JP7225652B2 - PHOTOSENSITIVE RESIN COMPOSITION, METHOD FOR MANUFACTURING PATTERN CURED PRODUCT, CURED PRODUCT, INTERLAYER INSULATING FILM, COVER COAT LAYER, SURFACE PROTECTIVE FILM AND ELECTRONIC COMPONENTS - Google Patents

Description

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

Conventionally, polyimide and polybenzoxazole, which have excellent heat resistance, electrical properties, mechanical properties, etc., have been used for surface protective films and interlayer insulating films of semiconductor devices. In recent years, photosensitive resin compositions obtained by imparting photosensitive properties to these resins themselves have been used, and the use of these can simplify the production process of the patterned cured product and shorten the complicated production process. (For example, see Patent Document 1)

By the way, in recent years, the miniaturization of transistors, which has supported the advancement of computer performance, has reached the limit of the scaling law. is attracting attention.

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

In the fabrication of multi-die fan-out wafer-level packages, low-temperature curability is strongly desired from the viewpoint of protecting high-performance dies and sealing materials with low heat resistance and improving yields (for example, patented Reference 2).

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

JP 2009-265520 A WO2008/111470 JP 2016-199662 A

An object of the present invention is to provide a photosensitive resin composition capable of forming a cured product having excellent chemical resistance and moisture resistance even when cured at a low temperature of 200 ° C. or less, a method for producing a pattern cured product, a cured product, an interlayer insulating film, An object of the present invention is to provide a cover coat layer, a surface protective film and an electronic component.

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

（式（２）中、Ｒ_３～Ｒ_５は、それぞれ独立に、水素原子又は炭素数１～３の脂肪族炭化水素基であり、ｍは１～１０の整数である。）

（式（１Ａ）中、Ｘ_１Ａは１以上の芳香族基を有する４価の基であって、－ＣＯＯＲ_１Ａ基と－ＣＯＮＨ－基とは互いにオルト位置にあり、－ＣＯＯＲ_２Ａ基と－ＣＯ－基とは互いにオルト位置にある。Ｙ_１Ａは２価の芳香族基である。Ｒ_１Ａ及びＲ_２Ａ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。）
２．前記（Ｂ）成分が、重合性の不飽和二重結合を含む基を有する重合性モノマーを含む１に記載の感光性樹脂組成物。
３．前記重合性の不飽和二重結合を含む基が、２以上である２に記載の感光性樹脂組成物。
４．前記（Ａ２）成分の含有量が、前記（Ａ１）成分１００質量部に対して、５～５５質量部である１～３のいずれかに記載の感光性樹脂組成物。
５．前記（Ａ２）成分の重量平均分子量が、前記（Ａ１）成分の重量平均分子量に対して、１．２～３．０倍である１～４のいずれかに記載の感光性樹脂組成物。
６．前記（Ａ２）成分の重量平均分子量が、３０，０００～２００，０００である１～５のいずれかに記載の感光性樹脂組成物。
７．さらに、（Ｅ）熱重合開始剤を含む１～６のいずれかに記載の感光性樹脂組成物。
８．１～７のいずれかに記載の感光性樹脂組成物を基板上に塗布、乾燥して感光性樹脂膜を形成する工程と、
前記感光性樹脂膜をパターン露光して、樹脂膜を得る工程と、
前記パターン露光後の樹脂膜を、有機溶剤を用いて、現像し、パターン樹脂膜を得る工程と、
前記パターン樹脂膜を加熱処理する工程と、を含むパターン硬化物の製造方法。
９．前記加熱処理の温度が２００℃以下である８に記載のパターン硬化物の製造方法。
１０．１～７のいずれかに記載の感光性樹脂組成物を硬化した硬化物。
１１．パターン硬化物である１０に記載の硬化物。
１２．１０又は１１に記載の硬化物を用いて作製された層間絶縁膜、カバーコート層又は表面保護膜。
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 photosensitive resin composition and the like are provided.
1. (A1) a polyimide precursor having a structural unit represented by the following formula (1);
(A2) a polyimide precursor having a structural unit represented by the following formula (1A);
(B) a polymerizable monomer,
(C) a photoinitiator, and
(D) A photosensitive resin composition containing a solvent.

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

(In Formula (2), R ₃ to R ₅ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and m is an integer of 1 to 10.)

(In formula (1A), X _1A is a tetravalent group having one or more aromatic groups, the -COOR _1A group and the -CONH- group are ortho to each other, and the -COOR _2A group and -CO - is ortho to each other Y _1A is a divalent aromatic group R _1A and R _2A are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms .)
2. 2. The photosensitive resin composition according to 1, wherein the component (B) contains a polymerizable monomer having a group containing a polymerizable unsaturated double bond.
3. 3. The photosensitive resin composition according to 2, wherein the group containing a polymerizable unsaturated double bond is 2 or more.
4. 4. The photosensitive resin composition according to any one of 1 to 3, wherein the content of component (A2) is 5 to 55 parts by mass with respect to 100 parts by mass of component (A1).
5. 5. The photosensitive resin composition according to any one of 1 to 4, wherein the weight average molecular weight of component (A2) is 1.2 to 3.0 times the weight average molecular weight of component (A1).
6. 6. The photosensitive resin composition according to any one of 1 to 5, wherein the component (A2) has a weight average molecular weight of 30,000 to 200,000.
7. 7. The photosensitive resin composition according to any one of 1 to 6, further comprising (E) a thermal polymerization initiator.
8. A step of applying the photosensitive resin composition according to any one of 1 to 7 on a substrate and drying it to form a photosensitive resin film;
a step of 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;
and a step of heat-treating the pattern resin film.
9. 9. The method for producing a patterned cured product according to 8, wherein the temperature of the heat treatment is 200° C. or less.
10. A cured product obtained by curing the photosensitive resin composition according to any one of 1 to 7.
11. 11. The cured product according to 10, which is a pattern cured product.
12. An interlayer insulating film, cover coat layer or surface protective film produced using the cured product according to 10 or 11.
13. An electronic component comprising the interlayer insulating film, cover coat layer or surface protective film according to 12.

According to the present invention, a photosensitive resin composition capable of forming a cured product having excellent chemical resistance and moisture resistance even when cured at a low temperature of 200 ° C. or less, a method for producing a pattern cured product, a cured product, an interlayer insulating film, Covercoat layers, surface protective films and electronic components can be provided.

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

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

As used herein, "A or B" may include either A or B, or may include both. In addition, the term "step" as used herein refers not only to an independent step, but also to the term if the desired action of the step is achieved even if it cannot be clearly distinguished from other steps. included.
A numerical range indicated using "-" indicates a range including the numerical values before and after "-" as the minimum and maximum values, respectively. In addition, in the present specification, the content of each component in the composition is the sum of the multiple substances present in the composition when there are multiple substances corresponding to each component in the composition, unless otherwise specified. means quantity. Further, unless otherwise specified, the exemplified materials may be used alone, or two or more of them may be used in combination.
"(Meth)acrylic group" as used herein means "acrylic group" and "methacrylic group".

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

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

（式（１Ａ）中、Ｘ_１Ａは１以上の芳香族基を有する４価の基であって、－ＣＯＯＲ_１Ａ基と－ＣＯＮＨ－基とは互いにオルト位置にあり、－ＣＯＯＲ_２Ａ基と－ＣＯ－基とは互いにオルト位置にある。Ｙ_１Ａは２価の芳香族基である。Ｒ_１Ａ及びＲ_２Ａは、それぞれ独立に、水素原子、又は炭素数１～４の脂肪族炭化水素基である。） The photosensitive resin composition of the present invention includes (A1) a polyimide precursor having a structural unit represented by the following formula (1) (hereinafter also referred to as "(A1) component"), (A2) the following formula (1A) ) Polyimide precursor having a structural unit represented by (hereinafter also referred to as "(A2) component".), (B) a polymerizable monomer (hereinafter also referred to as "(B) component"), (C) light A photosensitive resin composition containing a polymerization initiator (hereinafter also referred to as "(C) component") and (D) a solvent (hereinafter also referred to as "(D) component").

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

(In formula (2), R ₃ to R ₅ 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 5 , more preferably 2 or 3).)

(In formula (1A), X _1A is a tetravalent group having one or more aromatic groups, the -COOR _1A group and the -CONH- group are ortho to each other, and the -COOR _2A group and -CO - is ortho to each other Y _1A is a divalent aromatic group R _1A and R _2A are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms .)

As a result, a cured product having excellent chemical resistance and moisture resistance can be formed even when curing is performed at a low temperature of 200° C. or less.
In addition, as an optional effect, a cured product having excellent mechanical properties can be formed even when curing is performed at a low temperature of 200° C. or less.

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

Since the photosensitive resin composition of the present invention contains the component (A1), it has a high i-line transmittance and can form a good cured product even when cured at a low temperature of 200° C. or less.
The content of the structural unit represented by formula (1) is preferably 50 mol% or more, more preferably 80 mol% or more, and 90 mol% or more, based on all the structural units of component (A1). More preferred. The upper limit is not particularly limited, and may be 100 mol %.

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

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

（式（６）中、Ｘ及びＹは、それぞれ独立に、各々が結合するベンゼン環と共役しない２価の基又は単結合を示す。Ｚはエーテル基（－Ｏ－）又はスルフィド基（－Ｓ－）である（－Ｏ－が好ましい）。） Examples of the tetravalent group having one or more aromatic groups for X ₁ of formula (1) include, but are not limited to, the following tetravalent groups of formula (6).

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

In formula (6), the divalent group that is not conjugated with 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. is preferred, and -O- is more preferred.

The divalent aromatic group of Y ₁ in formula (1) may be a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group. Divalent aromatic hydrocarbon groups are preferred.

（式（７）中、Ｒ_１２～Ｒ_１９は、それぞれ独立に水素原子、１価の脂肪族炭化水素基又はハロゲン原子を有する１価の有機基である。） Examples of the divalent aromatic hydrocarbon group for Y ₁ in formula (1) include, but are not limited to, groups of the following formula (7).

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

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

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

Examples of aliphatic hydrocarbon groups having 1 to 4 carbon atoms (preferably 1 or 2) for R ₁ and R ₂ in formula (1) include methyl group, ethyl group, n-propyl group, 2-propyl group, n- A butyl group and the like can be mentioned.

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

Examples of aliphatic hydrocarbon groups having 1 to 3 carbon atoms (preferably 1 or 2) for R ₃ to R ₅ in formula (2) include methyl group, ethyl group, n-propyl group and 2-propyl group. be done. Methyl groups are preferred.

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

（式（８）中、Ｘ_１は式（１）のＸ_１に対応する基である。）

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

（式（９）中、Ｙ_１は式（１）で定義した通りである。）

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

（式（１０）中、Ｒは上述の式（２）で表される基である。）

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

（式（１１）中、Ｘ_２は１以上の芳香族基を有する４価の基であって、－ＣＯＯＲ_５１基と－ＣＯＮＨ－基とは互いにオルト位置にあり、－ＣＯＯＲ_５２基と－ＣＯ－基とは互いにオルト位置にある。Ｙ_２は２価の芳香族基である。Ｒ_５１及びＲ_５２は、それぞれ独立に、水素原子又は炭素数１～４の脂肪族炭化水素基である。） The (A1) component may have a structural unit other than the structural unit represented by formula (1).
Structural units other than the structural unit represented by formula (1) include structural units represented by formula (11).

(In formula (11), X ₂ is a tetravalent group having one or more aromatic groups, the —COOR ₅₁ group and the —CONH— group are ortho to each other, and the —COOR ₅₂ group and —CO - is ortho 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 tetravalent group having one or more aromatic groups for X ₂ of formula (11) include the same tetravalent groups having one or more aromatic groups as X ₁ for formula (1).
Examples of the divalent aromatic group for Y ₂ in formula (11) include the same divalent aromatic groups for Y ₁ in formula (1).
Examples of the aliphatic hydrocarbon groups having 1 to 4 carbon atoms for R ₅₁ and R ₅₂ in formula (11) include the same aliphatic hydrocarbon groups having 1 to 4 carbon atoms as R ₁ and R ₂ .

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

The content of structural units other than the structural units represented by formula (1) is preferably less than 50 mol % with respect to all structural units of component (A1).

In component (A1), the ratio of carboxy groups esterified with the group represented by formula (2) to all carboxy groups and all carboxy esters is preferably 50 mol% or more, preferably 60 mol%. The above is more preferable, and 70 mol % or more is even more preferable. The upper limit is not particularly limited, and may be 100 mol %.

The molecular weight of component (A1) is not particularly limited, but the weight average molecular weight is preferably from 10,000 to 50,000, more preferably from 15,000 to 45,000, more preferably from 18,000 to 40,000. 000 is more preferred.
The weight average molecular weights of component (A1) and component (A2) described below can be measured, for example, by gel permeation chromatography, and can be determined by conversion using a standard polystyrene calibration curve.

Examples of the tetravalent group having one or more aromatic groups for X _1A of formula (1A) include the same tetravalent groups having one or more aromatic groups as X ₁ for formula (1).
Examples of the divalent aromatic group for Y _1A in formula (1A) include the same divalent aromatic groups for Y ₁ in formula (1).
Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms for R _1A and R _2A in formula (1A) include the same aliphatic hydrocarbon groups having 1 to 4 carbon atoms for R ₁ and R ₂ .

The (A2) component may have a structural unit other than the structural unit represented by formula (1A).
Structural units other than the structural unit represented by formula (1A) include structural units represented by formula (1).

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

The content of structural units other than the structural units represented by formula (1A) is preferably less than 50 mol % with respect to all structural units of component (A2).

The molecular weight of component (A2) is not particularly limited, but from the viewpoint of developability, the weight average molecular weight is preferably 10,000 to 100,000, more preferably 20,000 to 90,000. More preferably 30,000 to 80,000.

From the viewpoint of developability, the weight average molecular weight of component (A2) is preferably 1.2 to 3.2 times the weight average molecular weight of component (A1), and 1.4 to 3.0. More preferably, 1.6 to 2.8 is even more preferable.

The content of component (A2) is preferably from 5 to 55 parts by mass, more preferably from 10 to 50 parts by mass, more preferably from 10 to 50 parts by mass, with respect to 100 parts by mass of component (A1), from the viewpoint of developability and sensitivity. 45 parts by mass is more preferable.

Component (B) is a polymerizable group containing (preferably two or more) polymerizable unsaturated double bonds (preferably, a (meth)acrylic group because it can be polymerized by a photopolymerization initiator) It preferably contains a monomer, and preferably has 2 to 3 groups containing polymerizable unsaturated double bonds in order to improve crosslink density and photosensitivity and suppress swelling of the pattern after development.

Component (B) includes, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate , pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate,
Tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated isocyanuric acid triacrylate, ethoxylated isocyanuric acid trimethacrylate, acryloyloxyethyl isocyanurate , methacryloyloxyethyl isocyanurate, and the like. Tetraethylene glycol dimethacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate are preferred.

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

The content of component (B) is preferably 1 to 50 parts by mass per 100 parts by mass of component (A1). From the viewpoint of improving the hydrophobicity of the cured product, it is more preferably 3 to 45 parts by mass, still more preferably 5 to 40 parts by mass.
Within the above range, it is easy to obtain a practical relief pattern, and it is easy to suppress the post-development residue in the unexposed area.

Component (C) includes, for example, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenylketone, dibenzylketone, benzophenone derivatives such as fluorenone,
Acetophenone derivatives such as 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone,
thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone;
benzyl derivatives such as benzyl, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal;
Benzoin, benzoin derivatives such as 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-(O-acetyloxime) and oxime esters such as compounds represented by the following formulas are preferred, but are not limited thereto.

Oxime esters are particularly preferred in view of photosensitivity.

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

The content of 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, relative to 100 parts by mass of component (A1). 5 parts by mass.
Within the above range, the photo-crosslinking tends to be uniform in the film thickness direction, making it easier to obtain a practical relief pattern.

The photosensitive resin composition of the present invention contains (D) a solvent.
Component (D) includes N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphorylamide, tetramethylenesulfone, cyclohexanone, cyclopentanone, diethylketone, diisobutylketone, methylamylketone, N-dimethylmorpholine and the like. There is usually no particular limitation as long as the other components can be sufficiently dissolved.
Among these, N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, and N,N-dimethylformamide are preferred from the viewpoint of the solubility of each component and the coating properties when forming a photosensitive resin film. , N,N-dimethylacetamide is preferably used.

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

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

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

(D) Component may be used individually by 1 type, and may combine 2 or more types.
The content of component (D) is not particularly limited, but is generally 50 to 1000 parts by mass per 100 parts by mass of component (A1).

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

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

When component (E) is contained, the content of component (E) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of component (A1). 2 to 20 parts by mass is more preferable, and 0.3 to 10 parts by mass is more preferable from the viewpoint of suppressing deterioration of solubility due to decomposition during drying.

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

Usually, the coupling agent reacts with the component (A1) or the component (A2) to crosslink in the heat treatment after development, or the coupling agent itself polymerizes in the heat treatment step. Thereby, the adhesion between the obtained cured product and the substrate can be further improved.

（式（１３）中、Ｒ_３１及びＲ_３２は、それぞれ独立に炭素数１～５のアルキル基である。ａは１～１０の整数であり、ｂは１～３の整数である。） Preferred silane coupling agents include compounds having a urea bond (--NH--CO--NH--). As a result, even when curing is performed at a low temperature of 200° C. or less, the adhesiveness to the substrate can be further enhanced.
A compound represented by the following formula (13) is more preferable because it exhibits excellent adhesiveness when cured at a low temperature.

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

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

A silane coupling agent having a hydroxyl group or a glycidyl group may be used as the silane coupling agent. 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 product to the substrate during low temperature curing can be further improved.
Silane coupling agents having a hydroxy group or a glycidyl group include methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert- Butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenyl silanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol, 1,4-bis(trihydroxysilyl)benzene, 1,4-bis(methyldihydroxysilyl)benzene, 1,4-bis(ethyldihydroxysilyl)benzene, 1,4-bis(propyldihydroxysilyl)benzene, 1,4-bis(butyldihydroxysilyl)benzene, 1,4-bis(dimethylhydroxysilyl)benzene, 1,4-bis(diethylhydroxysilyl)benzene, 1, 4-bis(dipropylhydroxysilyl)benzene, 1,4-bis(dibutylhydroxysilyl)benzene, compounds represented by the following formula (14), and the like. Among them, the compound represented by the formula (14) is particularly preferable in order to further improve the adhesiveness to the substrate.

（式（１４）中、Ｒ_３３はヒドロキシ基又はグリシジル基を有する１価の有機基であり、Ｒ_３４及びＲ_３５は、それぞれ独立に炭素数１～５のアルキル基である。ｃは１～１０の整数であり、ｄは１～３の整数である。）

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

Compounds represented by 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-glycidoxybutyltriethoxysilane and the like. be done.

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

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

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 0.3 to 10 parts by mass, with respect to 100 parts by mass of component (A1). ~10 parts by mass is more preferable.

By containing a surfactant or a leveling agent, it is possible to improve coatability (for example, suppression of striation (unevenness in film thickness)) and developability.

Examples of surfactants or leveling agents include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenol ether. ”, “F173”, “R-08” (manufactured by DIC Corporation), trade names “Fluorard FC430”, “FC431” (manufactured by Sumitomo 3M), trade names “organosiloxane polymer KP341”, “ KBM303", "KBM403", and "KBM803" (manufactured by Shin-Etsu Chemical Co., Ltd.).

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

When a surfactant or leveling agent is included, the content of the surfactant or leveling agent is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of component (A1). Preferably, 0.05 to 3 parts by mass is more preferable.

Containing a rust inhibitor can suppress corrosion and prevent discoloration of copper and copper alloys.
Rust inhibitors include, for example, triazole derivatives and tetrazole derivatives.
The rust preventives may be used singly or in combination of two or more.

When a rust inhibitor is used, the content of the rust inhibitor is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, more preferably 0.5 to 100 parts by mass, based on 100 parts by mass of component (A1). 3 parts by mass is more preferable.

Good storage stability can be ensured by containing a polymerization inhibitor.
Examples of polymerization inhibitors include radical polymerization inhibitors and radical polymerization inhibitors.

Examples of polymerization inhibitors include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N-phenyl-2- naphthylamine, cupferron, 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 a polymerization inhibitor is contained, the content of the polymerization inhibitor is 0 per 100 parts by mass of the component (A1) from the viewpoint of the storage stability of the photosensitive resin composition and the heat resistance of the resulting cured product. 0.01 to 30 parts by weight is preferred, 0.01 to 10 parts by weight is more preferred, and 0.05 to 5 parts by weight is even more preferred.

The photosensitive resin composition of the present invention essentially comprises components (A1), (A2), (B) to (D) and optionally component (E), a coupling agent, a surfactant, a leveling agent, It consists of a rust inhibitor and a polymerization inhibitor, and may contain other unavoidable impurities within a range that does not impair the effects of the present invention.
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,
(A1), (A2), (B) to (D) components,
Components (A1), (A2), (B) to (E), or components (A1), (A2), (B) to (D), and optionally component (E), coupling agents, surfactants , a leveling agent, a rust inhibitor, and a polymerization inhibitor.

The cured product of the present invention can be obtained by curing the photosensitive resin composition described above.
The cured product of the present invention may be used as a patterned cured product or as a non-patterned cured product.
The film thickness of the cured product of the present invention is preferably 5 to 20 μm.

In the method for producing a patterned cured product of the present invention, the above photosensitive resin composition is coated on a substrate and dried to form a photosensitive resin film, and the photosensitive resin film is pattern-exposed to form a resin film. a step of obtaining a patterned resin film, a step of developing the resin film after pattern exposure using an organic solvent to obtain a patterned resin film, and a step of heat-treating the patterned resin film.
Thereby, a pattern hardened material can be obtained.

A method for producing a pattern-free cured product includes, for example, the steps of forming the above-described photosensitive resin film and heat-treating. Furthermore, you may provide the process of exposing.

Examples of the substrate include glass substrates, semiconductor substrates such as Si substrates (silicon wafers), metal oxide insulator substrates such as _TiO2 substrates and _SiO2 substrates, silicon nitride substrates, copper substrates, copper alloy substrates, and the like.

The coating method is not particularly limited, but 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 90 to 150°C, more preferably 90 to 120°C from the viewpoint of ensuring the dissolution contrast.
The drying time is preferably 30 seconds to 5 minutes.
Drying may be performed twice or more.
As a result, a photosensitive resin film formed by forming the above photosensitive resin composition into a film can be obtained.

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

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

By developing, a patterned resin film (patterned resin film) can be obtained. In general, when a negative photosensitive resin composition is used, the unexposed area is removed with a developer.
As for 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 as the developer.
Good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, gamma-butyrolactone, α-acetyl-gamma-butyrolactone, cyclopenta non, cyclohexanone, and the like.
Poor solvents include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and water.

A surfactant may be added to the developer. The amount to be added is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the developer.

The development time can be, for example, double the time required for the photosensitive resin film to be immersed and completely dissolved.
The development time varies depending on the components (A1) and (A2) used, but is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and more preferably 20 seconds to 5 minutes from the viewpoint of productivity. .

After development, washing may be performed with a rinse liquid.
As the rinse liquid, distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. may be used singly or in an appropriate mixture, or may be used in a stepwise combination. good.

A pattern cured product can be obtained by heat-treating the pattern resin film.
The polyimide precursors of the components (A1) and (A2) undergo a dehydration ring-closure reaction in the heat treatment step, and usually become the corresponding polyimides.

The temperature of the heat treatment is preferably 250°C or lower, more preferably 120 to 250°C, and even more preferably 200°C or lower or 140 to 200°C.
Within the above range, damage to substrates and devices can be minimized, devices can be produced with high yield, and energy saving in 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 cross-linking reaction or the dehydration ring-closing reaction can proceed sufficiently.
The atmosphere of the heat treatment may be the air or an inert atmosphere such as nitrogen, but the nitrogen atmosphere is preferable from the viewpoint of preventing the pattern resin film from being oxidized.

Devices used for the heat treatment include quartz tube furnaces, hot plates, rapid thermal annealing, vertical diffusion furnaces, infrared curing furnaces, electron beam curing furnaces, microwave curing furnaces, and the like.

The cured product of the present invention can be used as a passivation film, a buffer coat film, an interlayer insulating film, a cover coat layer, a surface protection film, or the like.
Highly reliable semiconductor devices, multilayer wiring boards, various electronic devices, laminates using one or more selected from the group consisting of the passivation film, buffer coat film, interlayer insulating film, cover coat layer, surface protective film, etc. Electronic parts such as devices (multi-die fan-out wafer level packages, etc.) can be manufactured.

An example of the manufacturing process of the semiconductor device, which is the electronic component of the present invention, will be described with reference to the drawings.
FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure, which is an electronic component according to one 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 predetermined portions 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 made of chlorinated rubber, phenol novolac, or the like is formed on the interlayer insulating film 4, and windows 6A are formed by a known photolithography technique so that a predetermined portion of the interlayer insulating film 4 is exposed. be provided.

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

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

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

Hereinafter, the present invention will be described more specifically based on examples and comparative examples. It should be noted that the present invention is not limited to the following examples.

Synthesis Example 1 (Synthesis of A1)
7.07 g of 3,3′,4,4′-diphenylethertetracarboxylic dianhydride (ODPA), 0.831 g of 2-hydroxyethyl methacrylate (HEMA) and a catalytic amount of 1,4-diazabicyclo [2.2. 2. ] Octanetriethylenediamine was dissolved in 30 g of N-methyl-2-pyrrolidone (NMP), stirred at 45°C for 1 hour, and then cooled to 25°C. After adding a solution of 4.12 g of 2,2′-dimethylbiphenyl-4,4′-diamine (DMAP) dissolved in N-methyl-2-pyrrolidone (NMP), the mixture was stirred at 30° C. for 4 hours. After that, the mixture was stirred overnight at room temperature to obtain a reaction solution.
9.45 g of trifluoroacetic anhydride was added to this reaction solution and stirred at 45° C. for 3 hours, and 7.08 g of 2-hydroxyethyl methacrylate (HEMA) was added and stirred at 45° C. for 20 hours. This reaction liquid was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyimide precursor A1.
Using a gel permeation chromatography (GPC) method, the weight average molecular weight was obtained under the following conditions by standard polystyrene conversion. A1 had a weight average molecular weight of 25,575.

Measurement was performed using a solution of 1 mL of solvent [tetrahydrofuran (THF)/dimethylformamide (DMF)=1/1 (volume ratio)] with respect to 0.5 mg of A1.

Measuring device: Detector L4000UV manufactured by Hitachi, Ltd.
Pump: L6000 manufactured by Hitachi, Ltd.
Shimadzu Corporation C-R4A Chromatopac
Measurement conditions: column Gelpack GL-S300MDT-5 × 2 eluent: THF/DMF = 1/1 (volume ratio)
LiBr (0.03 mol/L), _H3PO4 ( _0.06 mol/L)
Flow rate: 1.0 mL/min, detector: UV270 nm

Further, the esterification rate of A1 (reaction rate of the carboxy group of ODPA with HEMA) was calculated by NMR measurement under the following conditions. The esterification rate was 80 mol % with respect to all carboxy groups and all carboxy esters (the remaining 20 mol % being carboxy groups).

Measuring instrument: AV400M manufactured by Bruker Biospin
Magnetic field strength: 400MHz
Reference substance: Tetramethylsilane (TMS)
Solvent: dimethyl sulfoxide (DMSO)

Synthesis Example 2 (Synthesis of A2)
3,3′,4,4′-Diphenylethertetracarboxylic dianhydride (ODPA) 37.23 g and 2,2′-dimethylbiphenyl-4,4′-diamine (DMAP) 24.97 g, 583.19 g of KJCMPA-100 (described later) and stirred overnight at room temperature to obtain a polyimide precursor A2.
Using the GPC method, the weight average molecular weight was obtained under the same conditions as in Synthesis Example 1. A2 had a weight average molecular weight of 64,872.

Examples 1-2 and Comparative Example 1
(Preparation of photosensitive resin composition 1)
Using the components and blending amounts shown in Table 1, photosensitive resin compositions of Examples 1 and 2 and Comparative Example 1 were prepared. The blending amounts in Table 1 are parts by mass of each component with respect to 100 parts by mass of A1.

Each component used is as follows. A1 obtained in Synthesis Example 1 was used as the component (A1). A2 obtained in Synthesis Example 2 was used as the component (A2).

(B) component: polymerizable monomer B1: tetraethylene glycol dimethacrylate B2: ATM-4E (manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated pentaerythritol tetraacrylate, compound represented by the following formula (n11 + n12 + n13 + n14 is 4) )

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

(D) Component: Solvent D1: KJCMPA-100 (manufactured by KJ Chemicals, a compound represented by the following formula D2)

(Production of pattern cured product 1)
The obtained photosensitive resin composition is spin-coated on a silicon wafer using a coating device Act8 (manufactured by Tokyo Electron Co., Ltd.), dried at 100 ° C. for 2 minutes, and dried at 110 ° C. for 2 minutes to form a dry film. A photosensitive resin film having a thickness of 10 to 15 μm was formed.
The development time was set to twice the time required for completely dissolving the obtained photosensitive resin film by immersing it in cyclopentanone.
In addition, a photosensitive resin film was prepared in the same manner as described above, and an i-ray stepper FPA-3000iW (manufactured by Canon Inc.) was used to apply 1000 mJ/cm ² of i-rays to the obtained photosensitive resin film. A pattern (a pattern in which seven 100 μm×100 μm grids (unexposed portions) are arranged at intervals of 10 μm) was exposed to light.
After exposure, the resin film was puddle-developed with cyclopentanone using Act8 for the above development time, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a patterned resin film.
The resulting patterned resin film was heated at 150° C. for 2 hours in a nitrogen atmosphere using a vertical diffusion furnace μ-TF (manufactured by Koyo Thermo Systems Co., Ltd.) to form a patterned cured product (film thickness after curing: 10 μm). Obtained.

(Chemical resistance evaluation 1)
The film thickness of the patterned cured product obtained in Production 1 of the patterned cured product was measured. Using a stylus type profiler Dektak 150 (manufactured by Bruker), a stylus is placed on the pattern cured product, and the stylus is scanned so as to include the exposed portion of the silicon wafer, thereby curing the pattern from the silicon wafer surface. The height to the surface of the object was measured (the film thickness measurement is the same below).
After that, the patterned cured product obtained in Production 1 of the patterned cured product was immersed in Dynastrip 7700 (manufactured by Dynaloy) heated to 70° C. for 30 minutes. After cooling, it was washed with distilled water and dried.

The film thickness of the pattern cured product after drying is measured, and the absolute value of "(film thickness before immersion in Dynastrip 7700) - (film thickness of pattern cured product after immersion in Dynastrip 7700, drying)" is the film thickness before immersion in Dynastrip 7700. The film thickness change rate was calculated by dividing and converting to percentage. The film thickness change rate was evaluated with A when the film thickness change rate was less than 50%, B when the film thickness change rate was 50% or more and less than 70%, and C when the film thickness change rate exceeded 70%. . Table 1 shows the results.

In addition, the pattern cured product after drying was observed with an optical microscope, and the width of Dynastrip 7700 permeation into the cured product around the grid of 100 μm×100 μm was visually measured to evaluate the permeation.
A was given when the penetration was less than 5 µm, B was given when the penetration was between 5 µm and less than 35 µm, and C was given when the penetration was 35 µm or more. Table 1 shows the results.

In addition, the cured pattern after drying was observed with an optical microscope to measure the average spacing of 100 μm×100 μm grids. When the average spacing of the 100 μm×100 μm grid was 5.0 μm or more, it was rated A; when it was 2.5 μm or more and less than 5.0 μm, it was rated B; Table 1 shows the results.

(Production of patterned cured product 2)
The above photosensitive resin composition was spin-coated on a Si substrate and dried by heating on a hot plate at 110° C. for 180 seconds to form a photosensitive resin film of 15.0 to 16.0 μm.
The obtained photosensitive resin film is subjected to broadband (BB) exposure using a mask aligner MA-8 (manufactured by Suss Microtech), and the exposed resin film is developed with cyclopentanone to obtain a width of 10 mm. strip-shaped patterned resin films were obtained.
The resulting patterned resin film was cured at 150° C. for 2 hours to obtain a patterned cured product with a film thickness of 10 μm.

(Evaluation of moisture resistance)
The patterned cured product obtained in production 2 of the patterned cured product was immersed in a 4.9% by mass hydrofluoric acid aqueous solution, and the cured product with a width of 10 mm was peeled off from the wafer.
A tensile test was performed on the peeled cured product having a width of 10 mm using Autograph AGS-X 100 N (manufactured by Shimadzu Corporation). The distance between chucks was 20 mm, the tensile speed was 5 mm/min, and the measurement temperature was 18 to 25°C. In the obtained graph of tensile elongation and tensile stress, the maximum point was determined in the range of tensile elongation of 10% or less. This was measured 6 times and an average value of 1 was obtained.
In addition, the patterned cured product obtained in Production 2 of the patterned cured product described above was subjected to a PCT (pressure cooker test) test device HASTEST (Hirayama Seisakusho Co., Ltd., PC-R8D) at 121 ° C. and 100 RH (Relative Humidity). %, 2 atm for 100 hours.
The pattern cured product was taken out from the PCT tester, and the pattern cured product was peeled off and subjected to a tensile test in the same manner as described above, and an average value of 2 was obtained. In addition, when there is no maximum point in the range of tensile elongation rate of 10% or less, 0.2% proof stress is substituted.
The value obtained by subtracting the average value 2 from the average value 1 is divided by the average value 1, and the percentage value is A when it is less than 20%, and B when it is 20% or more and less than 30%, and 30%. C is the above case. Table 1 shows the results.

Examples 11-13 and Comparative Example 11
(Preparation 1A of photosensitive resin composition)
The photosensitive resin compositions of Examples 11 to 13 and Comparative Example 11 were prepared using the components and blending amounts shown in Table 2. The blending amounts in Table 1 are parts by mass of each component with respect to 100 parts by mass of A1.
The above-mentioned Example 1 and Example 11 have the same composition. The above-mentioned Example 2 and Example 12 have the same composition. Comparative Examples 1 and 11 described above have the same composition.
Each component used the above-mentioned thing.

(Production of pattern cured product 1A)
Using the photosensitive resin composition obtained in Preparation 1A of the photosensitive resin composition, pattern curing was performed in the same manner as in Production 1 of the patterned cured product, except that the temperature in the vertical diffusion furnace μ-TF was set to 175 ° C. A product (10 μm film thickness after curing) was produced.

(Chemical resistance evaluation 1A)
The film thickness of the patterned cured product obtained in Production 1A of the patterned cured product was measured. After that, the patterned cured product obtained in Production 1A of the patterned cured product was immersed in Dynastrip 7700 (manufactured by Dynaloy) heated to 70° C. for 30 minutes. After cooling, it was washed with distilled water and dried.

The film thickness of the pattern cured product after drying is measured, and the absolute value of "(film thickness before immersion in Dynastrip 7700) - (film thickness of pattern cured product after immersion in Dynastrip 7700, drying)" is the film thickness before immersion in Dynastrip 7700. The film thickness change rate was calculated by dividing and converting to percentage. The film thickness change rate was evaluated with A for a film thickness change rate of less than 15%, B for a film thickness change rate of 15% or more and less than 20%, and C for a film thickness change rate of 20% or more. . Table 2 shows the results.

In addition, the cured pattern after drying was observed with an optical microscope to measure the average spacing of 100 μm×100 μm grids. When the average spacing of the 100 μm×100 μm grid was 7.5 μm or more, it was rated A; when it was 6.5 μm or more and less than 7.5 μm, it was rated B; Table 2 shows the results.

(Production of patterned cured product 2A)
Using the photosensitive resin composition obtained in Preparation 1A of the photosensitive resin composition, pattern curing was performed in the same manner as in Production 2 of the patterned cured product, except that the temperature in the vertical diffusion furnace μ-TF was set to 175 ° C. A product (10 μm film thickness after curing) was produced.

(Evaluation of elongation rate)
The patterned cured product obtained in Production 2A of the patterned cured product was immersed in a 4.9 mass % hydrofluoric acid aqueous solution, and the cured product with a width of 10 mm was peeled off from the wafer.
A tensile test was performed on the peeled 10 mm wide cured product using Autograph AGS-X 100 N. The distance between chucks was 20 mm, the tensile speed was 5 mm/min, and the measurement temperature was 18 to 25°C. Six measurements were taken and averaged to obtain the elongation.
When the elongation rate was 45% or more, it was rated A, when it was 40% or more and less than 45%, it was rated B, and when it was less than 40%, it was rated C. Table 2 shows the results.

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

REFERENCE SIGNS LIST 1 semiconductor substrate 2 protective film 3 first conductor layer 4 interlayer insulating film 5 photosensitive resin layer 6A, 6B, 6C window 7 second conductor layer 8 surface protective film

Claims (13)

(A1) a polyimide precursor having a structural unit represented by the following formula (1),
(A2) a polyimide precursor having a structural unit represented by the following formula (1A);
(B) a polymerizable monomer,
(C) a photoinitiator, and
(D) A photosensitive resin composition containing a solvent.

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

(In Formula (2), R ₃ to R ₅ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and m is an integer of 1 to 10.)

(In formula (1A), X _1A is a tetravalent group having one or more aromatic groups, the -COOR _1A group and the -CONH- group are ortho to each other, and the -COOR _2A group and -CO - is ortho to each other Y _1A is a divalent aromatic group R _1A and R _2A are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms .) 2. The photosensitive resin composition according to claim 1, wherein the component (B) contains a polymerizable monomer having a group containing a polymerizable unsaturated double bond. 3. The photosensitive resin composition according to claim 2, wherein the number of groups containing polymerizable unsaturated double bonds is two or more. The photosensitive resin composition according to any one of claims 1 to 3, wherein the content of component (A2) is 5 to 55 parts by mass with respect to 100 parts by mass of component (A1). The photosensitive resin composition according to any one of claims 1 to 4, wherein the weight average molecular weight of component (A2) is 1.2 to 3.0 times the weight average molecular weight of component (A1). . The photosensitive resin composition according to any one of claims 1 to 5, wherein the weight average molecular weight of component (A2) is from 30,000 to 200,000. 7. The photosensitive resin composition according to any one of claims 1 to 6, further comprising (E) a thermal polymerization initiator. A step of applying the photosensitive resin composition according to any one of claims 1 to 7 on a substrate and drying it to form a photosensitive resin film;
a step of 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;
and a step of heat-treating the pattern resin film. 9. The method for producing a pattern-cured product according to claim 8, wherein the temperature of the heat treatment is 200[deg.] C. or less. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 7. The cured product according to claim 10, which is a pattern cured product. An interlayer insulating film, a cover coat layer, or a surface protective film produced using the cured product according to claim 10 or 11. An electronic component comprising the interlayer insulating film, cover coat layer or surface protective film according to claim 12 .

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