JP7238316B2 - 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 References 2-4).

JP 2009-265520 A WO2008/111470 JP 2016-199662 A WO2015/052885

An object of the present invention is to provide a photosensitive resin composition that can form a cured product with excellent resolution even when cured at a low temperature of 200 ° C. or less and can suppress discoloration of copper, a method for producing a pattern cured product, and a cured product. , an interlayer insulating film, a cover coat layer, a surface protective film and an electronic component.

Electronic devices are required to be miniaturized and highly integrated. The inventors of the present invention have found that there is a problem of increasing the resolution of a patterned cured film formed by heating and curing a patterned resin film.
In addition, it was found that oxidation and discoloration of the copper wiring were problems.

In view of the above problems, the present inventors have made repeated studies and found that by using a combination of specific components in a photosensitive resin composition, it is possible to form a cured product of a pattern cured film with excellent resolution, and copper The inventors have found that the discoloration can be suppressed, and have completed the present invention.

（式（１０１）～（１０７）中、
Ｒ_１０１～Ｒ_１１０は、それぞれ独立に水素原子、炭素数１～３の脂肪族炭化水素基、炭素数１～３のアルコキシ基、又はヒドロキシ基であり、
Ｒ_１０１～Ｒ_１０５のうち少なくとも１つはヒドロキシ基であり、Ｒ_１０６～Ｒ_１１０のうち少なくとも１つはヒドロキシ基であり、
Ｒ_１１１～Ｒ_１１４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、
Ｒ_１１５は、２価の基、又は単結合であり、
Ｒ_１２１、Ｒ_１３１、Ｒ_１４１、Ｒ_１５１～Ｒ_１５４、Ｒ_１６１、Ｒ_１６２、Ｒ_１７１及びＲ_１７２は、それぞれ独立に、水素原子、炭素数１～３の脂肪族炭化水素基、炭素数１～３のアルコキシ基、又は、ヒドロキシ基である。）
２．前記（Ａ）成分が、下記式（１）で表される構造単位を有するポリイミド前駆体である１に記載の感光性樹脂組成物。

（式（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１以上の芳香族基を有する２価の基である。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。）
３．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又は２に記載の感光性樹脂組成物。
４．前記重合性の不飽和二重結合を含む基が、２以上である３に記載の感光性樹脂組成物。
５．前記重合性モノマーが、脂肪族環状骨格を有する１～４のいずれかに記載の感光性樹脂組成物。
６．前記（Ｂ）成分が、下記式（３）で表される重合性モノマーを含む１～３のいずれかに記載の感光性樹脂組成物。

（式（３）中、Ｒ_６及びＲ_７は、それぞれ独立に、炭素数１～４の脂肪族炭化水素基又は下記式（４）で表される基である。ｎ１は０又は１であり、ｎ２は０～２の整数であり、ｎ１＋ｎ２は１以上である。ｎ１個のＲ_６及びｎ２個のＲ_７の少なくとも１つは、下記式（４）で表される基である。）

（式（４）中、Ｒ_９～Ｒ_１１は、それぞれ独立に、水素原子又は炭素数１～３の脂肪族炭化水素基であり、ｌは０～１０の整数である。）
７．ｎ１＋ｎ２が、２又は３である６に記載の感光性樹脂組成物。
８．前記（Ｂ）成分が、下記式（５）で表される重合性モノマーを含む１～７のいずれかに記載の感光性樹脂組成物。

９．前記（Ｄ）成分が、前記式（１０１）で表される化合物である１～８のいずれかに記載の感光性樹脂組成物。
１０．Ｒ_１１５がメチレン基である９に記載の感光性樹脂組成物。
１１．前記（Ｄ）成分が、下記式（１０１Ａ）で表される化合物である１～１０のいずれかに記載の感光性樹脂組成物。

（式（１０１Ａ）中、Ｒ_１０２Ａ及びＲ_１０７Ａは、それぞれ独立に、水素原子、又はメトキシ基である。）
１２．さらに、（Ｉ）熱重合開始剤を含む１～１１のいずれかに記載の感光性樹脂組成物。
１３．１～１２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。
１４．前記加熱処理の温度が２００℃以下である１３に記載のパターン硬化物の製造方法。
１５．１～１２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。
１６．パターン硬化物である１５に記載の硬化物。
１７．１５又は１６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。
１８．１７に記載の層間絶縁膜、カバーコート層又は表面保護膜を含む電子部品。 According to the present invention, the following photosensitive resin composition and the like are provided.
1. (A) a polyimide precursor having a polymerizable unsaturated bond,
(B) a polymerizable monomer,
(C) a photopolymerization initiator, and (D) a photosensitive resin composition containing compounds represented by the following formulas (101) to (107).

(In formulas (101) to (107),
R ₁₀₁ to R ₁₁₀ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a hydroxy group;
at least one of R ₁₀₁ to R ₁₀₅ is a hydroxy group and at least one of R ₁₀₆ to R ₁₁₀ is a hydroxy group;
R ₁₁₁ to R ₁₁₄ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms,
R ₁₁₅ is a divalent group or a single bond,
R ₁₂₁ , R ₁₃₁ , R ₁₄₁ , R ₁₅₁ to R ₁₅₄ , R ₁₆₁ , R ₁₆₂ , R ₁₇₁ and R ₁₇₂ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, or 1 1 to 3 alkoxy groups or hydroxy groups. )
2. 2. The photosensitive resin composition according to 1, wherein the component (A) is a polyimide precursor having a structural unit represented by the following formula (1).

(In 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 - groups are ortho positions to each other, Y ₁ is a divalent group having one or more aromatic groups, R ₁ and R ₂ are each independently a hydrogen atom, represented by the following formula (2): or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, 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.)
3. 3. The photosensitive resin composition according to 1 or 2, wherein the component (B) contains a polymerizable monomer having a group containing a polymerizable unsaturated double bond.
4. 4. The photosensitive resin composition according to 3, wherein the number of groups containing polymerizable unsaturated double bonds is 2 or more.
5. 5. The photosensitive resin composition according to any one of 1 to 4, wherein the polymerizable monomer has an aliphatic cyclic skeleton.
6. 4. The photosensitive resin composition according to any one of 1 to 3, wherein the component (B) contains a polymerizable monomer represented by the following formula (3).

(In formula (3), R ₆ and R ₇ are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following formula (4); n1 is 0 or 1; , n2 is an integer of 0 to 2, and n1+n2 is 1 or more.At least one of n1 R ₆ and n2 R ₇ is a group represented by the following formula (4).)

(In Formula (4), R ₉ to R ₁₁ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and l is an integer of 0 to 10.)
7. 7. The photosensitive resin composition according to 6, wherein n1+n2 is 2 or 3.
8. 8. The photosensitive resin composition according to any one of 1 to 7, wherein the component (B) contains a polymerizable monomer represented by the following formula (5).

9. 9. The photosensitive resin composition according to any one of 1 to 8, wherein the component (D) is a compound represented by the formula (101).
10. 9. The photosensitive resin composition according to 9, wherein _R115 is a methylene group.
11. 11. The photosensitive resin composition according to any one of 1 to 10, wherein the component (D) is a compound represented by the following formula (101A).

(In formula (101A), R _102A and R _107A are each independently a hydrogen atom or a methoxy group.)
12. 12. The photosensitive resin composition according to any one of 1 to 11, further comprising (I) a thermal polymerization initiator.
13. A step of applying the photosensitive resin composition according to any one of 1 to 12 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.
14. 14. The method for producing a patterned cured product according to 13, wherein the temperature of the heat treatment is 200° C. or less.
15. A cured product obtained by curing the photosensitive resin composition according to any one of 1 to 12.
16. 16. The cured product according to 15, which is a pattern cured product.
17. An interlayer insulating film, a cover coat layer or a surface protective film produced using the cured product according to 15 or 16.
18. An electronic component comprising the interlayer insulating film, cover coat layer or surface protective film according to 17.

According to the present invention, a photosensitive resin composition capable of forming a cured product with excellent resolution even when cured at a low temperature of 200 ° C. or less and suppressing discoloration of copper, a method for producing a pattern cured product, and a cured product , an interlayer insulating film, a cover coat layer, a surface protective film, and an electronic component.

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（１０１）～（１０７）中、
Ｒ_１０１～Ｒ_１１０は、それぞれ独立に水素原子、炭素数１～３の脂肪族炭化水素基、炭素数１～３のアルコキシ基、又はヒドロキシ基であり、
Ｒ_１０１～Ｒ_１０５のうち少なくとも１つ（式（１０２）～（１０６）においては、Ｒ_１０１～Ｒ_１０４のうち少なくとも１つ）はヒドロキシ基であり、Ｒ_１０６～Ｒ_１１０のうち少なくとも１つはヒドロキシ基であり、
Ｒ_１１１～Ｒ_１１４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、
Ｒ_１１５は、２価の基、又は単結合であり、
Ｒ_１２１、Ｒ_１３１、Ｒ_１４１、Ｒ_１５１～Ｒ_１５４、Ｒ_１６１、Ｒ_１６２、Ｒ_１７１及びＲ_１７２は、それぞれ独立に、水素原子、炭素数１～３の脂肪族炭化水素基、炭素数１～３のアルコキシ基、又は、ヒドロキシ基である。） The photosensitive resin composition of the present invention includes (A) a polyimide precursor having a polymerizable unsaturated bond (hereinafter also referred to as "(A) component"), (B) a polymerizable monomer (hereinafter, "(B ) component”.), (C) a photopolymerization initiator (hereinafter also referred to as “(C) component”), and (D) a group consisting of compounds represented by the following formulas (101) to (107) Contains one or more compounds selected from (hereinafter also referred to as "(D) component").

(In formulas (101) to (107),
R ₁₀₁ to R ₁₁₀ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a hydroxy group;
At least one of R ₁₀₁ to R ₁₀₅ (at least one of R ₁₀₁ to R ₁₀₄ in formulas (102) to (106)) is a hydroxy group, and at least one of R ₁₀₆ to R ₁₁₀ is is a hydroxy group,
R ₁₁₁ to R ₁₁₄ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms,
R ₁₁₅ is a divalent group or a single bond,
R ₁₂₁ , R ₁₃₁ , R ₁₄₁ , R ₁₅₁ to R ₁₅₄ , R ₁₆₁ , R ₁₆₂ , R ₁₇₁ and R ₁₇₂ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, or 1 1 to 3 alkoxy groups or hydroxy groups. )

As a result, even when curing is performed at a low temperature of 200° C. or less, a cured product with excellent resolution can be formed, and discoloration of copper can be suppressed.

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

Component (A) is not particularly limited, but is preferably a polyimide precursor that exhibits high transmittance when i-line is used as a light source during patterning and exhibits high cured product properties even when cured at a low temperature of 200° C. or less.

Examples of polymerizable unsaturated bonds include carbon-carbon double bonds.

Component (A) is preferably a polyimide precursor having a structural unit represented by the following formula (1). As a result, the transmittance of the i-line is high, and a good cured product can be formed 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 more preferably 90 mol% or more, relative to all structural units of 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１以上の芳香族基を有する２価の基である。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（好ましくは１又は２）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, the -COOR ₁ group and the -CONH- group are ortho to each other, and the -COOR ₂ group and the -CO - groups are ortho positions to each other, Y ₁ is a divalent group having one or more aromatic groups, R ₁ and R ₂ are each independently a hydrogen atom, represented by the following formula (2): or an aliphatic hydrocarbon group having 1 to 4 (preferably 1 or 2) carbon atoms, and at least one of R ₁ and R ₂ is a group represented by the 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 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 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.

In the divalent group having one or more (preferably 1 to 3, more preferably 1 or 2) aromatic groups for Y 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 Y ₁ in formula (1) includes a divalent to tetravalent group formed from a benzene ring, a divalent to tetravalent group formed from naphthalene, and a divalent to tetravalent group formed from perylene. and the like.

The divalent group having one or more aromatic groups for Y ₁ of formula (1) includes, for example, a divalent group in which two aromatic groups are bonded via an ether group (—O—). , but not limited to.

（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 group having one or more aromatic groups for Y ₁ of 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１以上の芳香族基を有する２価の基である。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 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 group having one or more aromatic groups, and R ₅₁ and R ₅₂ are each independently a hydrogen atom or an aliphatic group having 1 to 4 carbon atoms. It is a hydrocarbon group.)

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 group having one or more aromatic groups for Y ₂ in formula (11) include the same divalent groups as the divalent groups having one or more 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 % of all structural units of component (A).

In component (A), 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 to 100 mol % is more preferred, and 70 to 90 mol % is even more preferred.

The molecular weight of component (A) is not particularly limited, but the weight average molecular weight is preferably from 10,000 to 200,000.
The weight average molecular weight can be measured, for example, by gel permeation chromatography, and can be obtained by conversion using a standard polystyrene calibration curve.

The photosensitive resin composition of the present invention contains (B) a polymerizable monomer. Thereby, the heat resistance, mechanical properties and chemical resistance of the cured product to be formed can be improved.

Component (B) is a group containing (preferably two or more) polymerizable unsaturated double bonds (preferably polymerizable by a photopolymerization initiator, from the viewpoint of improving the crosslink density with component (A). Therefore, it is preferable to contain a polymerizable monomer having a (meth)acrylic group.

The polymerizable monomer preferably has an aliphatic cyclic skeleton (preferably 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms). This makes it possible to impart hydrophobicity to the cured product that can be formed, and to suppress deterioration in adhesiveness between the cured product and the substrate under high temperature and high humidity conditions.

The polymerizable monomer preferably has 2 or 3 groups containing polymerizable unsaturated double bonds in order to improve crosslink density and photosensitivity and suppress swelling of the pattern after development.

（式（３）中、Ｒ_６及びＲ_７は、それぞれ独立に、炭素数１～４の脂肪族炭化水素基又は下記式（４）で表される基である。ｎ１は０又は１であり、ｎ２は０～２の整数であり、ｎ１＋ｎ２は１以上（好ましくは２又は３）である。ｎ１個のＲ_６及びｎ２個のＲ_７の少なくとも１つ（好ましくは２又は３）は、下記式（４）で表される基である。） (B) Component preferably contains a polymerizable monomer represented by the following formula (3).

(In formula (3), R ₆ and R ₇ are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following formula (4); n1 is 0 or 1; , n2 is an integer of 0 to 2, and n1+n2 is 1 or more (preferably 2 or 3).At least one of n1 R ₆ and n2 R ₇ (preferably 2 or 3) is the following It is a group represented by formula (4).)

When there are two _R7 's, the two R7 _'s may be the same or different.

（式（４）中、Ｒ_９～Ｒ_１１は、それぞれ独立に、水素原子又は炭素数１～３の脂肪族炭化水素基であり、ｌは０～１０の整数（好ましくは０、１又は２）である。）

(In formula (4), R ₉ to R ₁₁ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, l is an integer of 0 to 10 (preferably 0, 1 or 2 ).)

Component (B) more preferably contains a polymerizable monomer represented by the following formula (5).

Moreover, as the component (B), for example, the following polymerizable monomers may be used.

式（１２）中、Ｒ_２１～Ｒ_２４は、それぞれ独立に、炭素数１～４の脂肪族炭化水素基又は上記式（４）で表される基である。ｎ３は１～３の整数（好ましくは２又は３）である。ｎ４は１～３の整数（好ましくは２又は３）である。ｎ５は０又は１であり、ｎ６は０又は１である。ｎ５＋ｎ６は１以上（好ましくは２）である。

In formula (12), R ₂₁ to R ₂₄ are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by formula (4) above. n3 is an integer of 1 to 3 (preferably 2 or 3). n4 is an integer of 1 to 3 (preferably 2 or 3). n5 is 0 or 1 and n6 is 0 or 1. n5+n6 is 1 or more (preferably 2).

When two or more R ₂₁ are present, the two or more R ₂₁ may be the same or different.
When two or more R ₂₂ are present, the two or more R ₂₂ may be the same or different.

At least one (preferably 2 or 3) of n3 R ₂₁ is a group represented by the above formula (4).
At least one (preferably 2 or 3) of n4 R ₂₂ is a group represented by the above formula (4).
At least one (preferably 2) of n5 R ₂₃ and n6 R ₂₄ is a group represented by the above formula (4).

Aliphatic hydrocarbon groups having 1 to 4 carbon atoms for R ₆ and R ₇ in formula (3) and R ₂₁ to R ₂₄ in formula (12) include 1 carbon atom for R ₁ and R ₂ in formula (1). The same as the aliphatic hydrocarbon groups of 1 to 4 can be mentioned.

The aliphatic hydrocarbon groups having 1 to 3 carbon atoms for R ₉ to R ₁₁ in formula (4) are the same as the aliphatic hydrocarbon groups having 1 to 3 carbon atoms for R ₃ to R ₅ in formula (2). things are mentioned.

As the component (B), polymerizable monomers other than polymerizable monomers having an aliphatic cyclic skeleton may be used. Polymerizable monomers other than polymerizable monomers having an aliphatic cyclic skeleton include 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 and the like.
Also, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate,
Tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tetrakisacrylate methanetetrayltetrakis(methyleneoxyethylene), ethoxylated isocyanuric acid triacrylate, ethoxylated isocyanuric acid trimethacrylate , acryloyloxyethyl isocyanurate, methacryloyloxyethyl isocyanurate, and the like.

Among them, tetraethylene glycol dimethacrylate, pentaerythritol tetraacrylate, and tetrakis methanetetrayl tetrakis(methyleneoxyethylene) acrylate 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 (A). From the viewpoint of improving the hydrophobicity of the cured product, it is more preferably 3 to 50 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 post-development residues in unexposed areas.

Component (C) includes, for example, benzophenone, methyl 2-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.

Component (C) is (C1) one or more compounds selected from the group consisting of compounds represented by the following formula (15-1) and compounds represented by the following formula (15-2) (hereinafter, "( (also referred to as "C1) component").
Component (C1) preferably has higher sensitivity to actinic rays than component (C2), which will be described later, and is preferably a highly sensitive photosensitizer.

式（１５－１）中、Ｒ_１１Ａは炭素数１～１２のアルキル基であり、ａ１は０～５の整数である。Ｒ_１２Ａは水素原子又は炭素数１～１２のアルキル基である。Ｒ_１３Ａ及びＲ_１４Ａは、それぞれ独立に水素原子、炭素数１～１２（好ましくは炭素数１～４）のアルキル基、フェニル基又はトリル基を示す。ａ１が２以上の整数の場合、Ｒ_１１Ａはそれぞれ同一でもよく、異なっていてもよい。

In formula (15-1), R _11A is an alkyl group having 1 to 12 carbon atoms, and a1 is an integer of 0-5. R _12A is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. R _13A and R _14A each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms), a phenyl group or a tolyl group. When a1 is an integer of 2 or more, each R _11A may be the same or different.

R _11A is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group. a1 is preferably 1. R _12A is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an ethyl group. R _13A and R _14A are preferably each independently an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

Examples of the compound represented by formula (15-1) include a compound represented by the following formula (15A), which is available as "IRGACURE OXE 02" manufactured by BASF Japan Ltd.

式（１５－２）中、Ｒ_１５Ａは、－ＯＨ、－ＣＯＯＨ、－Ｏ（ＣＨ_２）ＯＨ、－Ｏ（ＣＨ_２）_２ＯＨ、－ＣＯＯ（ＣＨ_２）ＯＨ又は－ＣＯＯ（ＣＨ_２）_２ＯＨであり、Ｒ_１６Ａ及びＲ_１７Ａは、それぞれ独立に水素原子、炭素数１～１２（好ましくは炭素数１～６）のアルキル基、炭素数４～１０のシクロアルキル基、フェニル基又はトリル基である。ｂ１は０～５の整数である。ｂ１が２以上の整数の場合、Ｒ_１５はそれぞれ同一でもよく、異なっていてもよい。
Ｒ_１５Ａは、好ましくは－Ｏ（ＣＨ_２）_２ＯＨである。ｂ１は好ましくは０又は１である。Ｒ_１６Ａは、好ましくは炭素数１～６のアルキル基であり、より好ましくはメチル基又はヘキシル基である。Ｒ_１７Ａは、好ましくは炭素数１～６のアルキル基又はフェニル基であり、より好ましくはメチル基又はフェニル基である。

In formula (15-2), R _15A is —OH, —COOH, —O(CH ₂ )OH, —O(CH ₂ ) ₂ OH, —COO(CH ₂ )OH or —COO(CH ₂ ) ₂ OH, and R _16A and R _17A are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms), a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group is. b1 is an integer of 0-5. When b1 is an integer of 2 or more, each _R15 may be the same or different.
R _15A is preferably —O(CH ₂ ) ₂ OH. b1 is preferably 0 or 1; R _16A is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or a hexyl group. R _17A is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group, more preferably a methyl group or a phenyl group.

Examples of the compound represented by the formula (15-2) include the compound represented by the following formula (15B), which is available as "NCI-930" manufactured by ADEKA Corporation.

In addition, the (C) component preferably contains (C2) a compound represented by the following formula (16) (hereinafter also referred to as "(C2) component").
Component (C2) preferably has lower sensitivity to actinic rays than component (C1), and is preferably a photosensitizer with standard sensitivity.

式（１６）中、Ｒ_２１Ａは炭素数１～１２のアルキル基であり、Ｒ_２２Ａ及びＲ_２３Ａは、それぞれ独立に水素原子、炭素数１～１２のアルキル基（好ましくは炭素数１～４）、炭素数１～１２のアルコキシ基（好ましくは炭素数１～４）、炭素数４～１０のシクロアルキル基、フェニル基又はトリル基であり、ｃ１は０～５の整数である。ｃ１が２以上の整数の場合、Ｒ_２１Ａはそれぞれ同一でもよく、異なっていてもよい。

In formula (16), R _21A is an alkyl group having 1 to 12 carbon atoms, and R _22A and R _23A are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms). , an alkoxy group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms), a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group, and c1 is an integer of 0 to 5. When c1 is an integer of 2 or more, each R _21A may be the same or different.

c1 is preferably zero. R _22A is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group. R _23A is preferably an alkoxy group having 1 to 12 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, still more preferably a methoxy group or an ethoxy group.

Examples of the compound represented by formula (16) include a compound represented by the following formula (16A), which is available as "G-1820 (PDO)" manufactured by Lambson.

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

Component (C) preferably contains one or more selected from the group consisting of component (C1) and component (C2).
In addition, the (C) component preferably contains the (C1) component and the (C2) component from the viewpoint of adjusting the transmittance.

The content of component (C) is preferably from 0.1 to 20 parts by mass, more preferably from 0.1 to 15 parts by mass, and even more preferably from 0.1 to 100 parts by mass of component (A). 10 parts by mass.
Within the above range, the photocrosslinking tends to be uniform in the film thickness direction, making it easier to obtain a practical relief pattern.

When component (C1) is contained, the content of component (C1) is usually 0.05 to 5.0 parts by mass, preferably 0.1 to 2.0 parts by mass, per 100 parts by mass of component (A). 5 parts by mass, more preferably 0.2 to 2.0 parts by mass.

When component (C2) is contained, the content of component (C2) is usually 0.5 to 15.0 parts by mass, preferably 1.0 to 10.0 parts by mass, per 100 parts by mass of component (A). It is 0 parts by mass.

When component (C1) and component (C2) are contained, the content of component (C1) is 0.05 to 5.0 parts by mass per 100 parts by mass of component (A), and component (C2) is preferably 0.5 to 15.0 parts by mass per 100 parts by mass of component (A).

When the component (C1) and the component (C2) are contained, the mass ratio of the content of the component (C1) and the component (C2) is preferably 1:3 to 1:70, more preferably 1:5 to It is 1:50.

（式（１０１）～（１０７）中、
Ｒ_１０１～Ｒ_１１０は、それぞれ独立に水素原子、炭素数１～３の脂肪族炭化水素基、炭素数１～３のアルコキシ基、又はヒドロキシ基であり、
Ｒ_１０１～Ｒ_１０５のうち少なくとも１つはヒドロキシ基であり、Ｒ_１０６～Ｒ_１１０のうち少なくとも１つはヒドロキシ基であり、
Ｒ_１１１～Ｒ_１１４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、
Ｒ_１１５は、２価の基、又は単結合であり、
Ｒ_１２１、Ｒ_１３１、Ｒ_１４１、Ｒ_１５１～Ｒ_１５４、Ｒ_１６１、Ｒ_１６２、Ｒ_１７１及びＲ_１７２は、それぞれ独立に、水素原子、炭素数１～３の脂肪族炭化水素基、炭素数１～３のアルコキシ基、又は、ヒドロキシ基である。） The photosensitive resin composition of the present invention contains (D) one or more compounds selected from the group consisting of compounds represented by the following formulas (101) to (107).

(In formulas (101) to (107),
R ₁₀₁ to R ₁₁₀ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a hydroxy group;
at least one of R ₁₀₁ to R ₁₀₅ is a hydroxy group and at least one of R ₁₀₆ to R ₁₁₀ is a hydroxy group;
R ₁₁₁ to R ₁₁₄ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms,
R ₁₁₅ is a divalent group or a single bond,
R ₁₂₁ , R ₁₃₁ , R ₁₄₁ , R ₁₅₁ to R ₁₅₄ , R ₁₆₁ , R ₁₆₂ , R ₁₇₁ and R ₁₇₂ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, or 1 1 to 3 alkoxy groups or hydroxy groups. )

Number of carbon atoms of R ₁₀₁ to R ₁₁₀ , R 111 to R ₁₁₄ , R ₁₂₁ , R ₁₃₁ , R ₁₄₁ , R ₁₅₁ to R ₁₅₄ , _{R 161 ,} R ₁₆₂ , R ₁₇₁ and R ₁₇₂ in formulas (101) to (107) Examples of 1 to 3 aliphatic hydrocarbon groups include methyl group, ethyl group and propyl group. Methyl groups are preferred.

Number of carbon atoms of R ₁₀₁ to R ₁₁₀ , R _{111 to R 114 , R 121 ,} R ₁₃₁ , R ₁₄₁ , R ₁₅₁ to R ₁₅₄ , _{R 161 ,} R ₁₆₂ , R ₁₇₁ and R ₁₇₂ in formulas (101) to (107) The 1-3 alkoxy groups include a methoxy group, an ethoxy group, a propoxy group and the like. A methoxy group is preferred.

Component (D) is preferably a compound represented by the above formula (101).

R ₁₁₅ in formula (101) is preferably a methylene group.

Preferably, at least one of R ₁₀₃ and R ₁₀₈ (eg of formula (101)) is a hydroxy group. More preferably, R ₁₀₃ and R ₁₀₈ are hydroxy groups.

Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms for R ₁₁₁ to R ₁₁₄ in formula (101) include methyl group, ethyl group and propyl group. Methyl groups are preferred.

R ₁₁₁ to R ₁₁₄ in formula (101) are preferably hydrogen atoms.

（式（１０１Ａ）中、Ｒ_１０２Ａ及びＲ_１０７Ａは、それぞれ独立に、水素原子、又はメトキシ基である。） Component (D) is more preferably a compound represented by the following formula (101A). As a result, it is possible to suppress cross-linking of the unexposed portion due to irregular reflection during actinic ray irradiation. Furthermore, discoloration of the Cu plated substrate can be suppressed.

(In formula (101A), R _102A and R _107A are each independently a hydrogen atom or a methoxy group.)

Component (D) preferably has an absorbance at 365 nm of 0.05 or more, more preferably 0.1 or more at a concentration of 10 mg/L.

Component (D) includes, for example, flavone, flavonol, isoflavone, chalcone, aurone, flavan-3-ol, anthocyanidin, leucoanthocyanidin, (1E,6E)-1-(4-hydroxy-3-methoxyphenyl)-7- (4-hydroxyphenyl)-1,6-heptadiene-3,5-dione), (1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3, 5-dione, 1,7-bis(4-hydroxyphenyl)-1,6-heptadiene-3,5-dione and the like.

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

The content of component (D) is preferably 0.05 parts by mass or more, more preferably 0.1 part by mass or more, relative to 100 parts by mass of component (A) in terms of excellent resolution (resolution). 0.2 parts by mass or more is more preferable.
The content of component (D) is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less per 100 parts by mass of component (A). As a result, it is possible to prevent insufficient photocuring inside the composition due to increased absorption on the surface of the composition upon exposure to actinic rays.

From the viewpoint of ensuring storage stability, the photosensitive resin composition of the present invention may further contain (E) a polymerization inhibitor (hereinafter also referred to as "(E) component").
Component (E) includes radical polymerization inhibitors, radical polymerization inhibitors, and the like.

Examples of component (E) include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, and N-phenyl-2. -naphthylamine, cupferron, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines, and 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]-non-2-ene- 2,3-dixoid) and the like.

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

When the component (E) is contained, the content of the component (E) is, from the viewpoint of the storage stability of the photosensitive resin composition and the heat resistance of the resulting cured product, relative to 100 parts by mass of the component (A). , preferably 0.01 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, and even more preferably 0.05 to 5 parts by mass.

From the viewpoint of suppressing corrosion and preventing discoloration of copper and copper alloys, the photosensitive resin composition of the present invention may further contain (F) a rust inhibitor (hereinafter also referred to as "(F) component"). good.
Component (F) includes, for example, 1,2,4-triazole, 1,2,3-triazole, 1,2,5-triazole, 3-mercapto-4-methyl-4H-1,2,4-triazole , 3-mercapto-1,2,4-triazole, 4-amino-3,5-dimethyl-4H-1,2,4-triazole, 4-amino-3,5-dipropyl-4H-1,2,4 -triazole, 3-amino-5-isopropyl-1,2,4-triazole, 4-amino-3-mercapto-5-methyl-4H-1,2,4-triazole, 3-amino-5-mercapto-1 , 2,4-triazole, 3-amino-5-methyl-4H-1,2,4-triazole, 4-amino-1,2,4-triazole, 4-amino-3,5-dimethyl-1,2 ,4-triazole, 4-amino-5-methyl-4H-1,2,4-triazole-3-thiol, 3,5-diamino-1H-1,2,4-triazole, 5-methyl-1H-benzo Triazole derivatives such as triazole, 5,6-dimethylbenzotriazole, 5-amino-1H-benzotriazole, benzotriazole-4-sulfonic acid, 1,2,3-benzotriazole, and
1H-tetrazole, 5-methyl-1H-tetrazole, 5-(methylthio)-1H-tetrazole, 5-(ethylthio)-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-nitro-1H-tetrazole 1-methyl -1H-tetrazole, 5,5′-bis-1H-tetrazole, 5-amino-1H-tetrazole and other tetrazole derivatives.
Component (F) may be used singly or in combination of two or more.

When component (F) 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 parts by mass, per 100 parts by mass of component (A). ~4 parts by mass is more preferred.

From the viewpoint of improving the adhesion of the resulting cured film to the substrate, the photosensitive resin composition of the present invention further contains (G) a silane coupling agent (adhesion aid) (hereinafter referred to as "(G) component" Also called.) may be included.

Generally, the component (G) reacts with the component (A) to be crosslinked in the heat treatment after development, or the component (G) itself is polymerized 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。） Component (G) includes 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 in that 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 hydroxy group or a glycidyl group may be used as the component (G). 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.
Commercially available products include the product name "KBM403" (manufactured by Shin-Etsu Chemical Co., Ltd.).

The silane coupling agent having a hydroxy group or glycidyl group preferably further contains a group having a nitrogen atom, more 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, examples of the silane coupling agent having an amide bond include compounds represented by the following formulas.
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)

Also, triethoxysilylpropylethyl carbonate may be used as the component (G).

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

When component (G) is used, the content of component (G) is preferably 0.1 to 20 parts by mass, more preferably 1 to 15 parts by mass, more preferably 1 to 10 parts by mass, relative to 100 parts by mass of component (A). Parts by mass are more preferred.

The photosensitive resin composition of the present invention further contains (H) a sensitizer (hereinafter referred to as "(H) component") from the viewpoint of achieving both good resolution and maintenance of residual film ratio in a wide range of exposure doses. Also called.) may be included.

Component (H) includes Michler's ketone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, anthraquinone, methylanthraquinone, 4,4'-bis(diethylamino)benzophenone, acetophenone, benzophenone, thioxanthone, 1,5-acenaphthene, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl- [4-(methylthio)phenyl]-2-morpholino-1-propanone, diacetyl benzyl, benzyl dimethyl ketal, benzyl diethyl ketal, diphenyl disulfide, anthracene, phenanthrene quinone, riboflavin tetrabutyrate, acridine orange, erythrosine, phenanth Lenquinone, 2-isopropylthioxanthone, 2,6-bis(p-diethylaminobenzylidene)-4-methyl-4-azacyclohexanone, 6-bis(p-dimethylaminobenzylidene)-cyclopentanone, 2,6-bis( p-diethylaminobenzylidene)-4-phenylcyclohexanone, aminostyryl ketone, 3-ketocoumarin compound, biscoumarin compound, N-phenylglycine, N-phenyldiethanolamine, 3,3′,4,4′-tetra(t-butylper oxycarbonyl)benzophenone and the like.

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

When component (H) is contained, the amount of component (H) is preferably 0.1 to 2.0 parts by mass, preferably 0.2 to 1.5 parts by mass, per 100 parts by mass of component (A). is more preferred.

From the viewpoint of promoting the polymerization reaction, the photosensitive resin composition of the present invention may further contain (I) a thermal polymerization initiator (hereinafter also referred to as "(I) component").
Component (I) is not decomposed by heating (drying) for removing the solvent during film formation, but is decomposed by heating during curing to generate radicals, and component (B) itself, or component (A) and A compound that accelerates the polymerization reaction of component (B) is preferred.
Component (I) 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-hexylperoxyisopropylmonocarbonate, 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", "Perbutyl H", and "Perbutyl O" (manufactured by NOF Corporation).

When component (I) is contained, the content of component (I) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of component (A). 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.

Component (J) 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 (J) component, 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.)).

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

The photosensitive resin composition of the present invention may further contain surfactants or leveling agents.

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 “Florado FC430”, “FC431” (manufactured by Sumitomo 3M), trade name “Organosiloxane polymer KP341” (Shin-Etsu manufactured by Kagaku Kogyo Co., Ltd.) and the like.

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 (A). Preferably, 0.05 to 3 parts by mass is more preferable.

Except for component (J), the photosensitive resin composition of the present invention consists essentially of components (A) to (D) and optionally components (E) to (I), a surfactant, and a leveling agent. and may contain other unavoidable impurities within a range that does not impair the effects 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 of the photosensitive resin composition of the present invention, excluding the component (J),
(A) to (D) components,
It may consist of components (A)-(I) or components (A)-(D) and optionally components (E)-(I), surfactants and leveling agents.

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

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.
The actinic rays to be irradiated include ultraviolet rays such as i-rays, visible rays, and radiation, but i-rays are preferable.
As an exposure device, a parallel exposure machine, a projection exposure machine, a stepper, a scanner exposure machine, or the like can be used.

After exposure and before development, post-exposure baking (PEB) may be performed, if necessary. The post-exposure heating temperature is preferably 60° C. to 160° C., and the post-exposure heating time is preferably 0.5 to 5 minutes.

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, γ-butyrolactone, α-acetyl-γ-butyrolactone, Cyclopentanone, cyclohexanone and the like can be mentioned.
Poor solvents 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, 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 component (A) used, but is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and still 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 precursor of the component (A) undergoes a dehydration ring-closure reaction in the heat treatment step, and usually becomes the 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 160 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.

Components used in Examples and Comparative Examples are as follows.

(A) Component: Polyimide precursor A1 having a polymerizable unsaturated bond: Compound A2 obtained in Synthesis Example 1 described later: Compound A3 obtained in Synthesis Example 2 described later: Obtained in Synthesis Example 3 described later Compound A4: a compound obtained in Synthesis Example 4 described later

Ｂ２：ＡＴＭ－４Ｅ（新中村化学工業株式会社製、テトラキスアクリル酸メタンテトライルテトラキス(メチレンオキシエチレン)）
Ｂ３：ＴＥＧＤＭＡ（新中村化学工業株式会社製、テトラエチレングリコールジメタクリレート）
Ｂ４：Ａ－ＴＭＭＴ（新中村化学工業株式会社製、ペンタエリスリトールテトラアクリレート） (B) component: polymerizable monomer B1: A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd., tricyclodecanedimethanol diacrylate, compound represented by the following formula)

B2: ATM-4E (manufactured by Shin-Nakamura Chemical Co., Ltd., tetrakis methantetrayl tetrakis (methyleneoxyethylene) acrylate)
B3: TEGDMA (manufactured by Shin-Nakamura Chemical Co., Ltd., tetraethylene glycol dimethacrylate)
B4: A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd., pentaerythritol tetraacrylate)

(C) component: photopolymerization initiator C1: IRGACURE 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)
C3: NCI-930 (manufactured by ADEKA Corporation, 2-(acetoxyimino)-1-[4-[4-(2-hydroxyethoxy)phenylsulfanyl]phenyl]propan-1-one)

(D) component
D1: Curcumin (manufactured by Sanwa Chemical Co., Ltd., (1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione)
D2: HPH (manufactured by Sanwa Chemical Co., Ltd., 1,7-bis(4-hydroxyphenyl)-1,6-heptadiene-3,5-dione)
(D') Component D'1: ADEKA STAB LA-29 (manufactured by ADEKA Corporation, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol)
D'2: Adekastab LA-24 (manufactured by ADEKA Corporation, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol)
D'3: Adekastab LA-32 (manufactured by ADEKA Corporation, 2-(2H-benzotriazol-2-yl)-p-cresol)
D'4: SEESORB106 (manufactured by Shipro Kasei Co., Ltd., 2,2',4,4'-tetrahydroxybenzophenone)
D'5: SEESORB107 (manufactured by Shipro Kasei Co., Ltd., 2,2'-dihydroxy-4,4'-dimethoxybenzophenone)
D′6: Disperse Thread 1 (manufactured by Hitachi Chemical Techno Service Co., Ltd., 4-[ethyl (2-hydroxyethyl)amino]-4′-nitroazobenzene)

(E) component: polymerization inhibitor E1: Taobn (manufactured by Hampford Research, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]-non-2-ene-2,3-dixoid)
E2: Hydroquinone

Component (H): Sensitizer H1: EMK (manufactured by Aldrich, 4,4′-bis(diethylamino)benzophenone)

(I) Component: Thermal polymerization initiator I1: Permir D (manufactured by NOF Corporation, bis (1-phenyl-1-methylethyl) peroxide)

(J) Component: Solvent J1: N-methyl-2-pyrrolidone J2: γ-butyrolactone J3: KJCMPA-100 (manufactured by KJ Chemicals, 3-methoxy-N,N-dimethylpropanamide)

[Absorbance measurement]

Also, the absorbances of the components (D) and (D') were measured under the following conditions. Table 1 shows the results.
Components (D) and (D') were each dissolved in chloroform to prepare a solution of 10 mg/L, which was used as a sample for measurement.
Measuring instrument: U-3900H (manufactured by Hitachi High-Tech Science Co., Ltd.)
Measurement conditions: cell length: 10.0 mm

Synthesis Example 1 (Synthesis of A1)
47.1 g (152 mmol) of 3,3′,4,4′-diphenylethertetracarboxylic dianhydride (ODPA), 5.54 g (43 mmol) of 2-hydroxyethyl methacrylate (HEMA) and a catalytic amount of 1,4- diazabicyclo [2.2.2. ] Octanetriethylenediamine was dissolved in 380 g of N-methyl-2-pyrrolidone (NMP), stirred at 45° C. for 1 hour and then cooled to 25° C. to give 27.4 g (129 mmol) of 2,2′-dimethylbenzidine. and 145 mL of dry N-methyl-2-pyrrolidone were added, stirred at 45° C. for 150 minutes, and then cooled to room temperature. After 59.7 g (284 mmol) of trifluoroacetic anhydride was added dropwise to this solution and stirred for 120 minutes, a catalytic amount of benzoquinone was added, and 40.4 g (310 mmol) of HEMA was further 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 35,000.

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 81 mol % with respect to all carboxy groups in polyamic acid (remaining 19 mol % of 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)
47.1 g (152 mmol) of ODPA and 2.77 g (21 mmol) of HEMA and a catalytic amount of 1,4-diazabicyclo [2.2.2. ] Octanetriethylenediamine was dissolved in 500 g of NMP and stirred at 45° C. for 1 hour, then cooled to 25° C. and 30.0 g (141 mmol) of 2,2′-dimethylbenzidine and 145 mL of dry NMP were added. After stirring for 150 minutes at 0 C, it was cooled to room temperature. After 65.2 g (311 mmol) of trifluoroacetic anhydride was added dropwise to this solution, the mixture was stirred for 180 minutes, a catalytic amount of benzoquinone was added, and 43.1 g (331 mmol) of HEMA was further 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 a polyimide precursor A2.
Using a gel permeation chromatography (GPC) method, the weight average molecular weight was obtained under the following conditions by standard polystyrene conversion. A2 had a weight average molecular weight of 70,000.

Further, the esterification rate of A2 was calculated by NMR measurement under the same conditions as in Synthesis Example 1. The esterification rate was 73 mol % with respect to all carboxy groups in the polyamic acid (the remaining 27 mol % were carboxy groups).

Synthesis Example 3 (Synthesis of A3)
62.0 g (200 mmol) of ODPA, 5.2 g (40.0 mmol) of HEMA and a catalytic amount of 1,4-diazabicyclo[2.2.2]octanetriethylenediamine were dissolved in 250 g of NMP and stirred at 45° C. for 1 hour. 5.5 g (50.9 mmol) of m-phenylenediamine, 23.8 g (119 mmol) of oxydianiline (4,4′-diaminodiphenyl ether) and 100 mL of dry NMP were added and stirred at 45° C. for 150 minutes. After that, it was cooled to room temperature to obtain a polyamic acid. After 78.5 g (374 mmol) of trifluoroacetic anhydride was added dropwise to this solution and stirred for 20 minutes, 53.1 g (408 mmol) of 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 A3.
Using the GPC method, the weight average molecular weight was obtained under the same conditions as in Synthesis Example 1. A3 had a weight average molecular weight of 35,000.
Further, the esterification rate of A3 was calculated by NMR measurement under the same conditions as in Synthesis Example 1. The esterification rate was 70 mol % with respect to all carboxy groups in the polyamic acid (the remaining 30 mol % were carboxy groups).

Synthesis Example 4 (Synthesis of A4)
43.6 g (200 mmol) of pyromellitic dianhydride (PMDA), 54.9 g (401 mmol) of HEMA, and 0.220 g of hydroquinone were dissolved in 394 g of NMP, and after adding a catalytic amount of 1,8-diazabicycloundecene, 25 C. for 24 hours to effect esterification to obtain a solution of pyromellitic acid-hydroxyethyl methacrylate diester. This solution is designated as PMDA-HEMA solution.
Dissolve 49.6 g (160 mmol) of ODPA, 4.98 g (328 mmol) of HEMA and 0.176 g of hydroquinone in 378 g of NMP, add a catalytic amount of 1,8-diazabicycloundecene, stir at 25° C. for 48 hours, and esterify. to obtain a 3,3',4,4'-diphenyl ether tetracarboxylic acid-hydroxyethyl methacrylate diester solution. Let this solution be the ODPA-HEMA solution.
196 g of PMDA-HEMA solution and 58.7 g of ODPA-HEMA solution were mixed, and then 25.9 g (218 mmol) of thionyl chloride was added dropwise under ice cooling using a dropping funnel so that the temperature of the reaction solution was maintained at 10°C or less. bottom. After the dropwise addition of thionyl chloride was completed, reaction was carried out for 2 hours under ice-cooling to obtain a solution of acid chlorides of PMDA and ODPA. Then, using a dropping funnel, a solution of 31.7 g (99.0 mmol) of 2,2′-bis(trifluoromethyl)benzidine, 34.5 g (436 mmol) of pyridine, and 0.076 g (693 mmol) of hydroquinone in 90.2 g of NMP was added. The temperature of the reaction solution was added dropwise under ice-cooling while being careful not to exceed 10°C. 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 A4.
Using the GPC method, the weight average molecular weight was obtained under the same conditions as in Synthesis Example 1. A4 had a weight average molecular weight of 34,000.

Examples 1-13 and Comparative Examples 1-18
[Preparation of photosensitive resin composition]
The photosensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 18 were prepared using the components and blending amounts shown in Tables 2 to 4. The blending amounts in Tables 2 to 4 are parts by mass of each component with respect to 100 parts by mass of component (A).

[Production of patterned resin film]
The obtained photosensitive resin composition is spin-coated on a Cu-plated 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. A photosensitive resin film having a film thickness of 7 to 10 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-line stepper FPA-3000iW (manufactured by Canon Inc.) was applied to the obtained photosensitive resin film at the exposure amounts shown in Tables 2 to 4. , and exposure was performed by irradiating a photomask for via formation with a diameter of 1 μm to 100 μm.
Using Act8, post-exposure heating was performed at 120° C. for 3 minutes in the atmosphere.
After the post-exposure heating, 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.

[Evaluation of Cu discoloration]
The patterned resin film thus obtained was observed with an optical microscope for the color of Cu in the openings. The color was compared with the color of the Cu-plated wafer before spin coating and evaluated according to the following criteria.
A: No discoloration.
B: Discolored to red.
C: Discolored to white.
D: No discoloration was observed due to the generation of residue.
The results are shown in Tables 2-4.

[Production of pattern cured product]
The resulting patterned resin film was heated at 175° C. for 1 hour in a nitrogen atmosphere using a vertical diffusion furnace μ-TF (manufactured by Koyo Thermo Systems Co., Ltd.) to form a patterned cured product (film thickness after curing: 5 μm). Obtained.

[Resolution evaluation]
The obtained pattern cured product was observed using an optical microscope, and the minimum diameter at which an opening exposing 55% or more of the substrate surface was formed with respect to the area of the mask dimension of the via was defined as the resolution according to the following criteria. evaluated with
A: A pattern of less than 4 µm was opened.
B: A pattern of 4 μm or more and less than 6 μm was opened.
C: A pattern of 6 μm or more and less than 8 μm was opened.
D: A pattern of 8 μm or more was opened.
The results are shown in Tables 2-4.

Examples 1a, 9a-12a and Comparative Examples 5a, 6a, 12a-15a, 17a, 18a
[Preparation of photosensitive resin composition]
Using the components and blending amounts shown in Table 5, photosensitive resin compositions of Examples 1a, 9a to 12a and Comparative Examples 5a, 6a, 12a to 15a, 17a and 18a were prepared. The blending amounts in Table 5 are parts by mass of each component with respect to 100 parts by mass of component (A).

[Production of patterned resin film]
Using the obtained photosensitive resin composition, photosensitive resin films were formed in the same manner as in Examples 1 to 13 and Comparative Examples 1 to 18.
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 above, and FPA-3000iW was applied to the obtained photosensitive resin film at the exposure amount shown in Table 5 to form a via formation photomask with a diameter of 1 μm to 100 μm. Exposure was performed by irradiation.
The exposed resin film was puddle-developed using Act8 in cyclopentanone for the above development time, and then rinsed with PGMEA to obtain a patterned resin film.

[Evaluation of Cu discoloration]
Regarding the obtained patterned resin films, the color of Cu in the openings was evaluated in the same manner as in Examples 1 to 13 and Comparative Examples 1 to 18.
Table 5 shows the results.

[Production of pattern cured product]
The resulting patterned resin film was heated in a nitrogen atmosphere at 175° C. for 1 hour using μ-TF to obtain a patterned cured product (film thickness after curing: 5 μm).

[Resolution evaluation]
The obtained pattern cured products were evaluated for resolution in the same manner as in Examples 1 to 13 and Comparative Examples 1 to 18.
Table 5 shows the results.

Examples 14-16 and Comparative Examples 19-21
[Preparation of photosensitive resin composition]
The photosensitive resin compositions of Examples 14 to 16 and Comparative Examples 19 to 21 were prepared using the components and blending amounts shown in Table 6. The blending amounts in Table 6 are parts by mass of each component with respect to 100 parts by mass of component (A).

[Production of patterned resin film]
The obtained photosensitive resin composition is spin-coated on a Cu-plated 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. A photosensitive resin film having a film thickness of 12 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 above, and FPA-3000iW was applied to the obtained photosensitive resin film at the exposure amount shown in Table 6 to form a via formation photomask with a diameter of 1 μm to 100 μm. Exposure was performed by irradiation.
The exposed resin film was puddle-developed using Act8 in cyclopentanone for the above development time, and then rinsed with PGMEA to obtain a patterned resin film.

[Production of pattern cured product]
The resulting patterned resin film was heated in a nitrogen atmosphere at 175° C. for 1 hour using μ-TF to obtain a patterned cured product (film thickness after curing: 10 μm).

[Resolution evaluation]
The obtained pattern cured product was observed using an optical microscope, and the minimum diameter at which an opening exposing 55% or more of the substrate surface was formed with respect to the area of the mask dimension of the via was defined as the resolution according to the following criteria. evaluated with
A: A pattern of less than 8 μm was opened.
B: A pattern of 8 μm or more and less than 10 μm was opened.
C: A pattern of 10 μm or more and less than 15 μm was opened.
D: A pattern of 15 μm or more was opened.
Table 6 shows the results.

Examples 17, 18 and Comparative Examples 22, 23
[Preparation of photosensitive resin composition]
The photosensitive resin compositions of Examples 17 and 18 and Comparative Examples 22 and 23 were prepared using the components and blending amounts shown in Table 7. The blending amounts in Table 7 are parts by mass of each component with respect to 100 parts by mass of component (A).

[Production of patterned resin film]
The obtained photosensitive resin composition is spin-coated on a Cu-plated wafer using Act8, dried at 100 ° C. for 2 minutes, dried at 110 ° C. for 2 minutes, and has a dry film thickness of 12 to 15 μm. A resin film 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 above, and FPA-3000iW was applied to the obtained photosensitive resin film at the exposure amount shown in Table 7 to form a via formation photomask with a diameter of 1 μm to 100 μm. Exposure was performed by irradiation.
Using Act8, post-exposure heating was performed at 120° C. for 3 minutes in the atmosphere.
After the post-exposure heating, the resin film was puddle-developed with cyclopentanone using Act8 for the above development time, and then rinsed with PGMEA to obtain a patterned resin film.

[Production of pattern cured product]
The resulting patterned resin film was heated in a nitrogen atmosphere at 175° C. for 1 hour using μ-TF to obtain a patterned cured product (film thickness after curing: 10 μm).

[Resolution evaluation]
Examples 14 to 16 and Comparative Examples 19 to 21 for the resulting patterned cured product
The resolution was evaluated in the same manner as above.
Table 7 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.

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

Claims (16)

(A) a polyimide precursor having a polymerizable unsaturated bond;
(B) a polymerizable monomer,
(C) A photopolymerization initiator, and (D) a photosensitive resin composition for a copper substrate or copper wiring containing a compound represented by the following formula (101) .

( In formula (101) ,
R ₁₀₁ to R ₁₁₀ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a hydroxy group;
at least one of R ₁₀₁ to R ₁₀₅ is a hydroxy group and at least one of R ₁₀₆ to R ₁₁₀ is a hydroxy group;
R ₁₁₁ to R ₁₁₄ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms,
R ₁₁₅ is a methylene group. ) 2. The photosensitive resin composition according to claim 1, wherein the component (A) is a polyimide precursor having a structural unit represented by the following formula (1).

(In 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 - groups are ortho positions to each other, Y ₁ is a divalent group having one or more aromatic groups, R ₁ and R ₂ are each independently a hydrogen atom, represented by the following formula (2): or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, 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.) 3. 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. 4. The photosensitive resin composition according to claim 3, wherein the number of groups containing polymerizable unsaturated double bonds is two or more. 5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the polymerizable monomer has an aliphatic cyclic skeleton. The photosensitive resin composition according to any one of claims 1 to 3, wherein the component (B) contains a polymerizable monomer represented by the following formula (3).

(In formula (3), R ₆ and R ₇ are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following formula (4); n1 is 0 or 1; , n2 is an integer of 0 to 2, and n1+n2 is 1 or more.At least one of n1 R ₆ and n2 R ₇ is a group represented by the following formula (4).)

(In Formula (4), R ₉ to R ₁₁ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and l is an integer of 0 to 10.) 7. The photosensitive resin composition according to claim 6, wherein n1+n2 is 2 or 3. The photosensitive resin composition according to any one of claims 1 to 7, wherein the component (B) contains a polymerizable monomer represented by the following formula (5).

The photosensitive resin composition according to any one of claims 1 to 8 , wherein the component (D) is a compound represented by the following formula (101A).

(In formula (101A), R _102A and R _107A are each independently a hydrogen atom or a methoxy group.) 10. The photosensitive resin composition according to any one of claims 1 to 9 , further comprising (I) a thermal polymerization initiator. A step of applying the photosensitive resin composition according to any one of claims 1 to 10 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. 12. The method for producing a pattern-cured product according to claim 11 , wherein the heat treatment temperature is 200[deg.] C. or less. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 10 . The cured product according to claim 13 , 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 13 or 14 . An electronic component comprising the interlayer insulating film, cover coat layer or surface protective film according to claim 15 .

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