JP2018084626A - Photosensitive resin composition, method for producing patterned cured film, cured film, interlayer insulation film, cover coat layer, surface protective film and electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition that can form a cured film having excellent chemical resistance and adhesiveness even when cured at low temperature of 200°C or less, a method for producing a patterned cured film, a cured film, an interlayer insulation film, a cover coat layer, a surface protective film and an electronic component.SOLUTION: A photosensitive resin composition contains (A) a polyimide precursor having a polymerizable unsaturated bond, (B) a polymerizable monomer having an aliphatic cyclic skeleton, (C) a photopolymerization initiator, and (D) a heat crosslinker.SELECTED DRAWING: None

Description

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

  Conventionally, polyimide and polybenzoxazole 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. By using this, the process for producing a patterned cured film can be simplified and complicated production processes can be shortened (for example, patent documents). 1).

  By the way, in recent years, the miniaturization of transistors, which has supported the high performance of computers, has reached the limit of the scaling law, and a laminated device structure in which semiconductor elements are three-dimensionally stacked for further high performance and high speed. Has attracted attention (see, for example, Non-Patent Document 1).

  Among the stacked device structures, the multi-die fanout wafer level packaging is a package in which a plurality of dies are encapsulated in one package and has been proposed in the past. It is attracting much attention because it can be expected to achieve lower cost and higher performance than conventional fan-out wafer level packages (which are manufactured by sealing one die in one package).

  In the production of a multi-die fan-out wafer level package, low temperature curability is strongly demanded from the viewpoint of protecting high-performance die and sealing material with low heat resistance and improving yield (for example, patents) Reference 2).

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

“Semiconductor Technology Yearbook 2013 Packaging / Mounting”, Nikkei Business Publications, p41-p50.

  The object of the present invention is to provide a photosensitive resin composition capable of forming a cured film having excellent chemical resistance and adhesiveness even at low temperature curing of 200 ° C. or lower, a method for producing a patterned cured film, a cured film, an interlayer insulating film, It is to provide a cover coat layer, a surface protective film, and an electronic component.

When using a cured film for a rewiring layer, in addition to being high resolution in order to perform fine patterning, it turned out that adhesiveness with high copper is required.
In addition, as the degree of integration and functions are improved and the chip size is reduced, it is found that the cured film is required to have higher chemical resistance against organic solvents, strong acids, strong bases, etc., in order to make the package multilayer wiring. It was.
In CSP (chip size packaging) and the like capable of high-density mounting, the cured film is in direct contact with the solder bumps, so the cured film is in direct contact with the flux in the solder bump reflow process. It has been found that a further higher flux resistance is required.

  As a result of intensive studies in view of the above problems, the present inventors have combined a specific polyimide precursor, a polymerizable monomer having an aliphatic cyclic skeleton, a photosensitizer, and a thermal crosslinking agent, so that the low temperature of 200 ° C. or lower. The inventors have found that practical adhesiveness and chemical resistance can be achieved at the time of curing, and have completed the present invention.

（式中、Ｘ_１は４価の芳香族基であって、−ＣＯＯＲ_１基と−ＣＯＮＨ−基とは互いにオルト位置にあり、−ＣＯＯＲ_２基と−ＣＯ−基とは互いにオルト位置にある。Ｙ_１は２価の芳香族基である。Ｒ_１及びＲ_２は、それぞれ独立に、水素原子、下記式（４）で表される１価の基、又は炭素数１〜４の脂肪族炭化水素基であり、Ｒ_１及びＲ_２の少なくとも一方が前記式（４）で表される１価の基である。）

（式（４）中、Ｒ_３〜Ｒ_５は、それぞれ独立に、水素原子又は炭素数１〜３の脂肪族炭化水素基であり、ｍは２〜１０の整数である。）
３．前記（Ｄ）成分がメチロール基を有する１又は２に記載の感光性樹脂組成物。
４．前記（Ｄ）成分が、下記式（２）又は（３）で表される化合物を含む１〜３のいずれかに記載の感光性樹脂組成物。

（式中、Ｒ_４１及びＲ_４２は、水素原子又は−ＣＨ_２−Ｏ−Ｒ_４３である。Ｒ_４３は、水素原子、メチル基、エチル基又はブチル基である。複数のＲ_４１及びＲ_４２は、同一でも、異なっていてもよい。）
５．前記（Ｄ）成分が、下記式（２１）又は（２２）で表される化合物を含む１〜４のいずれかに記載の感光性樹脂組成物。

（式（２１）中、Ｍｅはメチル基である。）
６．さらに、（Ｅ）熱重合開始剤を含む１〜５のいずれかに記載の感光性樹脂組成物。
７．１〜６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。
８．前記加熱処理の温度が２００℃以下である７に記載のパターン硬化膜の製造方法。
９．１〜６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。
１０．パターン硬化膜である９に記載の硬化膜。
１１．９又は１０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。
１２．１１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 having an aliphatic cyclic skeleton,
(C) A photopolymerization initiator, and (D) a photosensitive resin composition containing a thermal crosslinking agent.
2. 2. The photosensitive resin composition according to 1, wherein the component (A) is a polyimide precursor having a structural unit represented by the following formula (1).

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

(In Formula (4), R < ₃ > -R < ₅ > is a hydrogen atom or a C1-C3 aliphatic hydrocarbon group each independently, and m is an integer of 2-10.)
3. 3. The photosensitive resin composition according to 1 or 2, wherein the component (D) has a methylol group.
4). The photosensitive resin composition in any one of 1-3 in which the said (D) component contains the compound represented by following formula (2) or (3).

(In the formula, R ₄₁ and R ₄₂ are a hydrogen atom or —CH ₂ —O—R _43. R ₄₃ is a hydrogen atom, a methyl group, an ethyl group, or a butyl group. Plural R ₄₁ and R _42. May be the same or different.)
5. The photosensitive resin composition in any one of 1-4 whose said (D) component contains the compound represented by following formula (21) or (22).

(In the formula (21), Me is a methyl group.)
6). Furthermore, (E) The photosensitive resin composition in any one of 1-5 containing a thermal-polymerization initiator.
The process of apply | coating the photosensitive resin composition in any one of 7.1-6 on a board | substrate, and drying and forming the photosensitive resin film,
Pattern exposure of the photosensitive resin film to obtain a resin film;
Developing the resin film after the pattern exposure using an organic solvent, and obtaining a pattern resin film;
And a step of heat-treating the pattern resin film.
8). The manufacturing method of the pattern cured film of 7 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 any one of 9.1 to 6.
10. 10. The cured film according to 9, 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 11.9 or 10.
An electronic component comprising the interlayer insulating film, cover coat layer or surface protective film according to 12.11.

  According to the present invention, a photosensitive resin composition capable of forming a cured film having excellent chemical resistance and adhesion even at low temperature curing of 200 ° C. or lower, a method for producing a patterned cured film, a cured film, an interlayer insulating film, A cover coat layer, a surface protective film, and an electronic component can be provided.

It is a manufacturing process figure 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 film using the same, cured film, 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 addition, in this specification, the term “process” is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used as long as the intended action of the process is achieved. 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. In addition, in the present specification, the content of each component in the composition is the sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means quantity. Further, the exemplary materials may be used singly or in combination of two or more unless otherwise specified.
The “(meth) acryl group” in the present specification means “acryl group” and “methacryl group”.

  The photosensitive resin composition of the present invention comprises (A) a polyimide precursor having a polymerizable unsaturated bond (hereinafter also referred to as “component (A)”), and (B) a polymerizable monomer having an aliphatic cyclic skeleton. (Hereinafter also referred to as “component (B)”), (C) photopolymerization initiator (hereinafter also referred to as “(C) component”), and (D) thermal crosslinking agent (hereinafter referred to as “(D) component”. ").

  Thereby, even if it hardens | cures at 200 degrees C or less which has the outstanding photosensitive characteristic, the cured film which is equivalent to the cured film obtained at the time of high temperature curing, and can make adhesiveness to copper and chemical resistance compatible can be formed. In addition, a cured film having high adhesion can be formed even after a durability test (pressure cooker test) under high temperature and high humidity conditions.

  The photosensitive resin composition of the present invention is preferably a negative photosensitive resin composition.

  (A) Although it does not restrict | limit especially as a component, The transmittance | permeability at the time of using i line | wire for the light source at the time of patterning is high, and the polyimide precursor which shows a high cured film characteristic also at the time of low temperature curing below 200 degreeC is preferable.

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

The component (A) is preferably a polyimide precursor having a structural unit represented by the following formula (1). Thereby, the transmittance | permeability of i line | wire is high and a favorable cured film can be formed also at the time of low temperature hardening below 200 degreeC.
The content of the structural unit represented by the formula (1) is preferably 50% or more, more preferably 80% or more, and still more preferably 90% or more with respect to all the structural units of the component (A). The upper limit is not particularly limited, and may be 100%.

（式中、Ｘ_１は４価の芳香族基であって、−ＣＯＯＲ_１基と−ＣＯＮＨ−基とは互いにオルト位置にあり、−ＣＯＯＲ_２基と−ＣＯ−基とは互いにオルト位置にある。Ｙ_１は２価の芳香族基である。Ｒ_１及びＲ_２は、それぞれ独立に、水素原子、下記式（４）で表される１価の基、又は炭素数１〜４の脂肪族炭化水素基であり、Ｒ_１及びＲ_２の少なくとも一方が前記式（４）で表される１価の基である。）

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

（式（４）中、Ｒ_３〜Ｒ_５は、それぞれ独立に、水素原子又は炭素数１〜３の脂肪族炭化であり、ｍは２〜１０の整数（好ましくは２〜５の整数、より好ましくは２又は３）である。）

(In Formula (4), R < ₃ > -R < ₅ > is respectively independently a hydrogen atom or C1-C3 aliphatic carbonization, and m is an integer of 2-10 (preferably an integer of 2-5, more Preferably 2 or 3).)

The tetravalent aromatic group of X _{1 in} the formula (1) may be a tetravalent aromatic hydrocarbon group or a tetravalent aromatic heterocyclic group. A tetravalent aromatic hydrocarbon group is preferred.

（式（５）中、Ｘ及びＹは、それぞれ独立に、各々が結合するベンゼン環と共役しない２価の基又は単結合を示す。Ｚはエーテル基（−Ｏ−）又はスルフィド基（−Ｓ−）である（−Ｏ−が好ましい）。） Examples of the tetravalent aromatic hydrocarbon group of X _{1 in} the formula (1) include, but are not limited to, the group of the following formula (5).

(In Formula (5), X and Y each independently represent a divalent group or a single bond that is not conjugated to the benzene ring to which each is bonded. Z represents an ether group (—O—) or a sulfide group (—S). -) (-O- is preferred).)

  In the formula (5), the divalent group that is not conjugated to the benzene ring to which each of X and Y is bonded is —O—, —S—, a methylene group, a bis (trifluoromethyl) methylene group, or a difluoromethylene group. It is preferable that -O- is more preferable.

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

（式（６）中、Ｒ_６〜Ｒ_１３は、それぞれ独立に水素原子、１価の脂肪族炭化水素基又はハロゲン原子を有する１価の有機基である。） Examples of the divalent aromatic hydrocarbon group represented by Y _{1 in} the formula (1) include the following formula (6), but are not limited thereto.

(In formula (6), R _{6 to} R ₁₃ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group, or a monovalent organic group having a halogen atom.)

As the monovalent aliphatic hydrocarbon group of R _{6 to} R _{13 in} Formula (6) (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), a methyl group is preferable.

The monovalent organic group having a halogen atom (preferably a fluorine atom) represented by R _{6 to} R _{13 in} Formula (6) is a monovalent aliphatic hydrocarbon group having a halogen atom (preferably having 1 to 10 carbon atoms). The number of carbon atoms is preferably 1-6, and a trifluoromethyl group is preferred.

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

At least one of R ₁ and R ₂ in Formula (1) is a monovalent group represented by Formula (4), and both are preferably monovalent groups represented by Formula (4).

Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms (preferably 1 or 2) of R _{3 to} R _{5 in} the formula (4) include a methyl group, an ethyl group, an n-propyl group, and a 2-propyl group. It is done. A methyl group is preferred.

A polyimide precursor having a structural unit represented by the formula (1) includes, for example, a tetracarboxylic dianhydride represented by the following formula (7) and a diamino compound represented by the following formula (8). It can be obtained by reacting in an organic solvent such as -methylpyrrolidone to obtain a polyamic acid, adding a compound represented by the following formula (9), reacting in an organic solvent and partially introducing an ester group it can.
The tetracarboxylic dianhydride represented by the formula (7) and the diamino compound represented by the formula (8) may be used singly or in combination of two or more.

（式中、Ｘ_１は式（１）で定義した通りである。）

(In the formula, X ₁ is as defined in formula (1).)

（式中、Ｙ_１は式（１）で定義した通りである。）

(In the formula, Y ₁ is as defined in Formula (1).)

（式中、Ｒ_１は式（１）で定義した通りである。）

(Wherein R ₁ is as defined in formula (1).)

（式中、Ｘ_２は４価の芳香族基であって、−ＣＯＯＲ_５１基と−ＣＯＮＨ−基とは互いにオルト位置にあり、−ＣＯＯＲ_５２基と−ＣＯ−基とは互いにオルト位置にある。Ｙ_２は２価の芳香族基である。Ｒ_５１及びＲ_５２は、それぞれ独立に、水素原子又は炭素数１〜４の脂肪族炭化水素基である。） (A) A component may have structural units other than the structural unit represented by Formula (1).
Examples of the structural unit other than the structural unit represented by the formula (1) include a structural unit represented by the formula (10).

(In the formula, X ₂ is a tetravalent aromatic group, the —COOR ₅₁ group and the —CONH— group are in the ortho position to each other, and the —COOR ₅₂ group and the —CO— group are in the ortho position to each other. Y ₂ is a divalent aromatic group, and R ₅₁ and R ₅₂ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.)

Examples of the X ₂ tetravalent aromatic group of the formula (10) include the same as the X ₁ tetravalent aromatic group of the formula (1).
Examples of the divalent aromatic group represented by Y _{2 in} the formula (10) include the same divalent aromatic groups represented by Y _{1 in} the formula (1).
Aliphatic hydrocarbon group having 1 to 4 carbon atoms _{R 51} and _{R 52} of formula (10) include the same aliphatic hydrocarbon group having 1 to 4 carbon atoms of _{R 1} and _{R 2.}

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

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

  In the component (A), the ratio of the carboxy group esterified with the monovalent group represented by the formula (4) to the total carboxy group and the total carboxy ester is preferably 50% or more, and 60 -100% is more preferable, and 70-90% 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 can be measured, for example, by a gel permeation chromatography method, and can be determined by conversion using a standard polystyrene calibration curve.

  The photosensitive resin composition of the present invention includes (B) a polymerizable monomer having an aliphatic cyclic skeleton (preferably having 4 to 15 ring-forming carbon atoms, more preferably 5 to 12). Thereby, hydrophobicity can be imparted to the cured film that can be formed, and a decrease in adhesion between the cured film and the substrate under high-temperature and high-humidity conditions can be suppressed.

The component (B) preferably has a polymerizable unsaturated double bond group (preferably a (meth) acryl group). For the purpose of improving the crosslinking density and photosensitivity, and suppressing the swelling of the pattern after development, 2 It is preferable to have ~ 3 polymerizable unsaturated double bond groups.
The component (B) is preferably a compound having a (meth) acryl group that can be polymerized by a photopolymerization initiator.

式中、Ｒ_１４〜Ｒ_２４は、それぞれ独立に、水素原子、炭素数１〜４の脂肪族炭化水素基又は下記式（１２）で表される１価の基である。
Ｒ_１４〜Ｒ_１６の少なくとも１つ（好ましくは２又は３）は、下記式（１２）で表される１価の基である。
Ｒ_１７〜Ｒ_１９の少なくとも１つ（好ましくは２又は３）は、下記式（１２）で表される１価の基である。
Ｒ_２０〜Ｒ_２２の少なくとも１つ（好ましくは２又は３）は、下記式（１２）で表される１価の基である。
Ｒ_２３〜Ｒ_２４の少なくとも１つ（好ましくは２）は、下記式（１２）で表される１価の基である。 Examples of the component (B) include, but are not limited to, the following compounds.

In the formula, R _{14 to} R ₂₄ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, or a monovalent group represented by the following formula (12).
At least one (preferably 2 or 3) of R _{14 to} R ₁₆ is a monovalent group represented by the following formula (12).
At least one (preferably 2 or 3) of R _{17 to} R ₁₉ is a monovalent group represented by the following formula (12).
At least one (preferably 2 or 3) of R _{20 to} R ₂₂ is a monovalent group represented by the following formula (12).
At least one (preferably 2) of R _{23 to} R ₂₄ is a monovalent group represented by the following formula (12).

（式（１２）中、Ｒ_２５〜Ｒ_２７は、それぞれ独立に、水素原子又は炭素数１〜３の脂肪族炭化水素基であり、ｌは０〜１０の整数（好ましくは０、１又は２）である。）

(In formula (12), R _{25 to} R ₂₇ 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 4 carbon atoms of R _{14 to} R _{24 in} formula (11) are the same as those of the aliphatic hydrocarbon group having 1 to 4 carbon atoms in R ₁ and R ₂ of formula (1). Things.

The R 1 to R ₂₇ aliphatic hydrocarbon group represented by R _{25 to} R _{27 in} the formula (12) is the same as the R 1 to R ₅ aliphatic hydrocarbon group represented by R _{3 to} R _{5 in} the formula (4). Things.

  (B) A component may be used individually by 1 type and may combine 2 or more types.

As for content of (B) component, 1-50 mass parts is preferable with respect to 100 mass parts of (A) component. From the viewpoint of improving the hydrophobicity of the cured film, the amount is more preferably 5 to 50 parts by mass, and still more preferably 5 to 30 parts by mass.
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 likely to be suppressed.

As the component (C), for example, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, fluorenone and other benzophenone derivatives,
Acetophenone derivatives such as 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone,
Thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone,
Benzyl derivatives such as benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal,
Benzoin derivatives such as benzoin and benzoin methyl ether, and 1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-methoxycarbonyl) Oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, 1,3-diphenylpropanetrione -2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (o-benzoyl) oxime, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- Carbazol-3-yl]-, 1- (0-acetyloxime), compounds such as the following formulae Although oxime ester etc. are mentioned preferably, it is not limited to these.

  In particular, oxime esters are preferable from the viewpoint of photosensitivity.

  (C) A component may be used individually by 1 type and may combine 2 or more types.

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. 5 parts by mass.
In the above range, photocrosslinking tends to be uniform in the film thickness direction, and a practical relief pattern is easily obtained.

The photosensitive resin composition of this invention contains (D) component. Thereby, in the heat treatment after exposure and development, the component (A) can react (crosslinking reaction), or the crosslinking agent itself can be polymerized, and can be cured at a relatively low temperature, for example, 200 ° C. or less. Excellent heat resistance, chemical resistance, and flux resistance.
Moreover, the combination of (B) component and (D) component can improve adhesiveness, flux tolerance, and chemical tolerance also at the time of low temperature curing below 200 degreeC.

The component (D) is not particularly limited as long as it is a compound that crosslinks or polymerizes, but an alkoxyalkyl group such as a methylol group or an alkoxymethyl group (the alkoxy group preferably has 1 to 3 carbon atoms, and the alkyl group has carbon atoms. Is preferably a compound having 1 to 3) from the viewpoint of high reactivity at low temperature curing.
Among them, a compound having two or more methylol groups or alkoxyalkyl groups is more preferable from the viewpoints of good sensitivity and varnish stability, and chemical resistance and flux resistance of the cured film.

（式中、Ｒ_４１及びＲ_４２は、水素原子又は−ＣＨ_２−Ｏ−Ｒ_４３である。Ｒ_４３は、水素原子、メチル基、エチル基又はブチル基である（好ましくはメチル基）。複数のＲ_４１及びＲ_４２は、同一でも、異なっていてもよい。） The component (D) is preferably a melamine resin or a urea resin, and particularly preferably a compound represented by the following formula (2) or (3) from the viewpoint of low reaction temperature.

(In the formula, R ₄₁ and R ₄₂ are a hydrogen atom or —CH ₂ —O—R _43. R ₄₃ is a hydrogen atom, a methyl group, an ethyl group or a butyl group (preferably a methyl group). R ₄₁ and R ₄₂ may be the same or different.)

Preferably at least one of _{R 41} of formula (2) is a _-CH 2 _{-O-R 43,} more preferably 2 or more _{R 41} is _-CH 2 _{-O-R 43,} 3 of _{R 41} More preferably, ˜6 is —CH ₂ —O—R ₄₃ .
Preferably at least one of _{R 42} of formula (3) _-CH 2 _{-O-R 43,} more preferably 2 or more _{R 42} is _-CH 2 _{-O-R 43,} 3 of _{R 42} Or 4 is more preferably —CH ₂ —O—R ₄₃ .

式（２１）中、Ｍｅはメチル基である。 From the viewpoint of obtaining a cured film having excellent chemical resistance and high temperature flux resistance when cured at a low temperature of 200 ° C. or lower as the component (D), the compound represented by the following formula (21) and the following The compound represented by formula (22) is most preferable.

In formula (21), Me is a methyl group.

  (D) A component may be used individually by 1 type and may combine 2 or more types.

  The content of the component (D) is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the component (A), more preferably 3 to 30 parts by mass for ensuring good flux resistance, and during development. From the viewpoint of elution of the unreacted (D) component, and from the viewpoint of coexistence of flux resistance and photosensitive characteristics, 5 to 20 parts by mass is more preferable.

The photosensitive resin composition of the present invention may further contain (E) a thermal polymerization initiator.
The component (E) is not decomposed by heating (drying) to remove the solvent during film formation, but decomposes by heating at the time of curing to generate radicals, and the components (B) or (A) and (B) The compound which accelerates | stimulates the polymerization reaction of a component is preferable. Therefore, the component (E) is preferably a compound having a decomposition point of 110 ° C. or higher and 200 ° C. or lower, and more preferably a compound of 110 ° C. or higher and 175 ° C. or lower from the viewpoint of promoting the polymerization reaction at a lower temperature.

  Examples of the component (E) include bis (1-phenyl-1-methylethyl) peroxide.

  (E) A component may be used individually by 1 type and may combine 2 or more types.

  When the component (E) is contained, the content of the component (E) is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the component (A), and 1 for ensuring good flux resistance. -20 mass parts is more preferable, and 1-10 mass parts is still more preferable from a viewpoint of the solubility fall suppression by decomposition | disassembly at the time of drying.

The photosensitive resin composition of the present invention usually contains a solvent.
Examples of the solvent include organic solvents such as N-methylpyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, and dimethyl sulfoxide.
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.

  The photosensitive resin composition of the present invention may contain a coupling agent, a surfactant or a leveling agent, a rust inhibitor, a polymerization inhibitor, and the like.

  Usually, in the heat treatment after development, the coupling agent itself is polymerized in the step of reacting with the polyimide precursor as the component (A) to crosslink or heat-treat. Thereby, the adhesiveness of the cured film obtained and a board | substrate can be improved more.

（式中、Ｒ_３１及びＲ_３２は、それぞれ独立に炭素数１〜５のアルキル基である。ａは１〜１０の整数であり、ｂは１〜３の整数である。） 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 (13) is more preferable in that it exhibits excellent adhesion when cured at a low temperature.

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

  Specific examples of the compound represented by the formula (13) 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.
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 (14) below. Especially, in order to improve adhesiveness with a board | substrate more, the compound represented by Formula (14) is preferable.

（式中、Ｒ_３３はヒドロキシ基又はグリシジル基を有する１価の有機基、Ｒ_３４及びＲ_３５はそれぞれ独立に炭素数１〜５のアルキル基である。ｃは１〜１０の整数であり、ｄは１〜３の整数である。）

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

  Examples of the compound represented by the formula (14) 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.

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

  A silane coupling agent may be used individually by 1 type, and may combine 2 or more types.

  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 More preferably, it is 10 mass parts.

  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 Dainippon Ink & Chemicals, Inc.), trade names "Florard FC430", "FC431" (above, manufactured by Sumitomo 3M Limited), trade names "organosiloxane" Polymer KP341 ”,“ KBM303 ”,“ KBM403 ”,“ KBM803 ”(manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

  Surfactants and leveling agents may be used alone or in combination of two or more.

  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.

By containing a rust preventive agent, it is possible to suppress corrosion and discoloration of copper and copper alloy.
Examples of the rust inhibitor include triazole derivatives and tetrazole derivatives.
A rust preventive may be used individually by 1 type, and may combine 2 or more types.

  When using a 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 parts by mass is more preferable.

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.

  A polymerization inhibitor may be used individually by 1 type, and may combine 2 or more types.

  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) to (D) component, and optionally (E) component, a coupling agent, a surfactant, a leveling agent, and a rust preventive agent, except for the solvent. It is made of a polymerization inhibitor and may contain other inevitable impurities as long as the effects of the present invention are not impaired.
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, or 100% by mass, excluding the solvent,
Components (A) to (D),
(A)-(E) component, or (A)-(D) component, and optionally (E) component, coupling agent, surfactant, leveling agent, rust inhibitor, polymerization inhibitor Good.

The cured product of the present invention can be obtained by curing the above-described photosensitive resin composition.
The cured product 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 hardened | cured material of this invention, 5-20 micrometers is preferable.

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 step of forming the above-described photosensitive resin film and a step 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 90 to 120 ° C. is more preferable in order to suppress the reaction between the component (A) and the component (D) from the viewpoint of ensuring 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 the photosensitive resin composition is used, the 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 appropriately mixed as the developer.
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 completely 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 further preferably 200 ° C. or lower or 160 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.

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 formed so that a predetermined portion of the interlayer insulating film 4 is exposed by a known photolithography technique. Provided.

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 completely removed using an etching solution that corrodes only 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, it demonstrates further more concretely about this invention. In addition, this invention is not limited to the following Example.

Synthesis Example 1 (Synthesis of Polymer I)
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-methylpyrrolidone. (NMP) It melt | dissolved in 30 g, and it stirred at 30 degreeC for 4 hours, and then overnight at room temperature, 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 I).
The number average molecular weight was calculated | required on condition of the following by standard polystyrene conversion using the gel permeation chromatograph (GPC) method. The number average molecular weight of the polymer I was 40,000.

  It measured using 1 mL of solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1/1 (volume ratio)] with respect to 0.5 mg of polymer I.

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

  Moreover, the esterification rate of polymer I (reaction rate of carboxy group of ODPA with HEMA) was calculated by performing NMR measurement under the following conditions. The esterification rate was 80% based on the total carboxy groups (the remaining 20% was carboxy groups).

Measuring instrument: AV400M manufactured by Bruker BioSpin
Magnetic field strength: 400MHz
Reference material: Tetramethylsilane (TMS)
Solvent: Dimethyl sulfoxide (DMSO)

Examples 1-9 and Comparative Examples 1-3
(Preparation of photosensitive resin composition)
Photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 3 were prepared using the components and blending amounts shown in Table 1. The compounding quantity of Table 1 is a mass part of (B)-(E) component with respect to 100 mass parts polymer I.

  Each component used is as follows. As the component (A), the polymer I obtained in Synthesis Example 1 was used.

(B) Component: Polymerizable monomer B1 having an aliphatic cyclic skeleton B1: A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd., tricyclodecane dimethanol diacrylate)
B2: 1,3-diacrylate adamantane (Mitsubishi Gas Chemical Co., Ltd.)
B3: Tetraethylene glycol dimethacrylate B4: A-TMMT (made by Shin-Nakamura Chemical Co., Ltd., pentaerythritol tetraacrylate)

(C) Component: Photopolymerization initiator C1: NCI-930 (manufactured by ADEKA Corporation, O-acyloxime compound)
C2: IRUGCURE OXE 02 (manufactured by BASF Japan Ltd., Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime))
C3: PDO (Lambson, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime)

(D) Component: Thermal crosslinking agent D1: Nicalak MW-390 (manufactured by Sanwa Chemical Co., Ltd., a compound represented by the following formula D1, wherein Me is a methyl group)
D2: Nicalak MX-270 (manufactured by Sanwa Chemical Co., Ltd., 1,3,4,6-tetrakis (methoxymethyl) glycoluril, a compound represented by the following formula D2)

(E) Component: Thermal polymerization initiator E1: Park mill D (Nippon Yushi Co., Ltd., bis (1-phenyl-1-methylethyl) peroxide, compound represented by the following formula E1)

  NMP: N-methylpyrrolidone

(Evaluation of sensitivity)
The obtained photosensitive resin composition is spin-coated on a silicon wafer using a coating apparatus Act8 (manufactured by Tokyo Electron Ltd.), dried at 100 ° C. for 2 minutes, and then dried at 110 ° C. for 2 minutes to obtain a dried film. A photosensitive resin film having a thickness of 12 μm was formed.
The development time was set to twice the time required for the obtained photosensitive resin film to be immersed in cyclopentanone and completely dissolved.
In addition, a photosensitive resin film was prepared in the same manner as described above, and i-line stepper FPA-3000iW (manufactured by Canon Inc.) was used for the obtained photosensitive resin film, and i-line of 50 to 500 mJ / cm ² was obtained. Exposure was performed by irradiating a predetermined pattern with an irradiation amount of 50 mJ / cm ² .
The exposed resin film was subjected to paddle development on cyclopentanone with Act 8 using Act8, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a patterned resin film.
The exposure amount that can form a hole pattern having a diameter of 10 μm was evaluated as sensitivity. The results are shown in Table 1.

(Resolution evaluation)
A pattern resin film was obtained in the same manner as in the sensitivity evaluation except that the photomask was a line and space photomask and the exposure amount was the exposure amount of the sensitivity shown in Table 1.
The line width of the smallest line that could be patterned without peeling or residue was taken as the resolution. The results are shown in Table 1.

(Manufacture of patterned cured film)
The patterned resin film obtained by the sensitivity evaluation was heated at 175 ° C. for 1 hour in a nitrogen atmosphere using a vertical diffusion furnace μ-TF (manufactured by Koyo Thermo Systems Co., Ltd.) to obtain a cured pattern film (film thickness after curing) 10 μm) was obtained.

(Evaluation of NMP resistance)
The obtained pattern cured film was immersed in NMP heated to 80 ° C. for 30 minutes. After cooling, it was washed with acetone and dried.
Measure the film thickness of the pattern cured film after drying, and divide the absolute value of “(film thickness before NMP immersion) − (film thickness of the pattern cured film after drying)” by the film thickness before NMP immersion. The percentage of change in film thickness was calculated as a percentage. The film thickness change rate was evaluated with a film thickness change rate of less than 5% as ◯, a film thickness change rate of 5-10% as Δ, and a film thickness change rate of over 10% as x. The results are shown in Table 1.
Further, the pattern cured film after drying was observed with an optical microscope to evaluate pattern damage. The case where there was no crack or wrinkle was rated as “◯”, and the case where crack or wrinkle occurred was marked as “X”. The results are shown in Table 1.

(Evaluation of flux resistance)
Water-soluble flux WS-600 (manufactured by Cookson Electronics Co., Ltd.) was applied to the above-mentioned pattern cured film, and heated on a hot plate at 245 ° C. for 1 minute. After cooling, it was washed with water heated to 60 ° C. to remove the flux and dried.
Measure the film thickness of the pattern cured film after drying, and divide the absolute value of (film thickness before flux immersion-film thickness of pattern cured film after drying) by the film thickness before flux immersion to obtain a percentage. Thus, the film thickness change rate was calculated. The film thickness change rate was evaluated with a film thickness change rate of less than 5% as ◯, a film thickness change rate of 5-10% as Δ, and a film thickness change rate of over 10% as x. The results are shown in Table 1.
Further, the pattern cured film after drying was observed with an optical microscope to evaluate pattern damage. The case where cracks, wrinkles, and pattern shape did not change was evaluated as “◯”, and the case where cracks, wrinkles and pattern shape were generated was evaluated as “X”. The results are shown in Table 1.

(Adhesive evaluation)
The above-mentioned photosensitive resin composition was spin-coated on a Cu plated wafer using a coating apparatus Act8 (manufactured by Tokyo Electron Ltd.), dried at 100 ° C. for 2 minutes, and then dried at 110 ° C. for 2 minutes to be photosensitive. A resin film was formed.
The obtained photosensitive resin film was exposed to 500 mJ / cm ² using a proximity exposure machine mask aligner MA8 (manufactured by SUSS Microtec).
About the resin film after exposure, it hardened | cured similarly to manufacture of the above-mentioned pattern cured film, and the cured film was obtained.
The obtained cured film was placed in a saturated pressure cooker apparatus (manufactured by Hirayama Manufacturing Co., Ltd.) and treated for 200 hours under conditions of a temperature of 121 ° C. and a relative humidity of 100%.
After 200 hours of treatment, the cured film was taken out, the epoxy resin layer at the tip of the aluminum stud was fixed to the surface of the cured film, and heated in an oven at 120 ° C. for 1 hour to bond the epoxy resin layer and the cured film. Then, the stud was pulled using a thin film adhesion strength measuring apparatus ROMUS (manufactured by QUAD Group), and the peeling mode at the time of peeling was observed.
Those that were cohesive failure (no separation between the cured film and the Cu-plated wafer) were marked with ◯, and those that were peeled between the cured film and the Cu-plated wafer were marked with x.
In the case of cohesive failure, it indicates that the adhesive strength between the cured film and the Cu plated wafer is stronger than the cohesive failure strength of the cured film.
The results are shown in Table 1.

  The photosensitive resin composition of the present invention can be used for an interlayer insulating film, a cover coat layer, or a surface protective film, and the interlayer insulating film, the cover coat layer, or 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 (12)

(A) a polyimide precursor having a polymerizable unsaturated bond,
(B) a polymerizable monomer having an aliphatic cyclic skeleton,
(C) A photopolymerization initiator, and (D) a photosensitive resin composition containing a thermal crosslinking agent. The photosensitive resin composition according to claim 1, wherein the component (A) is a polyimide precursor having a structural unit represented by the following formula (1).

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

(In Formula (4), R < ₃ > -R < ₅ > is a hydrogen atom or a C1-C3 aliphatic hydrocarbon group each independently, and m is an integer of 2-10.)   The photosensitive resin composition according to claim 1, wherein the component (D) has a methylol group. The photosensitive resin composition in any one of Claims 1-3 in which the said (D) component contains the compound represented by following formula (2) or (3).

(In the formula, R ₄₁ and R ₄₂ are a hydrogen atom or —CH ₂ —O—R _43. R ₄₃ is a hydrogen atom, a methyl group, an ethyl group, or a butyl group. Plural R ₄₁ and R _42. May be the same or different.) The photosensitive resin composition in any one of Claims 1-4 in which the said (D) component contains the compound represented by following formula (21) or (22).

(In the formula (21), Me is a methyl group.)   Furthermore, (E) The photosensitive resin composition in any one of Claims 1-5 containing a thermal-polymerization initiator. Applying the photosensitive resin composition according to any one of claims 1 to 6 on a substrate and drying to form a photosensitive resin film;
Pattern exposure of the photosensitive resin film to obtain a resin film;
Developing the resin film after the pattern exposure using an organic solvent, and obtaining a pattern resin film;
And a step of heat-treating the pattern resin film.   The manufacturing method of the pattern cured film of Claim 7 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 9, 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 or 10.   An electronic component comprising the interlayer insulating film according to claim 11, a cover coat layer, or a surface protective film.

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