the present invention contains (D) a thermal radical generator, the crosslinking reaction of the component (B) is promoted in the heat treatment step, and a dense higher-order structure is formed. This makes it possible to produce a cured film having excellent chemical resistance. Specifically, the component (D) is decomposed by heating during curing to generate radicals, and promotes a polymerization reaction between the components (B) or the components (A) and (B) to form a crosslinked structure.

As the component (D), an organic peroxide is preferable.
Examples of the organic peroxide include dialkyl peroxide, ketone peroxide, peroxyketal, hydroperoxide, diacyl peroxide, peroxydicarbonate, peroxyester, and the like, with dialkyl peroxide being preferred.

Dialkyl peroxide is a compound represented by the following general formula.
ROOR '
In the formula, R and R ′ are each independently a substituted or unsubstituted alkyl group. Examples of the substituent include an aryl group having 6 to 10 carbon atoms. The carbon number of the alkyl group is, for example, 1 to 20 or 1 to 10.

  Specific examples of the dialkyl peroxide include dicumyl peroxide, di-t-butyl peroxide, di (2-t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butyl). Peroxy) hexane, t-butylcumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexine-3 and the like.

  Commercially available products include “Parkmill D”, “Perbutyl P”, “Perhexa 25B”, “Perbutyl C”, “Perhexyl D”, “Perbutyl D”, “Perhexin 25B”, “Perhexin 25B-40” (or more) And NOF Corporation).

  The organic peroxide is preferably a compound having a one-hour half-life temperature of 50 ° C. or more and 200 ° C. or less, and from the viewpoint of promoting the polymerization reaction at a lower temperature, a compound having a one-hour half-life temperature of 50 ° C. or more and 175 ° C. or less is more preferable. preferable.

The one-hour half-life temperature is measured as follows.
An organic peroxide is dissolved in benzene to prepare a 0.1 mol / L solution, which is sealed in a glass tube purged with nitrogen. This is immersed in a constant temperature bath set at a predetermined temperature, pyrolysis, and plotting the relationship of time (t) Ina / (ax), k is obtained from the slope of the obtained straight line, and the half-life ( t _1/2 ).
dx / dt = k (ax)
ln a / (ax) = kt
x = a / 2
kt _1/2 = ln2
x: Decomposed organic peroxide amount k: Decomposition rate constant t: Time a: Organic peroxide initial concentration Since k is represented by the following formula, k is measured at several temperatures, and the relationship between lnk and 1 / T is obtained. Are plotted, the activation energy ΔE is determined from the slope of the straight line obtained, and the frequency factor A is determined from the y-intercept.
k = Aexp [-ΔE / RT]
lnk = lnA-ΔE / RT
A: Frequency factor (1 / h)
ΔE: activation energy (J / mol)
R: gas constant (8.314 J / mol · K)
T: Absolute temperature (K)
Decomposition temperature at which the half-life of the organic peroxide at an arbitrary temperature is obtained from a straight line obtained by plotting the relationship of lnt _1/2 to 1 / T instead of lnk to obtain an arbitrary half-life (1 hour) Is obtained.

  The content of the component (D) is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 20 parts by mass, and further preferably 0.3 to 10 parts by mass, based on 100 parts by mass of the component (A). preferable.

((E) component: solvent)
The photosensitive resin composition of the present invention usually contains a solvent.
As the solvent, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide, 3-methoxy-N, N-dimethylpropanamide (for example, “KJCMPA-100” manufactured by KJ Chemicals Corporation) And organic solvents such as N-dimethylmorpholine.
The content of the solvent is not particularly limited, but is generally 50 to 1000 parts by mass with respect to 100 parts by mass of the component (A).

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

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

（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。） As the coupling agent, a silane coupling agent is preferable.
Preferred silane coupling agents include compounds having a urea bond (—NH—CO—NH—). Thereby, even when the curing is performed at a low temperature of 200 ° C. or less, the adhesiveness to the substrate can be further improved.
The compound represented by the following formula (31) is more preferable in that it exhibits excellent adhesion when cured at a low temperature.

(In the 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. And 3-ureidopropyltriethoxysilane, 4-ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane, and the like, and 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 together, 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, and tert- Butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenyl Silanol, ethyl isopropyl phenyl silanol, n-butyl ethyl phenyl silanol, 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, 1, 1,4-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. Among them, a compound represented by the formula (32) is particularly preferable in order to further improve the adhesiveness to the substrate.

(In the 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. And p is an integer of 1 to 3.)

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

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-glycidyl) (Xymethyl) -3-aminopropyltriethoxysilane, bis (2-hydroxymethyl) -3-aminopropyltrimethoxysilane and the like.

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 the 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 0.3 to 10 parts by mass, and preferably 1 to 10 parts by mass, per 100 parts by mass of the component (A). -10 parts by mass is more preferred.

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

  Examples of the surfactant or the leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, and the like. "," F173 "," R-08 "(above, manufactured by DIC Corporation), trade names" Floraldo FC430 "," FC431 "(above, manufactured by 3M Japan Co., Ltd.), trade names" organosiloxane polymer KP341 "," KBM303 "," KBM403 "," KBM803 "(all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

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

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

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

(Other components)
The photosensitive resin composition of the present invention may contain a sensitizer.
Examples of the sensitizer include 7-N, N-diethylaminocoumarin, 7-diethylamino-3-thenonylcoumarin, 3,3′-carbonylbis (7-N, N-diethylamino) coumarin, and 3,3′-. Carbonyl bis (7-N, N-dimethoxy) coumarin, 3-thienylcarbonyl-7-N, N-diethylaminocoumarin, 3-benzoylcoumarin, 3-benzoyl-7-N, N-methoxycoumarin, 3- (4 ′ -Methoxybenzoyl) coumarin, 3,3'-carbonylbis-5,7- (dimethoxy) coumarin, benzalacetophenone, 4'-N, N-dimethylaminobenzalacetophenone, 4'-acetoaminobenzal-4- Methoxyacetophenone, dimethylaminobenzophenone, diethylaminobenzophenone, 4,4′-bis (N-ethyl, (N-methyl) benzophenone, 4,4'-bis- (diethylamino) benzophenone and the like.

  When a sensitizer is contained, it is more preferably 0.1 to 3.0 parts by mass, and more preferably 0.1 to 1.0 part by mass, based on 100 parts by mass of the polyimide precursor (a). More preferred.

The photosensitive resin composition of the present invention may contain a rust inhibitor from the viewpoint of further improving rust prevention. Examples of the rust inhibitor include 5-amino-1H-tetrazole, 1-methyl-5-amino-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 1-carboxymethyl-5-amino-tetrazole and the like. . These tetrazole compounds may be water-soluble salts thereof.
When the rust inhibitor is contained, the content is preferably 0.05 to 5.0 parts by mass, more preferably 0.1 to 4.0 parts by mass, per 100 parts by mass of the component (a).

Further, the photosensitive resin composition of the present invention may contain a stabilizer. Known compounds such as 1,4,4-trimethyl-2,3-diazabicyclo [3.2.2] -non-2-ene-N, N-dixoid can be used as the stabilizer.
When the stabilizer is contained, the content is preferably 0.05 to 5.0 parts by mass, more preferably 0.1 to 2.0 parts by mass, per 100 parts by mass of the component (a).

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

[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. The thickness of the cured film of the present invention is preferably 5 to 20 μm.

[Production method of pattern cured film]
In the method for producing a pattern cured film of the present invention, a step of applying the above-described photosensitive resin composition on a substrate and drying to form a photosensitive resin film, and pattern-exposing the photosensitive resin film to form a resin film And a step of developing the resin film after the pattern exposure using an organic solvent to obtain a pattern resin film, and a step of heat-treating the pattern resin film. Thus, a cured pattern film can be obtained.

  In the method for producing a pattern cured film of the present invention, the above-mentioned photosensitive resin composition of the present invention is used to carry out the above-mentioned steps, whereby the (B) crosslinking reaction of the polymerizable monomer (crosslinking agent) during the heat treatment step is carried out. Is promoted, and the crosslinking progresses between the components (B) or between the components (A) and (B), whereby a higher-order structure is obtained. This makes it possible to manufacture a pattern cured film having little chemical liquid infiltration and high chemical liquid resistance. In addition, since the volatilization amount of the polymerizable monomer (B) in the heat treatment step is small, film shrinkage (shrinkage) is small and dimensional accuracy is excellent.

  A method of manufacturing a cured film having no pattern includes, for example, a step of forming the above-described photosensitive resin film and a step of performing a heat treatment. Further, a step of exposing may be provided.

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

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

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

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

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

By performing development, a patterned resin film (patterned resin film) can be obtained. Generally, when a negative photosensitive resin composition is used, unexposed portions are removed with a developer.
As the organic solvent used as the developer, a good solvent for the photosensitive resin film can be used alone, or a good solvent and a poor solvent can be appropriately mixed and used.
Examples of good solvents include N-methylpyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, α-acetyl-γ-butyrolactone, and cyclopentanone. , Cyclohexanone and the like.
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 from 0.01 to 10 parts by mass, more preferably from 0.1 to 5 parts by mass, based on 100 parts by mass of the developer.

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

After the development, washing may be performed with a rinsing solution.
As the rinsing liquid, distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, or the like may be used alone or in a suitable mixture, or may be used in a stepwise combination. Good.

  By subjecting the pattern resin film to heat treatment, a cured pattern film can be obtained. The polyimide precursor of the component (A) undergoes a dehydration ring-closing reaction by the heat treatment step, and a part or all of the precursor becomes polyimide.

The temperature of the heat treatment is preferably 250 ° C or lower, more preferably 120 to 250 ° C, and still 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 small, the device can be produced with high yield, and energy saving in the process can be realized.

The time of the heat treatment is preferably 5 hours or less, more preferably 30 minutes to 3 hours. When the content is within the above range, the crosslinking reaction or the dehydration ring-closing reaction can sufficiently proceed.
The atmosphere for the heat treatment may be the air or an inert atmosphere such as nitrogen, but is preferably under a nitrogen atmosphere 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-mentioned passivation film, buffer coat film, interlayer insulating film, cover coat layer, surface protection film, etc., a highly reliable semiconductor device, multilayer wiring board, various electronic devices, etc. Electronic components and the like can be manufactured.

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

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

The interlayer insulating film 4 with the window 6A exposed is selectively etched to provide a window 6B.
Next, the photosensitive resin layer 5 is 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 is electrically connected to the first conductor layer 3.
When a multilayer wiring structure of three or more layers is formed, each layer can be formed by repeating the above steps.

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

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

Synthesis Example 1 (Synthesis of polymer A1)
7.07 g of 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride (ODPA) and 4.12 g of 2,2′-dimethylbiphenyl-4,4′-diamine (DMAP) were combined with N-methyl- It was dissolved in 30 g of 2-pyrrolidone (NMP), stirred at 30 ° C. for 4 hours, and then stirred at room temperature overnight to obtain a polyamic acid. Under water cooling, 9.45 g of trifluoroacetic anhydride was added thereto, and the mixture was stirred at 45 ° C. for 3 hours, and 7.08 g of 2-hydroxyethyl methacrylate (HEMA) was added. The reaction solution was dropped into distilled water, the precipitate was collected by filtration, and dried under reduced pressure to obtain a polyimide precursor (hereinafter, referred to as polymer A1).

The number average molecular weight of the polymer A1 was determined by gel permeation chromatography (GPC) in terms of standard polystyrene under the following conditions. 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)] with respect to 0.5 mg of the polymer A1.
Measuring device: detector L4000UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
Shimadzu Corporation C-R4A Chromatopac
Measurement conditions: Column Gelpack GL-S300MDT-5 × 2 eluents: 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 (reaction rate between carboxy groups derived from ODPA and HEMA) of the polymer A1 was calculated by NMR measurement under the following conditions. The esterification rate was 80 mol% based on the total carboxy groups of the polyamic acid (the remaining 20 mol% was carboxy groups).
Measuring equipment: Bruker BioSpin AV400M
Magnetic field strength: 400 MHz
Reference substance: Tetramethylsilane (TMS)
Solvent: dimethyl sulfoxide (DMSO)

  The components used in the following Examples and Comparative Examples are as follows.

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

Ｂ２：「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）

Ｂ３：「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）

(Component (B): polymerizable monomer)
B1: “TAIC” (Tokyo Kasei Kogyo Co., Ltd., triallyl isocyanurate, compound represented by the following formula)

B2: “A-DCP” (manufactured by Shin-Nakamura Chemical Co., Ltd., tricyclodecane dimethanol diacrylate, a compound represented by the following formula)

B3: “ATM-4E” (Shin Nakamura Chemical Co., Ltd., ethoxylated pentaerythritol tetraacrylate, a compound represented by the following formula)

Ｃ２：「ＩＲＧＡＣＵＲＥ ＯＸＥ ０２」（ＢＡＳＦジャパン株式会社製、下記式で表される化合物）

Ｃ３：「Ｇ−１８２０（ＰＤＯ）」（Ｌａｍｂｓｏｎ社製、下記式で表される化合物）

(Component (C): photopolymerization initiator)
C1: "NCI-930" (manufactured by ADEKA Corporation, O-acyl oxime-based compound, compound represented by the following formula)

C2: “IRGACURE OXE 02” (manufactured by BASF Japan Ltd., compound represented by the following formula)

C3: “G-1820 (PDO)” (a compound represented by the following formula, manufactured by Lambson)

((D) component: thermal radical generator)
D1: “Park Mill D” (manufactured by NOF CORPORATION, dicumyl peroxide, a compound represented by the following formula, 1 hour half-life temperature: 135.7 ° C.)

((E) component: solvent)
E1: NMP
E2: “KJCMPA-100” (manufactured by KJ Chemicals Co., Ltd., compound represented by the following formula)

(Other components: polymerization inhibitor)
"Taobn" (1,4,4-trimethyl-2,3-diazabicyclo [3.2.2] -non-2-ene-N, N-dixoid, manufactured by Hampford Research)

(Other components: rust inhibitor)
"5ATz" (manufactured by Tokyo Chemical Industry Co., Ltd., trade name "5-amino-1H-tetrazole", a compound represented by the following formula)

(Other components: adhesive aid)
"UCT-801" (3-ureidopropyltriethoxysilane, manufactured by United Chemical Technologies)

(Other components: sensitizer)
"EMK" (manufactured by Aldrich, a compound represented by the following formula, Et represents an ethyl group)

Examples 1 to 3 and Comparative Example 1
[Preparation of photosensitive resin composition]
The photosensitive resin compositions of Examples 1 to 3 and Comparative Example 1 were prepared using the components and amounts shown in Table 1. The compounding amounts in Table 1 are parts by mass of each component with respect to 100 parts by mass of the component (A).

[Production and evaluation of pattern cured film]
(Production of cured pattern film)
The obtained photosensitive resin composition is spin-coated on a silicon wafer using a coating apparatus “Act8” (manufactured by Tokyo Electron Limited), dried at 100 ° C. for 2 minutes, and then dried at 110 ° C. for 2 minutes. A photosensitive resin film having a thickness of 13 μm was formed. The development time was set to twice the time required for the obtained photosensitive resin film to be completely dissolved by immersion in cyclopentanone.
A photosensitive resin film was prepared in the same manner as above, and an i-line of 400 mJ / cm ² was applied to the obtained photosensitive resin film in a predetermined pattern using an i-line stepper “FPA-3000iW” (manufactured by Canon Inc.). Was exposed to light. The exposed resin film was paddle-developed with "Act8" using cyclopentanone for the above-mentioned development time, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a patterned resin film. The obtained pattern resin film was heated at 175 ° C. for 1 hour in a nitrogen atmosphere using a vertical diffusion furnace “μ-TF” (manufactured by Koyo Thermo System Co., Ltd.) to obtain a pattern cured film (film thickness after curing of 10 μm). ) Got.

(Evaluation of chemical resistance: appearance)
The obtained pattern cured film was immersed in NMP (chemical solution) heated to 80 ° C. for 30 minutes. Thereafter, the pattern cured film was cooled, washed with acetone, and dried.
The pattern cured film after drying was observed with an optical microscope, and the damage of the pattern was evaluated as follows. Table 1 shows the results.
A: No crack was observed.
B: Fine cracks were observed around the corner of the opening.
C: Cracks were observed around the corner of the opening.
D: Cracks were observed over the entire surface of the cured film.

Example 4 and Comparative Example 2
[Preparation of photosensitive resin composition]
The photosensitive resin compositions of Example 4 and Comparative Example 2 were prepared using the components and amounts shown in Table 2. The compounding amounts in Table 2 are parts by mass of each component with respect to 100 parts by mass of the component (A).

[Production and evaluation of pattern cured film]
(Production of cured pattern film)
A test substrate for a biasHAST (high-speed accelerated life test) (a wafer having a layer structure of silicon wafer / polyimide layer (7 μm) / TiCu seed layer (25/150 nm) / Cu layer (3.5 μm), and a TiCu seed layer and a Cu layer A tooth pattern (having a comb tooth line width: 2 μm, the number of teeth: 10 anodes, 10 cathodes, interval: 2 μm) was used.
The obtained photosensitive resin composition is spin-coated on a test substrate for biasHAST, dried at 105 ° C. for 2 minutes, and then dried at 110 ° C. for 2 minutes to form a photosensitive resin film having a thickness of 7 μm after drying. did. In addition, there was a pad portion on the surface of the biasHAST test substrate, and the application was performed so that the photosensitive resin composition was not applied to the pad portion. The resulting photosensitive resin film was subjected to broadband exposure (i-line conversion: 500 mJ / cm ² ) using “Mask Aligner MA-8” (manufactured by SUSS Microtech). Thereafter, the exposed resin film was heated at 180 ° C. for 2 hours in a nitrogen atmosphere using μ-TF to obtain a test substrate having a cured film (thickness after curing was 6 μm).

(Evaluation of chemical resistance: film thickness change rate)
The obtained cured film was immersed in NMP (chemical solution) heated to 80 ° C. for 30 minutes. Thereafter, the cured film was cooled, washed with acetone, and dried.
The film thickness of the cured film after drying is measured, and the film thickness is obtained by dividing “(film thickness before chemical solution immersion) − (film thickness before chemical solution immersion)” by (film thickness before chemical solution immersion) to obtain a percentage. The thickness change rate was calculated. Table 2 shows the results.

  From Tables 1 and 2, it can be seen that the cured film obtained from the photosensitive resin composition of the present invention has a small film thickness change rate after being immersed in a chemical solution, and has a small swelling of the film due to penetration of the chemical solution. In addition, it can be seen that cracks and cracks are suppressed and the appearance is excellent.

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

Reference Signs List 1 semiconductor substrate 2 protective film 3 first conductive layer 4 interlayer insulating film 5 photosensitive resin layer 6A, 6B, 6C window 7 second conductive layer 8 surface protective film

Claims (13)

A photosensitive resin composition comprising (A) a polyimide precursor having a polymerizable unsaturated bond, (B) a polymerizable monomer, (C) a photopolymerization initiator, and (D) a thermal radical generator. Coating on a substrate and drying 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 patterned resin film,
Heating the pattern resin film,
A method for producing a cured pattern film comprising:   The method according to claim 1, wherein the temperature of the heat treatment is 200 ° C. or less.   The method according to claim 1, wherein the component (D) is an organic peroxide.   The method for producing a cured pattern film according to any one of claims 1 to 3, wherein the component (D) is a dialkyl peroxide. The method for producing a cured pattern film according to any one of claims 1 to 4, wherein the component (A) is a polyimide precursor having a structural unit represented by the following formula (11).

(In the formula (11), X ¹ is a tetravalent group having one or more aromatic groups. Y ¹ is a divalent aromatic group. R ¹¹ and R ¹² are each independently a hydrogen atom And a group represented by 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). ^{(The 11} groups and the -CONH- groups are ortho to each other, and the -COOR ¹² groups and the -CO- groups are ortho to each other.)

(In the formula (12), R ^{13 to} R ¹⁵ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. M is an integer of 1 to 10.) (A) a polyimide precursor having a polymerizable unsaturated bond;
(B) a polymerizable monomer;
(C) a photopolymerization initiator,
(D) a thermal radical generator;
A photosensitive resin composition containing:   The photosensitive resin composition according to claim 6, wherein the component (D) is an organic peroxide.   8. The photosensitive resin composition according to claim 6, wherein the component (D) is a dialkyl peroxide. The photosensitive resin composition according to any one of claims 6 to 8, wherein the component (A) is a polyimide precursor having a structural unit represented by the following formula (11).

(In the formula (11), X ¹ is a tetravalent group having one or more aromatic groups. Y ¹ is a divalent aromatic group. R ¹¹ and R ¹² are each independently a hydrogen atom And a group represented by 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). ^{(The 11} groups and the -CONH- groups are ortho to each other, and the -COOR ¹² groups and the -CO- groups are ortho to each other.)

(In the formula (12), R ^{13 to} R ¹⁵ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. M is an integer of 1 to 10.)   A cured film obtained by curing the photosensitive resin composition according to claim 6.   The cured film according to claim 10, which is a pattern cured film.   An interlayer insulating film, a cover coat layer or a surface protective film produced using the cured film according to claim 10.   An electronic component comprising the interlayer insulating film, the cover coat layer, or the surface protective film according to claim 12.

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