JP2022110710A - Photosensitive resin composition, method for producing cured pattern, cured product, interlayer insulation film, cover coat layer, surface protection film and electronic component - Google Patents

Abstract

To provide a photosensitive resin composition that can form a cured product having high resolution even when cured at low temperatures of 200°C or lower, a method for producing a cured pattern, a cured product, an interlayer insulation film, a cover coat layer, a surface protection film and an electronic component.SOLUTION: A photosensitive resin composition contains (A) a polyimide precursor having a polymerizable unsaturated bond, (B1) a polymerizable monomer having an aliphatic cyclic skeleton, and (C) a compound having an acyl phosphine oxide structure.SELECTED DRAWING: None

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 (see, for example, Patent Documents 1).

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

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

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

A technique using a negative photosensitive resin composition as a photosensitive resin composition has been disclosed (for example, Patent Document 3).

JP 2009-265520 A WO2008/111470 WO2019/087985

An object of the present invention is to provide 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, a method for producing a pattern cured product, a cured product, an interlayer insulating film, a cover coat layer, and a surface. It is to provide protective films and electronic components.

（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（Ｂ１）成分が、重合性の不飽和二重結合を含む基を有し、脂肪族環状骨格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（Ｂ１）成分が、２以上の重合性の不飽和二重結合を含む基を有し、脂肪族環状骨格を有す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。
５．前記（Ｂ１）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。）
６．ｎ１＋ｎ２が、２又は３である５に記載の感光性樹脂組成物。
７．前記（Ｂ１）成分が、下記式（５）で表される重合性モノマーを含む１～６のいずれかに記載の感光性樹脂組成物。

８．さらに、（Ｂ２）前記（Ｂ１）成分以外の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．さらに、（Ｄ）紫外線吸収剤を含む１～８のいずれかに記載の感光性樹脂組成物。
１０．さらに、（Ｅ）熱重合開始剤を含む１～９のいずれかに記載の感光性樹脂組成物。
１１．１～１０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。
１２．前記加熱処理の温度が２００℃以下である１１に記載のパターン硬化物の製造方法。
１３．１～１０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。
１４．パターン硬化物である１３に記載の硬化物。
１５．１３又は１４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。
１６．１５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;
A photosensitive resin composition containing (B1) a polymerizable monomer having an aliphatic cyclic skeleton, and (C) a compound containing an acylphosphine oxide structure.
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 (B1) has a group containing a polymerizable unsaturated double bond and contains a polymerizable monomer having an aliphatic cyclic skeleton.
4. 4. The photosensitive resin composition according to any one of 1 to 3, wherein the component (B1) has a group containing two or more polymerizable unsaturated double bonds and contains a polymerizable monomer having an aliphatic cyclic skeleton. .
5. 4. The photosensitive resin composition according to any one of 1 to 3, wherein the component (B1) 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.)
6. 6. The photosensitive resin composition according to 5, wherein n1+n2 is 2 or 3.
7. 7. The photosensitive resin composition according to any one of 1 to 6, wherein the component (B1) contains a polymerizable monomer represented by the following formula (5).

8. 8. The photosensitive resin composition according to any one of 1 to 7, further comprising (B2) a polymerizable monomer other than the component (B1).
9. 9. The photosensitive resin composition according to any one of 1 to 8, further comprising (D) an ultraviolet absorber.
10. 10. The photosensitive resin composition according to any one of 1 to 9, further comprising (E) a thermal polymerization initiator.
11. A step of applying the photosensitive resin composition according to any one of 1 to 10 on a substrate and drying 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. 12. The method for producing a patterned cured product according to 11, wherein the temperature of the heat treatment is 200° C. or less.
13. A cured product obtained by curing the photosensitive resin composition according to any one of 1 to 10.
14. 14. The cured product according to 13, which is a pattern cured product.
15. An interlayer insulating film, a cover coat layer or a surface protective film produced using the cured product according to 13 or 14.
16. An electronic component comprising the interlayer insulating film, cover coat layer or surface protective film according to 15.

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, a method for producing a patterned cured product, a cured product, an interlayer insulating film, a cover coat layer, and a surface Protective films and electronic components can be provided.

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

Embodiments of the photosensitive resin composition, the method for producing a patterned cured product, the cured product, the interlayer insulating film, the cover coat layer, the surface protective film and the electronic component of the present invention are described in detail below. 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".

The photosensitive resin composition of the present invention is
(A) a polyimide precursor having a polymerizable unsaturated bond (hereinafter also referred to as "(A) component"),
(B1) a polymerizable monomer having an aliphatic cyclic skeleton (hereinafter also referred to as "(B1) component"), and (C) a compound containing an acylphosphine oxide structure (hereinafter also referred to as "(C) component") contains

As a result, a cured product with excellent resolution can be formed even when curing is performed at a low temperature of 200° C. or less.
In addition, as an optional effect, a cured product having an excellent film retention rate can be formed.

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, based on 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 (B1) a polymerizable monomer having 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.

Component (B1) 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 preferably contains a polymerizable monomer having a (meth)acrylic group) and an aliphatic cyclic skeleton, and improves the crosslink density and photosensitivity, and suppresses swelling of the pattern after development. of groups containing polymerizable unsaturated double bonds.

（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。） The (B1) 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 ).)

The (B1) component more preferably contains a polymerizable monomer represented by the following formula (5).

Moreover, as the (B1) component, 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.

(B1) component may be used individually by 1 type, and may combine 2 or more types.

The content of component (B1) 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 the post-development residue in the unexposed area.

The photosensitive resin composition of the present invention contains (C) a compound containing (eg, one or more, preferably one or two) acylphosphine oxide structures. As a result, even a fine pattern does not easily leave residue, and the resolution can be improved.

Component (C) includes 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2,4, 4-trimethylpentyl)phosphine oxide (eg, Irgacure 1700 manufactured by BASF Japan) and the like, but are not limited thereto.

式（１５）中、Ｒ_２６及びＲ_２７は、それぞれ独立に炭素数１～１２（好ましくは炭素数１～４）のアルキル基（例えば、メチル基）であり、ｐ及びｒは、それぞれ独立に０～５の整数であり、ｓは０～２の整数であり、ｔは、１～３の整数であり、ｓとｔの和は３である。ｐが２以上の整数の場合、Ｒ_２６はそれぞれ同一でもよく、異なっていてもよい。ｒが２以上の整数の場合、Ｒ_２７はそれぞれ同一でもよく、異なっていてもよい。ｓが２の場合、括弧内の基はそれぞれ同一でもよく、異なっていてもよい。ｔが２以上の整数の場合、括弧内の基はそれぞれ同一でもよく、異なっていてもよい。 As component (C), for example, a compound represented by the following formula (15) is preferable.

In formula (15), R ₂₆ and R ₂₇ are each independently an alkyl group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms) (eg, methyl group), and p and r are each independently is an integer from 0 to 5, s is an integer from 0 to 2, t is an integer from 1 to 3, and the sum of s and t is 3; When p is an integer of 2 or more, each R ₂₆ may be the same or different. When r is an integer of 2 or more, each R ₂₇ may be the same or different. When s is 2, the groups in parentheses may be the same or different. When t is an integer of 2 or more, the groups in parentheses may be the same or different.

p is preferably zero. R ₂₇ is preferably each independently an alkyl group having 1 to 4 carbon atoms, preferably a methyl group. r is preferably an integer of 2-4, more preferably 3; The combination of s and t (s, t) is preferably (1,2) or (2,1).

Examples of the compound represented by formula (15) include a compound represented by formula (16) below and a compound represented by formula (17) below.

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

The content of component (C) is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and still more preferably 0.1 to 30 parts by mass based on 100 parts by mass of component (A). 15 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.

The photosensitive resin composition of the present invention preferably further contains a polymerizable monomer (hereinafter also referred to as "component (B2)") other than component (B2) and (B1). Thereby, the heat resistance, mechanical properties and chemical resistance of the cured product to be formed can be improved.

Component (B2) includes 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, ethoxylated pentaerythritol Tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, tetramethylolmethanetetraacrylate, tetramethylolmethanetetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tetrakis methanetetrayl acrylate tetrakis(methyleneoxyethylene), ethoxylated isocyanurate 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.

(B2) component may be used individually by 1 type, and may combine 2 or more types.

When component (B2) is included, the total content of component (B1) and component (B2) 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 the post-development residue in the unexposed area.

Further, when the (B2) component is included, from the viewpoint of improving the properties of the cured product, the total content of the (B2) component is preferably 1 to 40 parts by mass with respect to 100 parts by mass of the (A) component. 40 parts by mass is more preferable, and 5 to 30 parts by mass is even more preferable.

The photosensitive resin composition of the present invention may further contain (D) an ultraviolet absorber (hereinafter also referred to as "component (D)"). As a result, it is possible to suppress cross-linking of the unexposed portion due to irregular reflection during actinic light irradiation, and to further improve the resolution. 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.

As the component (D), for example,
2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole, 2-(3 ,5-di-tert-pentyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2H-benzotriazol-2-yl)-4-methyl-6-(3,4,5,6-tetrahydrophthal imidylmethyl)phenol, 2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, 2-(2H- benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1- benzotriazole compounds such as phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-p-cresol),
Salicylic acid ester compounds such as phenyl salicylate and 4-tert-butylphenyl salicylate,
2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 4-n-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5 - benzophenone compounds such as sulfonic acid trihydrate, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone,
Diphenyl acrylate compounds such as ethyl 2-cyano-3,3-diphenylacrylate,
a cyanoacrylate compound,
Diphenylcyanoacrylate compounds such as 2-cyano-3,3-diphenylacrylic acid (2'-ethylhexyl),
benzothiazole compounds,
azobenzene compounds such as 4-[ethyl(2-hydroxyethyl)amino]-4'-nitroazobenzene,
pyrogallol, phloroglycin, catechin, epicatechin, gallocatechin, catechin gallate, gallocatechin gallate, epicatechin gallate, epigallocatechin gallate, epigallocatechin, rutin, quercetin, quercetagin, quercetagetin, gossypetin, pelargonidin, cyanidin, aurantidin, Luteolinidin, Peonidin, Rocinidin, (1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione, 1,7-bis(4-hydroxyphenyl )-polyphenol compounds such as 1,6-heptadiene-3,5-dione,
[2,2′-thiobis(4-tert-octylphenolate)]-2-ethylhexylaminenickel(II) and other nickel complex compounds.

Benzotriazole-based compounds, benzophenone-based compounds, azobenzene-based compounds, and polyphenol-based compounds are particularly preferred.

Component (D) includes 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazol-2-yl)- 4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-p-cresol), 2,2′,4,4′-tetrahydroxybenzophenone, 2 ,2′-dihydroxy-4,4′-dimethoxybenzophenone, 4-[ethyl(2-hydroxyethyl)amino]-4′-nitroazobenzene, (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 is preferable from the viewpoint of

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

When component (D) is included, the content of component (D) is preferably 0.05 parts by mass or more per 100 parts by mass of component (A), from the viewpoint of improving resolution (resolution). 1 part by mass or more is more preferable, and 0.2 parts by mass or more is even more preferable.
When component (D) is included, 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 photosensitive resin composition due to increased absorption on the surface of the photosensitive resin composition upon exposure to actinic rays.

From the viewpoint of promoting the polymerization reaction, the photosensitive resin composition of the present invention may further contain (E) a thermal polymerization initiator (hereinafter also referred to as "component (E)").
The component (E) does not decompose by heating (drying) for removing the solvent during film formation, but decomposes by heating during curing to generate radicals. A compound that accelerates the polymerization reaction of component (B1) is preferred.
Component (E) is preferably a compound with a decomposition point of 110° C. or higher and 200° C. or lower, and more preferably a compound with a decomposition point of 110° C. or higher and 175° C. or lower from the viewpoint of promoting the polymerization reaction at a lower temperature.

Specific examples include ketone peroxides such as methyl ethyl ketone peroxide, 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, 1, Peroxyketals such as 1-di(t-butylperoxy)cyclohexane, hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, dicumyl peroxide, di - Dialkyl peroxides such as t-butyl peroxide, diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide, peroxys such as di(4-t-butylcyclohexyl)peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate Dicarbonate, t-butylperoxy-2-ethylhexanoate, t-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).

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

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

The photosensitive resin composition of the present invention may further contain a solvent.
Solvents include 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, tetramethylene sulfone, cyclohexanone, cyclopentanone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, N-dimethylmorpholine and the like. There is no particular limitation as long as it can sufficiently dissolve other components.
Among these, N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, and N,N-dimethylformamide are used 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。） A compound represented by the following formula (21) may also be used as the solvent.

(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.)).

A solvent may be used individually by 1 type, and may combine 2 or more types.
The content of the solvent is not particularly limited, but is generally 50 to 1,000 parts by weight per 100 parts by weight of component (A).

The photosensitive resin composition of the present invention may further contain polymerization inhibitors, rust preventives, silane coupling agents (adhesion aids), sensitizers, surfactants or leveling agents, and the like.

Storage stability can be ensured by including a polymerization inhibitor.
Examples of polymerization inhibitors include radical polymerization inhibitors and radical polymerization inhibitors.

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

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

When a polymerization inhibitor is contained, the content of the polymerization inhibitor is 0 per 100 parts by mass of component (A) from the viewpoint of the storage stability of the photosensitive resin composition and the heat resistance of the resulting cured product. 0.01 to 30 parts by weight is preferred, 0.01 to 10 parts by weight is more preferred, and 0.05 to 5 parts by weight is even more preferred.

By including a rust preventive agent, corrosion of copper and copper alloys can be suppressed and discoloration can be prevented.
Rust inhibitors include, 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-benzotriazole , 5,6-dimethylbenzotriazole, 5-amino-1H-benzotriazole, benzotriazole-4-sulfonic acid, triazole derivatives such as 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'- Examples include tetrazole derivatives such as bis-1H-tetrazole and 5-amino-1H-tetrazole.
The rust preventives may be used singly or in combination of two or more.

When a rust inhibitor is used, the content of the rust inhibitor is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of component (A). 4 parts by mass is more preferred.

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

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

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

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

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

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

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

Compounds represented by formula (14) include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3- Hydroxypropyltriethoxysilane, 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2- glycidoxyethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybutyltriethoxysilane and the like. be done.
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, the silane coupling agent may be triethoxysilylpropylethyl carbonate.

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

When a silane coupling agent is used, the content of the silane coupling agent is preferably 0.1 to 20 parts by mass, more preferably 1 to 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.

By including a sensitizer, it is possible to achieve both maintenance of the film retention rate in a wide range of exposure doses and good resolution (resolution).

Sensitizers include 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 and 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, phenanthrene quinone, 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 compounds, biscoumarin compounds, N-phenylglycine, N-phenyldiethanolamine, 3,3′,4,4′-tetra(t-butylperoxy carbonyl)benzophenone and the like.

A sensitizer may be used alone or in combination of two or more.

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

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

Examples of surfactants or leveling agents include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenol ether. ”, “F173”, “R-08” (manufactured by DIC Corporation), trade names “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 the solvent, the photosensitive resin composition of the present invention consists essentially of components (A), (B1) and (C), and optionally (B2), (D) and (E). Ingredients, polymerization inhibitor, rust preventive, silane coupling agent (adhesion aid), sensitizer, surfactant and leveling agent, and contain other unavoidable impurities within the range that does not impair the effects of the present invention. It's okay.
The photosensitive resin composition of the present invention, for example, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 100% by mass, excluding the solvent,
(A) component, (B1) component and (C) component,
(A) component, (B1) component, (C) component, and (B2) component or (A) component, (B1) component and (C) component, and optionally (B2) component, (D) component, ( It may consist of component E), a polymerization inhibitor, an antirust agent, a silane coupling agent (adhesion aid), a sensitizer, a surfactant and a leveling agent.

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 pattern-cured product described above, the opening width of the pattern is preferably 3 μm or less. The opening width of the pattern can be measured from the image obtained by photographing the cross section of the pattern cured product with a scanning electron microscope (SEM).

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

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

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

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

Drying can be performed using a hot plate, an oven, or the like.
The drying temperature is preferably 90 to 150°C, more preferably 90 to 120°C from the viewpoint of ensuring the dissolution contrast.
The drying time is preferably 30 seconds to 5 minutes.
Drying may be performed twice or more.
As a result, a photosensitive resin film formed by forming the above photosensitive resin composition into a film can be obtained.

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

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

After pattern 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 30 seconds 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 rinsing 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.

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) and stirred at 45°C for 1 hour and then cooled to 25°C.
To this solution, 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, the solution was stirred for 120 minutes. To this solution, a catalytic amount of benzoquinone was added, 40.4 g (310 mmol) of HEMA was further added, and the mixture was 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.
About obtained polyimide precursor A1, the weight average molecular weight was calculated|required on the following conditions by standard polystyrene conversion using the gel permeation chromatography (GPC) method. 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 % of all carboxy groups (to all carboxy groups and all carboxy esters) (the remaining 19 mol % being carboxy groups).

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

Synthesis Example 2 (Synthesis of A2)
In a 1.0 liter flask equipped with a stirrer and a thermometer, 62.0 g (199.9 mmol) of 4,4′-oxydiphthalic dianhydride, 5.2 g (40.0 mmol) of 2-hydroxyethyl methacrylate and A catalytic amount of 1,4-diazabicyclo [2.2.2. ] Octanetriethylenediamine was dissolved in 250.0 g of N-methyl-2-pyrrolidone, stirred at 45° C. for 1 hour and then cooled to 25° C., 5.5 g (50.9 mmol) of m-phenylenediamine, oxy After adding 23.8 g (118.9 mmol) of dianiline (4,4′-diaminodiphenyl ether) and 100 mL of dry N-methyl-2-pyrrolidone, the mixture was stirred at 45° C. for 150 minutes, and then cooled to room temperature. After 78.5 g (373.8 mmol) of trifluoroacetic anhydride was added dropwise to this solution and stirred for 20 minutes, 53.1 g (408.0 mmol) of 2-hydroxyethyl methacrylate 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 a polyamic acid ester. This is referred to as polyimide precursor A2.
The weight average molecular weight was determined in the same manner as in Synthesis Example 1. A2 had a weight average molecular weight of 35,000.

Further, in the same manner as in Synthesis Example 1, the esterification rate of A2 was determined. The esterification rate of A2 was 70 mol % relative to all carboxy groups (to all carboxy groups and all carboxy esters) (the remaining 30 mol % being carboxy groups).

Examples 1-3 and Comparative Examples 1-6
[Preparation of photosensitive resin composition]
Using the components and blending amounts shown in Table 1, photosensitive resin compositions of Examples 1-3 and Comparative Examples 1-6 were prepared. The blending amounts in Table 1 are parts by mass of each component with respect to 100 parts by mass of component (A).

Each component used is as follows. As the component (A), the polyimide precursor A1 obtained in Synthesis Example 1 and the polyimide precursor A2 obtained in Synthesis Example 2 were used.

(B1) Component B1: A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd., tricyclodecanedimethanol diacrylate, compound represented by the following formula)

(B2) Component B2: ATM-4E (manufactured by Shin-Nakamura Chemical Co., Ltd., tetrakis methantetrayl tetrakis (methyleneoxyethylene) acrylate)
B3: TEGDMA (manufactured by Sartomer, tetraethylene glycol dimethacrylate)

B4: A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd., tetramethylolmethane tetraacrylate, compound represented by the following formula)

B5: ATM-35E (manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated pentaerythritol tetraacrylate, compound represented by the following formula D2-6, n11 + n12 + n13 + n14 = 35)

(C) Component C1: Irgacure TPO (manufactured by BASF Japan, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide)
C2: Irgacure 819 (manufactured by BASF Japan, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide)

(C') Component C3: IRGACURE OXE 02 (manufactured by BASF Japan Ltd., ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O- Acetyl oxime))
C4: G-1820 (PDO) (manufactured by Lambson, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime)
C5: BTTB (manufactured by NOF Corporation, 3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone)

(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)

(E) Component E1: Percumyl D (manufactured by NOF Corporation, bis(1-phenyl-1-methylethyl) peroxide)

Polymerization inhibitor F1: Taobn (manufactured by Hampford Research, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]-non-2-ene-2,3-dixoid)

Sensitizer EMK (manufactured by Aldrich, 4,4′-bis(diethylamino)benzophenone)

Solvent KJCMPA-100 (manufactured by KJ Chemicals, 3-methoxy-N,N-dimethylpropanamide)
NMP (N-methyl-2-pyrrolidone)

[Measurement of absorbance of component (D)]
The absorbance of D1 as described above was measured.
D1 was dissolved in chloroform, adjusted to 10 mg/L, and used as a sample for measurement. The measuring equipment and measuring conditions are as follows. As a result, the absorbance of D1 was 0.25.
Measuring instrument: U-3900H (manufactured by Hitachi High-Tech Science Co., Ltd.)
Measurement conditions: cell length: 10.0 mm

[Production of patterned resin film]
The obtained photosensitive resin composition is spin-coated on a silicon wafer using a coating device Act8 (manufactured by Tokyo Electron Co., Ltd.), dried at 105 ° C. for 2 minutes, and dried at 115 ° C. for 2 minutes to form a dry film. A photosensitive resin film having a 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, in the same manner as above, a photosensitive resin film was prepared. Exposure was performed by irradiating a via-forming photomask of 1 μm to 100 μm.
After exposure, the resin film was puddle-developed with cyclopentanone using Act8 for the above development time, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a patterned resin film.

[Evaluation of residual film ratio]
For the photosensitive resin film before exposure and the patterned resin film obtained above, the film thickness was measured using an optical interference film thickness measuring device VM-2210 (manufactured by SCREEN Co., Ltd.), and the residual film rate was determined according to the following formula. Calculated.
Remaining film ratio (%)=(thickness of pattern resin film)/(thickness of photosensitive resin film)×100
Table 1 shows the results.

[Production of pattern cured product]
The resulting patterned 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 Systems Co., Ltd.) to give a patterned cured product (film thickness after curing: 6 to 7 μm ).

[Evaluation of aperture mask dimensions]
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 via mask dimension was evaluated as the opening mask dimension. .
Table 1 shows the results.

[Evaluation of opening width]
For the pattern cured products of Examples 1 to 3 and Comparative Examples 2 to 5 having a residual film rate of 80% or more, cross-sectional observation was performed using focused ion beam processing and a scanning electron microscope combined device (FIB-SEM) SMI500 (Co., Ltd. (manufactured by Hitachi High-Tech Science).
For each pattern, a pattern with a smooth forward tapered cross section was selected from the obtained cross-sectional images. Among the selected patterns, the width of the opening on the substrate with the smallest mask dimension was measured.
Table 1 shows the results. "-" indicates not measured.

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

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

Claims (16)

(A) a polyimide precursor having a polymerizable unsaturated bond,
A photosensitive resin composition containing (B1) a polymerizable monomer having an aliphatic cyclic skeleton, and (C) a compound containing an acylphosphine oxide structure. 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 (B1) contains a polymerizable monomer having a group containing a polymerizable unsaturated double bond and an aliphatic cyclic skeleton. The photosensitive resin according to any one of claims 1 to 3, wherein the component (B1) has a group containing two or more polymerizable unsaturated double bonds and contains a polymerizable monomer having an aliphatic cyclic skeleton. Composition. The photosensitive resin composition according to any one of claims 1 to 3, wherein the component (B1) 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.) 6. The photosensitive resin composition according to claim 5, wherein n1+n2 is 2 or 3. The photosensitive resin composition according to any one of claims 1 to 6, wherein the component (B1) contains a polymerizable monomer represented by the following formula (5).

8. The photosensitive resin composition according to any one of claims 1 to 7, further comprising (B2) a polymerizable monomer other than the component (B1). 9. The photosensitive resin composition according to any one of claims 1 to 8, further comprising (D) an ultraviolet absorber. 10. The photosensitive resin composition according to any one of claims 1 to 9, further comprising (E) 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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