JP7091881B2 - Resin composition, method of manufacturing cured product, cured product, interlayer insulating film, cover coat layer, surface protective film and electronic components - Google Patents

Description

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

Conventionally, a resin composition containing polyimide or polybenzoxazole, which has excellent heat resistance, electrical properties, mechanical properties, etc., has been used as a surface protective film and an interlayer insulating film of a semiconductor device. In recent years, photosensitive resin compositions in which photosensitive properties are imparted to these resins themselves have been used, and by using this, the manufacturing process of a cured pattern can be simplified and complicated manufacturing processes can be shortened (for example, Patent Documents). 1).

Further, in order to achieve miniaturization and weight reduction of the semiconductor package, a semiconductor packaging technique called a wafer level chip size package in which terminals on the surface of the semiconductor element are rewired using a polyimide copper laminate has been developed.

In the production of wafer level chip size packages, low temperature curability is strongly required from the viewpoint of protecting high-performance dies and encapsulants with low heat resistance and improving yield (see, for example, Patent Document 2).

Further, in terms of heat resistance and reliability of the package, it is required that the polyimide and the copper wiring in the polyimide copper laminate do not peel off when exposed to high temperature conditions in the atmosphere.

Further, in order to improve the adhesiveness with copper when exposed to high temperature conditions, a positive photosensitive resin composition containing triazole or tetrazole, which is a compound having a heterocycle (see, for example, Patent Document 3), and A negative photosensitive resin composition containing a compound containing two or more alcoholic hydroxyl groups (see, for example, Patent Document 4) has been proposed.

Japanese Unexamined Patent Publication No. 2009-265520 International Publication No. 2008/11470 Japanese Unexamined Patent Publication No. 2010-96927 Japanese Unexamined Patent Publication No. 2016-167036

An object of the present invention is to produce a resin composition and a cured product capable of forming a cured product having excellent adhesion to copper even after low-temperature curing at 200 ° C. or lower, after forming the cured product, storing at high temperature, and reflowing. The present invention is to provide a method, a cured product, an interlayer insulating film, a cover coat layer, a surface protective film, and an electronic component.

As a method for evaluating the heat resistance and reliability of the package, the present inventors conducted a high temperature storage test (HTS (High Temperature Corrosion) Test) and a test reproducing the reflow process. As a result, in the conventional resin composition, the carboxy group was used. Found that there is a problem of copper corrosion due to. Further, the present inventors have found that the conventional resin composition has a reduced adhesiveness to copper after formation of a cured product, storage at a high temperature, or reflow treatment.

As a result of diligent studies in view of the above problems, the present inventors have combined a polyimide precursor and a specific component with the resin composition to form a cured product even at a low temperature of 200 ° C. or lower. The present invention was completed by finding that a cured product having excellent adhesiveness to copper can be formed after high temperature storage and reflow treatment.

（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。）
４．前記窒素原子を含む複素環構造が１，２，３－トリアゾール環構造である１～３のいずれかに記載の樹脂組成物。
５．前記（Ｂ）成分が１，２，３－ベンゾトリアゾール又は１，２，３－トリアゾールを含む１～４のいずれかに記載の樹脂組成物。
６．さらに、（Ｆ）酸化防止剤を含む１～５のいずれかに記載の樹脂組成物。
７．１～６のいずれに記載の樹脂組成物を基板上に塗布、乾燥して樹脂膜を形成する工程と、
前記樹脂膜を加熱処理する工程と、を含む硬化物の製造方法。
８．２～６のいずれかに記載の樹脂組成物を基板上に塗布、乾燥して樹脂膜を形成する工程と、
前記樹脂膜をパターン露光して、パターン露光後の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。
９．１～６のいずれに記載の樹脂組成物を硬化した硬化物。
１０．２～６のいずれに記載の樹脂組成物を硬化したパターン硬化物。
１１．９に記載の硬化物又は１０に記載のパターン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。
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 resin compositions and the like are provided.
1. 1. (A) Polyimide precursor,
(B) A compound containing a heterocyclic structure containing a nitrogen atom having a pka of 8.30 to 8.80, and (C) a resin composition containing 5-amino-1H-tetrazole.
2. 2. The resin composition according to 1, further comprising (D) a polymerizable monomer and (E) a photopolymerization initiator.
3. 3. The resin composition according to 1 or 2, wherein the component (A) is a polyimide precursor having a structural unit represented by the following formula (1).

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

(In the formula (2), R ₃ to R ₅ are independently hydrogen atoms or aliphatic hydrocarbon groups having 1 to 3 carbon atoms, and m is an integer of 1 to 10.)
4. The resin composition according to any one of 1 to 3, wherein the heterocyclic structure containing a nitrogen atom is a 1,2,3-triazole ring structure.
5. The resin composition according to any one of 1 to 4, wherein the component (B) contains 1,2,3-benzotriazole or 1,2,3-triazole.
6. The resin composition according to any one of 1 to 5, further comprising (F) an antioxidant.
A step of applying the resin composition according to any one of 7.1 to 6 onto a substrate and drying the resin composition to form a resin film.
A method for producing a cured product, which comprises a step of heat-treating the resin film.
A step of applying the resin composition according to any one of 8.2 to 6 onto a substrate and drying it to form a resin film.
A step of pattern-exposing the resin film to obtain a resin film after pattern exposure, and
A step of developing the resin film after the pattern exposure using an organic solvent to obtain a pattern resin film, and
A method for producing a cured pattern product, which comprises a step of heat-treating the pattern resin film.
A cured product obtained by curing the resin composition according to any one of 9.1 to 6.
A pattern cured product obtained by curing the resin composition according to any one of 10.2 to 6.
An interlayer insulating film, a cover coat layer or a surface protective film produced by using the cured product according to 11.9 or the pattern cured product according to 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 resin composition and a cured product capable of forming a cured product having excellent adhesiveness to copper can be produced even after low-temperature curing at 200 ° C. or lower, after formation of the cured product, storage at high temperature, and reflow treatment. Methods, cured products, interlayer insulating films, covercoat layers, surface protective films and electronic components can be provided.

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

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

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

The resin composition of the present invention has a (A) polyimide precursor (hereinafter, also referred to as “(A) component”) and (B) a heterocyclic structure containing a nitrogen atom having pka of 8.30 to 8.80. Contains a compound (hereinafter, also referred to as “component (B)”) and (C) 5-amino-1H-tetrazole (hereinafter, also referred to as “component (C)”).

This makes it possible to form a cured product having excellent adhesion (adhesion) to copper even after low-temperature curing at 200 ° C. or lower, after forming the cured product, after HTS, and after reflow treatment.
As an optional effect, due to its good adhesion to a copper substrate, it can be used in further low temperature treatment of semiconductor packaging expected in the future.
Further, as an arbitrary effect, a cured product having excellent rust resistance can be obtained.
Further, as an arbitrary effect, it is possible to form a cured product having excellent adhesiveness to one or more of any substrate (for example, a substrate described later) even if it is cured at a low temperature of 200 ° C. or lower.

Further, the resin composition of the present invention is further referred to as (D) polymerizable monomer (hereinafter, also referred to as “(D) component”) and (E) photopolymerization initiator (hereinafter, also referred to as “(E) component”). ) Is preferably included. Thereby, excellent photosensitive characteristics can be imparted.
When the component (D) and the component (E) are contained, the resin composition of the present invention is a photosensitive resin composition. Negative photosensitive resin compositions are preferred.

The component (A) is not particularly limited, but a polyimide precursor having high transmittance when i-ray is used as a light source during patterning and exhibiting high cured product characteristics even when cured at a low temperature of 200 ° C. or lower is preferable.

The component (A) preferably has a polymerizable unsaturated bond. Thereby, when the component (D) and the component (E) are contained, the photosensitive characteristics and the chemical resistance can be improved.
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). As a result, the i-ray transmittance is high, and a good cured product can be formed even when cured at a low temperature of 200 ° C. or lower.
The content of the structural unit represented by the formula (1) is preferably 50 mol% or more, more preferably 80 mol% or more, and 90 mol% or more with respect to all the constituent units of the component (A). More preferred. The upper limit is not particularly limited and may be 100 mol%.

（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。）

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

（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。）

(In the formula (2), R ₃ to R ₅ are independently hydrogen atoms or aliphatic hydrocarbon groups having 1 to 3 carbon atoms, and m is an integer of 1 to 10 (preferably an integer of 2 to 5). , More preferably 2 or 3))

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

As the aromatic hydrocarbon group of X1 of the formula ( ₁ ), a divalent to tetravalent (divalent, trivalent or tetravalent) group formed from a benzene ring and a divalent to tetravalent group formed from naphthalene. , A divalent to tetravalent group formed from perylene and the like.

（式（３）中、Ｚはエーテル基（－Ｏ－）又はスルフィド基（－Ｓ－）である。） Examples of the tetravalent group having one or more aromatic groups of X ₁ of the formula (1) include, but are not limited to, the tetravalent group of the following formula (3).

(In formula (3), Z is an ether group (-O-) or a sulfide group (-S-).)

In the formula (3), Z is preferably —O—.

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（４）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 of Y ₁ in the formula (1) include, but are not limited to, the group of the following formula (4).

(In the formula (4), R ₆ to R ₁₃ are monovalent organic groups each independently having a hydrogen atom, a monovalent aliphatic hydrocarbon group or a halogen atom.)

As the monovalent aliphatic hydrocarbon group of R ₆ to R ₁₃ of the formula (4) (preferably 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) of R ₆ to R ₁₃ of the formula (4) 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 to 6), and a trifluoromethyl group is more preferable.

Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms (preferably 1 or 2) of R ₁ and R ₂ of the formula (1) include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group and an n-. Examples include butyl groups.

It is preferable that at least one of R ₁ and R ₂ of the formula (1) is a group represented by the formula (2), and both are groups represented by the formula (2).

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

The polyimide precursor having the structural unit represented by the formula (1) is, for example, a tetracarboxylic acid dianhydride represented by the following formula (5) and a diamino compound represented by the following formula (6). -By reacting in an organic solvent such as methyl-2-pyrrolidone to obtain a polyamic acid, adding a compound represented by the following formula (7), and reacting in an organic solvent to partially introduce an ester group. Obtainable.
The tetracarboxylic acid dianhydride represented by the formula (5) and the diamino compound represented by the formula (6) may be used alone or in combination of two or more.

（式（５）中、Ｘ_１は式（１）のＸ_１に対応する基である。）

(In equation (5), X ₁ is a group corresponding to X ₁ in equation (1).)

（式（６）中、Ｙ_１は式（１）で定義した通りである。）

(In equation (6), Y ₁ is as defined in equation (1).)

（式（７）中、Ｒは上述の式（２）で表される基である。）

(In the formula (7), R is a group represented by the above formula (2).)

（式（１０）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 component (A) may have a structural unit other than the structural unit represented by the formula (1).
Examples of the structural unit other than the structural unit represented by the formula (1) include the structural unit represented by the following formula (10).

(In formula (10), X ₂ is a tetravalent group having one or more aromatic groups, and the -COOR ₅₁ group and the -CONH- group are in ortho positions with each other, and the -COOR ₅₂ group and the -CO group are located. -The groups are in ortho positions with each other. Y ₂ is a divalent aromatic group. R ₅₁ and R ₅₂ are independently hydrogen atoms or aliphatic hydrocarbon groups having 1 to 4 carbon atoms. )

Examples of the tetravalent group having one or more aromatic groups of X ₂ of the formula (10) include the same tetravalent groups having one or more aromatic groups of X ₁ of the formula (1).
Examples of the Y ₂ divalent aromatic group of the formula (10) include those similar to the Y ₁ divalent aromatic group of the formula (1).
Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms of R ₅₁ and R ₅₂ of the formula (10) are the same as those of the aliphatic hydrocarbon group having 1 to 4 carbon atoms of R ₁ and R ₂ .

As the structural unit other than the structural unit represented by the formula (1), one type may be used alone, or two or more types may be combined.

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

In the component (A), the ratio of the carboxy group esterified with the group represented by the formula (2) to the total carboxy group and the total carboxy ester is preferably 50 mol% or more, preferably 60 to 100. More preferably mol%, more preferably 70-100 mol%.

The molecular weight of the component (A) is not particularly limited, but the number average molecular weight is preferably 10,000 to 200,000.
The number average molecular weight is measured by gel permeation chromatography and converted using a standard polystyrene calibration curve.

The resin composition of the present invention contains the component (B). As a result, oxidation of the copper surface can be prevented, and the adhesiveness between the formed cured product and copper can be improved.

(B) The pka value of the component is ChEMBL: https: // www. Which is managed and operated by the European Bioinformatics Institute. ebi. ac. The value of uk / chembl / (May 10, 2018) is used.

Examples of the heterocyclic structure containing the nitrogen atom of the component (B) include a 1,2,3-triazole ring structure and a 1,2,3-benzotriazole ring structure.
From the viewpoint of adhesive strength, a 1,2,3-benzotriazole ring structure is preferable.
Further, from the viewpoint of pka, a 1,2,3-triazole ring structure is preferable.

The pKa of the component (B) is 8.30 to 8.80, but from the viewpoint of improving the Cu adhesiveness, it is preferably 8.32 to 8.78, and more preferably 8.35 to 8.75.

Specific examples of the component (B) include 1,2,3-triazole (pKa: 8.73), 1,2,3-benzotriazole (pKa: 8.38), 5-methyl-1,2, 3-benzotriazole (pKa: 8.55), 4-methyl-1,2,3-benzotriazole (pKa: 8.74), 4-phenyl-1,2,3-triazole (pKa: 8.40) , 2,4-Dihydrotriazole-1,2,3-triazole (pKa: 8.72), 4,9-dihydrotriazole-4,5-quinoline (pKa: 8.42) and the like. It is not limited to these.
The component (B) preferably contains 1,2,3-benzotriazole or 1,2,3-triazole from the viewpoint of solubility.

The component (B) may be used alone or in combination of two or more.

The content of the component (B) is preferably 0.5 to 5 parts by mass, more preferably 0.5 to 3.5 parts by mass, and even more preferably 1 to 2 parts by mass with respect to 100 parts by mass of the component (A). 5 parts by mass.
When it is within the above range, practical adhesiveness to copper wiring can be easily obtained.

When the resin composition of the present invention contains the component (D) and the component (E), the content of the component (B) is 100 parts by mass of the component (A) from the viewpoint of solubility in a developing solution. It is preferably 0.5 to 3.5 parts by mass, and more preferably 1 to 2.5 parts by mass.
When it is within the above range, practical adhesiveness to copper wiring can be easily obtained, and peeling of the exposed portion after development can be easily suppressed.

The content of the component (C) is preferably 0.5 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, and further preferably 0.5 to 0.5 parts by mass with respect to 100 parts by mass of the component (A). 2 parts by mass.
Within the above range, the stability of the resin composition tends to be good.

The ratio of the component (B) to the component (C) (component (B): component (C) (mass ratio)) is preferably 45 to 80:20 to 55, more preferably 50 to 70:30 to 50.
The total content of the component (B) and the component (C) is preferably 1 to 6 parts by mass, more preferably 2 to 4 parts by mass with respect to 100 parts by mass of the component (A).

The resin composition of the present invention may contain the component (D) from the viewpoint of improving the photosensitive characteristics when imparting photosensitivity.

The component (D) preferably has a group containing a polymerizable unsaturated double bond (preferably a (meth) acrylic group because it can be polymerized by the component (E) or the like). It is more preferable to have 2 to 4 groups containing polymerizable unsaturated double bonds in order to improve the crosslink density, improve the photosensitivity, and suppress the swelling of the pattern after development.

Specific examples of the component (D) include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and 1,4-butanediol dimethacrylate. Examples thereof include acrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, and 1,6-hexanediol dimethacrylate.

In addition, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, tetramethylolmethanetetra. Acrylate, Tetramethylolmethane Tetramethacrylate, Dipentaerythritol Hexaacrylate, Dipentaerythritol Hexamethacrylate, Pentaerythritol tetraacrylate ethoxylated, Isocyanuric acid triacrylate ethoxylated, Isocyanuric acid trimethacrylate ethoxylated, Acryloyloxyethyl isocyanurate, Methacryloyloxyethyl Isocyanurate and the like can be mentioned.

The component (D) may be used alone or in combination of two or more.

When the component (D) is contained, 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). From the viewpoint of the thermal characteristics of the cured product, it is more preferably 5 to 50 parts by mass, still more preferably 5 to 40 parts by mass.
When it is within the above range, it is easy to obtain a practical relief pattern, and it is easy to suppress the post-development residue of the unexposed portion.

The resin composition of the present invention may contain the component (E) from the viewpoint of improving the sensitivity when imparting photosensitivity.

The component (E) includes, for example,
Benzophenone derivatives such as benzophenone, methyl o-benzoyl benzoate, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, fluorenone, etc.
Acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenylketone, etc.
Thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, etc.
Benzyl derivatives such as benzyl, benzyldimethylketal, benzyl-β-methoxyethyl acetal, etc.
Benzoin derivatives such as benzoin and benzoin methyl ether, and 1-phenyl-1,2-butandion-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-diphenylpropanthrion -2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrion-2- (o-benzoyl) oxime, etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- Carbazole-3-yl]-, 1- (0-acetyloxime), oxime esters such as compounds represented by the following formulas are preferable, but the present invention is not limited thereto.

Oxime esters are particularly preferable in terms of light sensitivity.

The component (E) may be used alone or in combination of two or more.

When the component (E) is contained, the content of the component (E) is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (A). , More preferably 0.1 to 8 parts by mass.
Within the above range, the photocrosslinking tends to be uniform in the film thickness direction, and a practical relief pattern can be easily obtained.

The resin composition of the present invention may further contain (F) an antioxidant (hereinafter, also referred to as “(F) component”). By containing the component (F), oxygen radicals and peroxide radicals generated by high temperature storage or reflow treatment can be captured, and deterioration of adhesiveness (adhesion) can be further suppressed.

The components (F) include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, and octadecyl-3- (3,5-di-t-butyl-4). -Hydroxyphenyl) propionate, 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-thio-bis (3-methyl-6-t-butylphenol), 4,4' -Butylidene-bis (3-methyl-6-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylene Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide) ), Isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris [4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl] -1 , 3,5-Triazine-2,4,6- (1H, 3H, 5H) -trione, 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2,2'-methylene- Bis (4-ethyl-6-t-butylphenol),
Tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4) -Hydroxybenzyl) benzene, 1,3,5-tris (3-hydroxy-2,6-dimethyl-4-isopropylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) ) -Trione, 1,3,5-Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) ) -Trione, 1,3,5-Tris (4-s-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) ) -Trione, 1,3,5-Tris [4- (1-ethylpropyl) -3-hydroxy-2,6-dimethylbenzyl] -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trion, 1,3,5-tris (4-t-butyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -Trion,
Pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4) -Hydroxyphenyl) propionate], 1,3,5-tris (4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl) -1,3,5-triazine-2,4,6-( 1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4 , 6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine -2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl) -1,3 , 5-Triazine-2,4,6- (1H, 3H, 5H) -Trione, 1,3,5-Tris (4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl) -1 , 3,5-Triazine-2,4,6- (1H, 3H, 5H) -Torion,
1,3,5-Tris (4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H)- Trion, 1,3,5-tris (3-hydroxy-2,6-dimethyl-4-phenylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trion, And 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid and the like.

The component (F) may be used alone or in combination of two or more.

When the component (F) is contained, the content of the component (F) is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (A). , More preferably 0.1 to 5 parts by mass.

The resin composition of the present invention usually preferably contains a (G) solvent (hereinafter, also referred to as “(G) component”).
Examples of the solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, 3-methoxy-N, N-dimethylpropanamide (for example, trade name "KJCMPA-100", KJ Chemicals). (Manufactured by Co., Ltd.), organic solvents such as N-dimethylmorpholine and propylene glycol 1-monomethyl ether-2-acetate can be mentioned.
The solvent may be used alone or in combination of two or more.
The content of the solvent is not particularly limited, but is generally 50 to 1000 parts by mass with respect to 100 parts by mass of the component (A).

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

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

（式（８）中、Ｒ_１４及びＲ_１５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, the adhesiveness to the substrate can be further improved even when the curing is performed at a low temperature of 200 ° C. or lower.
The compound represented by the following formula (8) is more preferable because it is excellent in the development of adhesiveness when cured at a low temperature.

(In the formula (8), R ₁₄ and R ₁₅ are independently alkyl groups 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 (8) 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 adhesiveness of the cured product at low temperature curing to the substrate 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, and tert-. Benzene phenyl silane diol, diphenyl silane diol, ethyl methyl phenyl silanol, n-propyl methyl phenyl silanol, isopropyl methyl phenyl silanol, n-butyl methyl phenyl silanol, isobutyl methyl phenyl silanol, tert-butyl methyl phenyl silanol, ethyl n-propyl phenyl Cyranol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, Isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol, 1,4-bis (trihydroxysilyl) benzene, 1,4-bis (methyldihydroxysilyl) benzene, 1,4-bis (ethyldihydroxysilyl) benzene, 1,4-bis (propyldihydroxysilyl) benzene, 1,4-bis (butyldihydroxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, 1, Examples thereof include 4-bis (dipropylhydroxysilyl) benzene, 1,4-bis (dibutylhydroxysilyl) benzene, and a compound represented by the following formula (9). Of these, the compound represented by the formula (9) is particularly preferable in order to further improve the adhesiveness to the substrate.

（式（９）中、Ｒ_１６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_１７及びＲ_１８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 (9), R ₁₆ is a monovalent organic group having a hydroxy group or a glycidyl group, and R ₁₇ and R ₁₈ are independently alkyl groups having 1 to 5 carbon atoms, and c is 1 to 10 each. And d is an integer of 1 to 3.)

Examples of the compound represented by the formula (9) include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, and 3-. Hydropylpropyltriethoxysilane, 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2- Glycydoxyethyl triethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybutyltriethoxysilane, etc. Be done.

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

Further, as a silane coupling agent having an amide bond, R _19- (CH ₂ ) _e -CO-NH- (CH ₂ ) _f -Si (OR ₂₀ ) ₃ (R ₁₉ is a hydroxy group or a glycidyl group, and e And f are independently integers of 1 to 3, and _R20 is a compound represented by a methyl group, an ethyl group or a propyl group).

The silane coupling agent may be used alone or in combination of two or more.

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 the component (A). Up to 10 parts by mass is more preferable.

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

Examples of the surfactant or leveling agent include polyoxyethylene uralyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether and the like, and commercial products include the trade name "Megafax". F171 "," F173 "," R-08 "(above, manufactured by DIC Co., Ltd.), product name" Florard FC430 "," FC431 "(above, manufactured by Sumitomo 3M Co., Ltd.), product name" Organosiloxane Polymer KP341 "(above, manufactured by Sumitomo 3M Co., Ltd.) As mentioned above, (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and the like.

The surfactant and the leveling agent may be used alone or in combination of two or more.

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

By containing a polymerization inhibitor, good storage stability can be ensured.
Examples of the polymerization inhibitor include a radical polymerization inhibitor, a radical polymerization inhibitor and the like.

Examples of the polymerization inhibitor include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, and N-phenyl-2-. Examples thereof include naphthylamine, cuperon, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosoamines and the like.

The polymerization inhibitor may be used alone or in combination of two or more.

When a polymerization inhibitor is contained, the content of the polymerization inhibitor is 0.01 with respect to 100 parts by mass of the component (A) from the viewpoint of storage stability of the resin composition and heat resistance of the obtained cured product. It is preferably from 30 parts by mass, more preferably 0.01 to 10 parts by mass, still more preferably 0.05 to 5 parts by mass.

The resin composition of the present invention essentially contains components (A) to (C), and optionally components (D) to (F), a coupling agent, a surfactant, a leveling agent, and a leveling agent, except for a solvent. It is composed of a polymerization inhibitor and may contain other unavoidable impurities as long as the effect of the present invention is not impaired.
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 of the resin composition of the present invention excludes the solvent.
Ingredients (A) to (C),
Components (A) to (C), and optionally components (D) to (F), coupling agents, surfactants, leveling agents, and polymerization inhibitors,
Ingredients (A) to (E),
Components (A) to (E), and optionally (F) components, coupling agents, surfactants, leveling agents, and polymerization inhibitors,
It may consist of the components (A) to (F), or the components (A) to (F), and optionally a coupling agent, a surfactant, a leveling agent, and a polymerization inhibitor.

The cured product of the present invention can be obtained by curing the above-mentioned resin composition.
The cured product of the present invention may be used as a patterned cured product or as a cured product without a pattern.
The film thickness of the cured product of the present invention is preferably 5 to 30 μm.

The method for producing a cured product of the present invention includes a step of applying the above-mentioned resin composition on a substrate and drying it to form a resin film, and a step of heat-treating the resin film. Further, it may be provided with a step of exposing (for example, without a pattern).
Thereby, the cured product of the present invention can be obtained.

In the method for producing a cured pattern of the present invention, the above-mentioned resin composition (preferably further containing the component (D) and the component (E)) is applied onto a substrate and dried to form a resin film. , The step of pattern-exposing the resin film to obtain the resin film after pattern exposure, the step of developing the resin film after pattern exposure with an organic solvent to obtain the pattern resin film, and the step of heating the pattern resin film. Including the process of processing.
Thereby, a pattern cured product can be obtained.

As a board,
Glass substrate,
Semiconductor substrates such as silicon carbide substrates, lithium tantalate substrates, lithium niobate substrates, and Si substrates (silicon wafers),
Metal oxide insulator substrate such as TiO ₂ substrate, SiO ₂ substrate, etc.
Examples thereof include Cu-plated wafers, silicon nitride substrates, aluminum substrates, copper substrates, and copper alloy substrates.

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

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

The pattern exposure exposes a predetermined pattern through, for example, a photomask.
The exposure performed without a pattern is performed without using, for example, a photomask.
Examples of the active light beam to be irradiated include broadband light (wavelength 350 to 450 nm), 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, a proximity exposure machine and the like can be used.

By developing, a patterned resin film (patterned resin film) can be obtained. Generally, when a negative photosensitive resin composition is used, the unexposed portion is removed with a developing solution.
As the developing solution, the organic solvent used as the developing solution may be a good solvent of the resin film alone or a mixture of a good solvent and a poor solvent as appropriate.
Good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, gamma-butyrolactone, α-acetyl-gamma-butyrolactone, cyclopentanone. Non, cyclohexanone and the like can be mentioned.
Examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, water and the like.

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 with respect to 100 parts by mass of the developing solution.

The development time can be, for example, twice the time required for the resin film to be immersed and completely dissolved.
The developing time varies depending on the component (A) used, but is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and even more preferably 20 seconds to 5 minutes from the viewpoint of productivity.

After development, it may be washed with a rinsing solution.
As the rinsing solution, distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and the like may be used alone or in an appropriate mixture, or may be used in a stepwise combination. good.

A cured pattern can be obtained by heat-treating the pattern resin film.
Further, a cured product can be obtained by heat-treating the resin film.
The polyimide precursor of the component (A) may undergo a dehydration ring closure reaction by a heat treatment step to become a corresponding polyimide.

The temperature of the heat treatment is preferably 250 ° C. or lower, more preferably 120 to 250 ° C., and even more preferably 200 ° C. or lower or 150 to 200 ° C.
Within the above range, damage to the substrate or the device can be suppressed to a small extent, the device can be produced at 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.
Within the above range, the cross-linking reaction or the dehydration ring closure reaction can be sufficiently proceeded.
The atmosphere of the heat treatment may be in the atmosphere or in an inert atmosphere such as nitrogen, but a nitrogen atmosphere is preferable from the viewpoint of preventing oxidation of the resin film or the pattern resin film.

Examples of the apparatus used for the heat treatment include a quartz tube furnace, a hot plate, a rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, a microwave curing furnace 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 protective film, or the like.
A highly reliable semiconductor device, multilayer wiring board, various electronic devices, etc. can be used by using one or more selected from the group consisting of the passion film, the buffer coat film, the interlayer insulating film, the cover coat layer, the surface protective film, and the like. It is possible to manufacture electronic parts and the like.

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

Next, a photosensitive resin layer 5 such as a rubber chloride type or a phenol novolac type is formed on the interlayer insulating film 4, and the window 6A is provided so that the interlayer insulating film 4 in a predetermined portion is exposed by a known photographic etching technique. It will be provided.

The interlayer insulating film 4 in which the window 6A is exposed is selectively etched to provide the window 6B.
Next, the photosensitive resin layer 5 is completely removed by 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 photographic etching technique, the second conductor layer 7 is formed and electrically connected to the first conductor layer 3.
When forming a multi-layer wiring structure having three or more layers, the above steps can be repeated to form each layer.

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

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

Synthesis Example 1 (Synthesis of A1)
7.07 g of 3,3', 4,4'-diphenyl ether tetracarboxylic acid dianhydride (ODPA) and 4.12 g of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) N-methyl- It was dissolved in 30 g of 2-pyrrolidone (NMP) and stirred at 30 ° C. for 4 hours and then at room temperature overnight to obtain polyamic acid. To this, 9.45 g of trifluoroacetic anhydride was added under water cooling, the mixture was stirred at 45 ° C. for 3 hours, and 7.08 g of 2-hydroxyethyl methacrylate (HEMA) was added. This reaction solution was added dropwise to distilled water, the precipitate was collected by filtration, and dried under reduced pressure to obtain a polyimide precursor A1.
Using the gel permeation chromatograph (GPC) method, the number average molecular weight was determined under the following conditions by standard polystyrene conversion. The number average molecular weight of A1 was 40,000.

The measurement was carried out using a solution of 1 mL of a 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.
C-R4A Chromatopac manufactured by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5 x 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: UV270 nm

Further, the esterification rate of A1 (reaction rate of the carboxy group of ODPA with HEMA) was calculated by performing NMR measurement under the following conditions. The esterification rate was 80 mol% with respect to the total carboxy group of the polyamic acid (the remaining 20 mol% was a carboxy group).

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

Examples 1 to 7 and Comparative Examples 1 to 5
(Preparation of resin composition)
The resin compositions of Examples 1 to 7 and Comparative Examples 1 to 5 were prepared with the components and blending amounts shown in Table 1. The blending amount in Table 1 is the mass part of each component with respect to 100 parts by mass of A1. In Table 1, the numerical values in parentheses after B1 to B5 represent each pKa.

Each component used is as follows. As the component (A), A1 obtained in Synthesis Example 1 was used.

(B) Ingredient B1: 1,2,3-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
B2: 1,2,3-triazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

(B') Ingredient B3: 3-Aminotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
B4: Tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
B5: 5-Phenyltetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

(C) Ingredient C1: 5-amino-1H-tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

(D) Component: Polymerizable monomer D1: TEGDMA (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., tetraethylene glycol dimethacrylate)

(E) Ingredient: Photopolymerization Initiator E1: G-1820 (PDO) (1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime manufactured by Rambuson)

(F) Component F1: Sianox CY-1790 (manufactured by Sun Chemical Co., Ltd., compound represented by the following formula)

(G) Ingredient G1: γ-Butyrolactone (manufactured by Wako Pure Chemical Industries, Ltd.)
G2: KJCMPA-100 (manufactured by KJ Chemicals Co., Ltd., 3-methoxy-N, N-dimethylpropanamide)

(Value of pKa)
The pka values of B1 to B5 are managed and operated by the European Bioinformatics Institute. ChEMBL: https: // www. ebi. ac. The value of uk / chembl / (May 10, 2018) was used.

(Preparation of cured product)
The above resin composition is spin-coated on a Cu-plated wafer (Si wafer having a thickness of 10 μm formed by Cu plating) using an coating device Act8 (manufactured by Tokyo Electron Co., Ltd.), dried at 100 ° C. for 2 minutes, and then dried. , It was dried at 110 ° C. for 2 minutes to form a resin film.
The obtained resin film was exposed to 500 mJ / cm ² using a proximity exposure machine MA8 (mask aligner manufactured by Susu Microtech, broadband light: wavelength 350 to 450 nm).
The exposed resin film was heated at 175 ° C. for 2 hours in a nitrogen atmosphere using a vertical diffusion furnace μ-TF (manufactured by Koyo Thermo System Co., Ltd.) to obtain a cured product (thickness after curing 10 μm). ..

(Adhesion test 1)
The adhesive properties of the cured product to the Cu-plated wafer were evaluated based on the following criteria according to the cross-cut method of JIS K 5600-5-6 standard for the cured product obtained by producing the cured product. Specifically, among the 10 × 10 lattices, the number of lattices of the cured product adhered to the Cu-plated wafer was evaluated. The results are shown in Table 1.
"A": The number of lattices of the cured product adhered to the Cu-plated wafer is 100.
"B": The number of lattices of the cured product adhered to the Cu-plated wafer is 80 to 99.
"C": Number of lattices of the cured product adhered to the Cu-plated wafer is 50 to 79.
"D": Number of lattices of the cured product adhered to the Cu-plated wafer is 20 to 49.
"E": The number of lattices of the cured product adhered to the Cu-plated wafer is less than 20.

(After adhesiveness test 2 HTS)
The cured product obtained by producing the above cured product was placed in a clean oven DT-41 (manufactured by Yamato Kagaku Co., Ltd.), stored at a temperature of 175 ° C. for 100 hours, and then taken out for a high temperature storage test (HTS (HTS). A Cu-plated wafer with a cured product for High Temperature Story) Test) was obtained.
With respect to the obtained Cu-plated wafer with a cured product for HTS Test, the adhesive properties of the cured product were evaluated in the same manner as in the adhesiveness test 1. The results are shown in Table 1.

(Adhesive test 3 after reflow processing)
Using the reflow furnace device compact N2 reflow system TNP25-337EM (manufactured by Tamura Corporation), the cured product obtained by producing the above cured product can be heated to a temperature of 260 ° C at a heating rate of 80 ° C / min in an air atmosphere. The temperature was raised and heat treatment was performed at 260 ° C. for 30 seconds. Then, the wafer was taken out when the temperature became 50 ° C. or lower. The process from the temperature rise to the removal was set as one cycle, and by performing this step for 10 cycles, a Cu-plated wafer with a cured product was obtained by performing the reflow process for 10 cycles.
The adhesive properties of the cured product of the obtained Cu-plated wafer with a cured product that had undergone 10 cycles of reflow treatment were evaluated in the same manner as in the adhesiveness test 1. The results are shown in Table 1.

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

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) Polyimide precursor,
(B) A compound containing a 1,2,3-triazole ring structure having a pka of 8.30 to 8.80, and (C) a resin composition containing 5-amino-1H-tetrazole. The resin composition according to claim 1, further comprising (D) a polymerizable monomer and (E) a photopolymerization initiator. The resin composition according to claim 1 or 2, wherein the component (A) is a polyimide precursor having a structural unit represented by the following formula (1).

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

(In the formula (2), R ₃ to R ₅ are independently hydrogen atoms or aliphatic hydrocarbon groups having 1 to 3 carbon atoms, and m is an integer of 1 to 10.) The component (B) is 1,2,3-triazole, 1,2,3-benzotriazole, 5-methyl-1,2,3-benzotriazole, 4-methyl-1,2,3-benzotriazole, 4 The resin composition according to any one of claims 1 to 3, which comprises phenyl-1,2,3-triazole or 2,4-dihydroindeno-1,2,3-triazole . The resin composition according to any one of claims 1 to 4, wherein the component (B) contains 1,2,3-benzotriazole or 1,2,3-triazole. The resin composition according to any one of claims 1 to 5, further comprising (F) an antioxidant. A step of applying the resin composition according to any one of claims 1 to 6 onto a substrate and drying the resin composition to form a resin film.
A method for producing a cured product, which comprises a step of heat-treating the resin film. A step of applying the resin composition according to any one of claims 2 to 6 onto a substrate and drying the resin composition to form a resin film.
A step of pattern-exposing the resin film to obtain a resin film after pattern exposure, and
A step of developing the resin film after the pattern exposure using an organic solvent to obtain a pattern resin film, and
A method for producing a cured pattern product, which comprises a step of heat-treating the pattern resin film. A cured product obtained by curing the resin composition according to any one of claims 1 to 6. A pattern cured product obtained by curing the resin composition according to any one of claims 2 to 6. An interlayer insulating film, a cover coat layer or a surface protective film produced by using the cured product according to claim 9 or the pattern cured product according to claim 10. An electronic component including the interlayer insulating film, cover coat layer or surface protective film according to claim 11.

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