JPWO2020071204A1 - Photosensitive resin composition, manufacturing method of pattern cured product, cured product, interlayer insulating film, cover coat layer, surface protective film and electronic components - Google Patents

Abstract

(A) a polyimide precursor having a polymerizable unsaturated bond, (B) a polymerizable monomer having an aliphatic cyclic skeleton, (C) a photopolymerization initiator, (D) a compound containing an anthracene structure, and (E) a solvent. A photosensitive resin composition containing.

Description

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

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

By the way, in recent years, the miniaturization of transistors, which has supported the high performance of computers, has reached the limit of the scaling law, and a laminated device structure in which semiconductor elements are three-dimensionally laminated for further high performance and high speed. Is attracting attention.

Among the laminated device structures, the multi-die fanout wafer level package (Multi-die Fanout Wafer Level Packaging) is a package manufactured by collectively encapsulating a plurality of dies in one package, and has been conventionally proposed. It is attracting a lot 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 production of multi-die fan-out wafer level packages, low temperature curability is strongly required from the viewpoint of protecting high-performance dies, protecting encapsulants with low heat resistance, and improving yield (for example, patents). Reference 2).

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

Japanese Unexamined Patent Publication No. 2009-265520 International Publication No. 2008/111470 Japanese Unexamined Patent Publication No. 2016-199662

An object of the present invention is a photosensitive resin composition having excellent resolution and patterning property after development, which can form a good cured product even at a low temperature of 200 ° C. or lower, a method for producing a patterned cured product, a cured product, and layers. It is to provide an insulating film, a cover coat layer, a surface protective film and an electronic component.

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

（式（２）中、Ｒ_３〜Ｒ_５は、それぞれ独立に、水素原子又は炭素数１〜３の脂肪族炭化水素基であり、ｍは１〜１０の整数である。）
３．前記（Ｂ）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（Ｂ）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である３に記載の感光性樹脂組成物。
５．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。）
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（Ｂ）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．前記（Ｄ）成分が、下記式（３１）で表される化合物を含む１〜７のいずれかに記載の感光性樹脂組成物。

（式（３１）中、Ｒ_６１は、それぞれ独立に、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数６〜１８のアリール基、原子数５〜１８のヘテロアリール基、又はハロゲン原子であり、ｎ１０は０〜８の整数である。）
９．前記（Ｄ）成分が、ジブトキシアントラセン、ジメトキシアントラセン、ジエトキシアントラセン及びジエトキシエチルアントラセンからなる群から選択される１以上である１〜７のいずれかに記載の感光性樹脂組成物。
１０．さらに、（Ｆ）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．パネルレベルパッケージ用である１〜１０のいずれかに記載の感光性樹脂組成物。
１２．１〜１１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。
１３．前記加熱処理の温度が２００℃以下である１２に記載のパターン硬化物の製造方法。
１４．１〜１１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。
１５．パターン硬化物である１４に記載の硬化物。
１６．１４又は１５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。
１７．１６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 compositions and the like are provided.
1. 1. (A) Polyimide precursor having a polymerizable unsaturated bond,
(B) Polymerizable monomer having an aliphatic cyclic skeleton,
(C) Photopolymerization initiator,
A photosensitive resin composition containing (D) a compound containing an anthracene structure and (E) a solvent.
2. The photosensitive resin composition according to 1, wherein the component (A) is a polyimide precursor having a structural unit represented by the following formula (1).

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

(In the formula (2), R _{3 to} R ₅ are independently hydrogen atoms or aliphatic hydrocarbon groups having 1 to 3 carbon atoms, and m is an integer of 1 to 10.)
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 and having an aliphatic cyclic skeleton.
4. 3. The photosensitive resin composition according to 3, wherein the component (B) is a polymerizable monomer having a group containing two or more polymerizable unsaturated double bonds and having an aliphatic cyclic skeleton.
5. 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 the formula (3), R ₆ and R ₇ are independently aliphatic hydrocarbon groups having 1 to 4 carbon atoms or groups represented by the following formula (4). N1 is 0 or 1. , n2 is an integer of 0 to 2, n1 + n2 is at least one of .n1 one of _{R 6} and n2 amino _{R 7} is 1 or more, a group represented by the following formula (4).)

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

8. The photosensitive resin composition according to any one of 1 to 7, wherein the component (D) contains a compound represented by the following formula (31).

In formula (31), R ₆₁ independently has an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a heteroaryl having 5 to 18 atoms. It is a group or a halogen atom, and n10 is an integer of 0 to 8.)
9. The photosensitive resin composition according to any one of 1 to 7, wherein the component (D) is one or more selected from the group consisting of dibutoxyanthracene, dimethoxyanthracene, diethoxyanthracene and diethoxyethyl anthracene.
10. The photosensitive resin composition according to any one of 1 to 9, further comprising (F) a thermal polymerization initiator.
11. The photosensitive resin composition according to any one of 1 to 10 for a panel level package.
A step of applying the photosensitive resin composition according to any one of 12.1 to 11 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, and
A step of developing the resin film after the pattern exposure using an organic solvent to obtain a pattern resin film, and
A method for producing a cured pattern product, which comprises a step of heat-treating the pattern resin film.
13. The method for producing a patterned cured product according to 12, wherein the temperature of the heat treatment is 200 ° C. or lower.
A cured product obtained by curing the photosensitive resin composition according to any one of 14.1 to 11.
15. The cured product according to 14, which is a pattern cured product.
An interlayer insulating film, a cover coat layer or a surface protective film produced by using the cured product according to 16.14 or 15.
An electronic component comprising the interlayer insulating film, covercoat layer or surface protective film according to 17.16.

According to the present invention, a photosensitive resin composition having excellent resolution and patterning property after development, a method for producing a patterned cured product, a cured product, and layers, which can form a good cured product even at a low temperature of 200 ° C. or lower. Insulating films, covercoat layers, surface protective films and electronic components can be provided.

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

Hereinafter, embodiments of the 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. The present invention is not limited to the following embodiments.

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

The photosensitive resin composition of the present invention comprises (A) a polyimide precursor having a polymerizable unsaturated bond (hereinafter, also referred to as “component (A)”), and (B) a polymerizable monomer having an aliphatic cyclic skeleton. (Also referred to as "crosslinking agent") (hereinafter, also referred to as "(B) component"), (C) photopolymerization initiator (hereinafter, also referred to as "(C) component"), (D) anthracene structure. It contains a compound containing (hereinafter, also referred to as "(D) component") and (E) solvent (hereinafter, also referred to as "(E) component").

As a result, a good cured product can be formed even when cured at a low temperature of 200 ° C. or lower, and the resolution and patterning property after development are excellent.
Further, as an arbitrary effect, a good cured product can be formed even at a low temperature curing of 200 ° C. or lower, and a cured product having excellent resolution after curing can be formed.

The photosensitive resin composition of the present invention is preferably a negative photosensitive resin composition.
Further, the photosensitive resin composition of the present invention has an external terminal due to a panel level package (for example, a rewiring layer that draws out wiring from a chip terminal instead of having no package substrate) from the viewpoint of photosensitive characteristics during h-line exposure. It is preferable that it is for a package having a structure that can be connected to. The photosensitive resin composition of the present invention is preferably a material for a panel level package or a material for an electronic component.

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

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

The component (A) is preferably a polyimide precursor having a structural unit represented by the following formula (1). As a result, the i-ray transmittance is high, and a good cured product can be formed even when cured at a low temperature of 200 ° C. or lower.
The content of the structural unit represented by the formula (1) is preferably 50 mol% or more, more preferably 80 mol% or more, and 90 mol% or more with respect to all the constituent units of the component (A). More preferred. The upper limit is not particularly limited, and may be 100 mol%.

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

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

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

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

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

Examples of the aromatic hydrocarbon group of X ₁ of the formula (1), a divalent to tetravalent formed from a benzene ring (divalent, trivalent or tetravalent) group, a divalent to tetravalent radical formed from naphthalene , 2-4 valent 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 of X 1} of the formula (1) include, but are not limited to, the tetravalent group of the following formula (6).

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

In formula (6), the divalent groups of X and Y that are not conjugated to the benzene ring to which they are bonded are -O-, -S-, methylene group, bis (trifluoromethyl) methylene group, or difluoromethylene group. Is preferable, and —O— is more preferable.

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

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

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

Examples of the monovalent aliphatic hydrocarbon group (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms _{) of R 12 to} R ₁₉ of the formula (7) include a 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) of R 12 to} R ₁₉ of the formula (7) is a monovalent aliphatic hydrocarbon group having a halogen atom (preferably having 1 to 10 carbon atoms). The number of carbon atoms is preferably 1 to 6), and examples thereof include a trifluoromethyl group.

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

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

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

The polyimide precursor having the structural unit represented by the formula (1) is composed of, for example, a tetracarboxylic acid dianhydride represented by the following formula (8) and a diamino compound represented by the following formula (9). -Methyl-2-pyrrolidone or the like is reacted in an organic solvent to obtain a polyamic acid, a compound represented by the following formula (10) is added, and the reaction is carried out in an organic solvent to partially introduce an ester group. Obtainable.
The tetracarboxylic dianhydride represented by the formula (8) and the diamino compound represented by the formula (9) may be used alone 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 the formula (8), _{X 1} is a group corresponding to _{X 1} of the formula (1).)

（式（９）中、Ｙ_１は式（１）で定義した通りである。）

(In equation (9), Y ₁ is as defined in equation (1).)

（式（１０）中、Ｒは上述の式（２）で表される基である。）

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

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

(In formula (11), X ₂ is a tetravalent group having one or more aromatic groups, and the -COOR ₅₁ group and the -CONH- group are in ortho positions with each other, and the -COOR ₅₂ group and the -CO are in the ortho position. -The groups are in ortho positions with each other. Y ₂ is a divalent aromatic group. R ₅₁ and R ₅₂ are independently hydrogen atoms or aliphatic hydrocarbon groups having 1 to 4 carbon atoms. )

_{Examples of the tetravalent group having one or more aromatic groups of X 2} of the formula (11) are the same as those of the tetravalent group having one or more aromatic groups of X ₁ of the formula (1).
Examples of the Y ₂ divalent aromatic group of the formula (11) include those similar to the _{Y 1 divalent aromatic group of the formula (1).}
Examples of the aliphatic hydrocarbon groups having 1 to 4 carbon atoms _{of R 51} and R ₅₂ of the formula (11) are the same as those of the aliphatic hydrocarbon groups having 1 to 4 carbon atoms of _{R 1} and R _2.

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

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

In the component (A), the ratio of the carboxy group esterified with the group represented by the formula (2) to the total carboxy group and the total carboxy ester is preferably 50 mol% or more, preferably 60 to 100. More preferably mol%, more preferably 70-90 mol%.

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

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

The component (B) has a group containing a polymerizable unsaturated double bond (preferably two or more) (preferably a (meth) acrylic group because it can be polymerized by a photopolymerization initiator). It is preferable to contain a polymerizable monomer having an aliphatic cyclic skeleton, and in order to improve the crosslink density and photosensitivity and suppress the swelling of the pattern after development, a group containing 2 to 3 polymerizable unsaturated double bonds. It is preferable to have.

（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 component (B) preferably contains a polymerizable monomer represented by the following formula (3).

(In the formula (3), R ₆ and R ₇ are independently aliphatic hydrocarbon groups having 1 to 4 carbon atoms or groups represented by the following formula (4). N1 is 0 or 1. , n2 is an integer of 0 to 2, n1 + n2 is 1 or more .n1 one at least one of _{R 6} and n2 amino _{R 7} (preferably 2 or 3) (preferably 2 or 3), below It is a group represented by the formula (4).)

When R ₇ is two, the two R ₇ may be the same or may be 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 the formula (4), R _{9 to} R ₁₁ are independently hydrogen atoms or aliphatic hydrocarbon groups having 1 to 3 carbon atoms, and l is an integer of 0 to 10 (preferably 0, 1 or 2). ).)

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

Further, as the component (B), for example, the following polymerizable monomer 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 the formula (12), R _{21 to} R ₂₄ are independently aliphatic hydrocarbon groups having 1 to 4 carbon atoms or groups represented by the above formula (4). n3 is an integer of 1-3 (preferably 2 or 3). n4 is an integer of 1-3 (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 21s} are present, the two or more R _21s may be the same or different.
When _{two or more R 22s} are present, the two or more R _22s may be the same or different.

At least one (preferably 2 or 3) of n3 R _21s is a group represented by the above formula (4).
At least one (preferably 2 or 3) of n4 R _22s is a group represented by the above formula (4).
At least one (preferably 2) of n5 R ₂₃ and n 6 R ₂₄ is a group represented by the above formula (4).

As the aliphatic hydrocarbon group having 1 to 4 carbon atoms _{of R 6} and R ₇ of the formula (3) _{and R 21 to} R ₂₄ of the formula (12), _{the carbon number 1 of R 1} and R ₂ of the formula (1) The same as the aliphatic hydrocarbon group of ~ 4 can be mentioned.

The aliphatic hydrocarbon group having 1 to 3 carbon atoms _{of R 9 to} R ₁₁ of the formula (4) is the same as the aliphatic hydrocarbon group having 1 to 3 carbon atoms _{of R 3 to} R _{5 of the formula (2).} Things can be mentioned.

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

The content of the component (B) is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the component (A). From the viewpoint of improving the hydrophobicity of the cured product, it is more preferably 3 to 50 parts by mass, and further preferably 5 to 35 parts by mass.
When it is within the above range, a practical relief pattern can be easily obtained, and post-development residue in the unexposed portion can be easily suppressed.

Examples of the component (C) include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, and fluorenone.
Acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, etc.
Thioxantone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethyl thioxanthone,
Benzyl derivatives such as benzyl, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal, etc.
Benzoin derivatives such as benzoin and benzoin methyl ether, and 1-phenyl-1,2-butandion-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-methoxycarbonyl) Oxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-benzoyl) oxime, 1,3-diphenylpropanthrion -2- (O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanthrion-2- (O-benzoyl) oxime, etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- Carbazole-3-yl]-, 1- (O-acetyloxime), oxime esters such as compounds represented by the following formulas are preferable, but the present invention is not limited thereto.

Oxime esters are particularly preferable in terms of photosensitivity.

The component (C) preferably contains (C1) a compound represented by the following formula (15) (hereinafter, also referred to as “component (C1)”).
The component (C1) preferably has a higher sensitivity to active light than the component (C2) described later, and is preferably a highly sensitive photosensitizer.

式（１５）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), R _11A is an alkyl group having 1 to 12 carbon atoms, and a1 is an integer of 0 to 5. R _12A is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. R _13A and R _14A 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, respectively. When a1 is an integer of 2 or more, R _11A may be the same or different.

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

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

Further, the component (C) preferably contains (C2) a compound represented by the following formula (16) (hereinafter, also referred to as “component (C2)”).
The component (C2) preferably has a lower sensitivity to active light than the component (C1), and is preferably a photosensitizer having a 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 independently hydrogen atoms and alkyl groups 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 trill group, and c1 is an integer of 0 to 5. When c1 is an integer of 2 or more, R _21A may be the same or different.

c1 is preferably 0. R _22A is preferably an alkyl group having 1 to 4 carbon atoms, and 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, and further preferably a methoxy group or an ethoxy group.

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

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

The component (C) preferably contains one or more selected from the group consisting of the component (C1) and the component (C2).
Further, the component (C) preferably contains the component (C1) and the component (C2).

The content of the component (C) is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and further preferably 0.2 to 20 parts by mass with respect to 100 parts by mass of the component (A). It is 10 parts by mass.
Within the above range, the photocrosslinking tends to be uniform in the film thickness direction, and a practical relief pattern can be easily obtained.

When the component (C1) is contained, the content of the component (C1) is usually 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the component (A), preferably 0.07 to 2. It is 5 parts by mass, more preferably 0.09 to 1.0 parts by mass.

When the component (C2) is contained, the content of the component (C2) is usually 0.5 to 15.0 parts by mass with respect to 100 parts by mass of the component (A), preferably 1.0 to 13. It is 0 parts by mass.

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

When the component (C1) and the component (C2) are contained, the mass ratio of the contents of the component (C1) and the component (C2) is preferably 1:30 to 1:70, more preferably 1:35 to 1. It is 1:65.

（式（３１）中、Ｒ_６１は、それぞれ独立に、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数６〜１８のアリール基、原子数５〜１８のヘテロアリール基、又はハロゲン原子（好ましくは、フッ素原子）であり、ｎ１０は０〜８の整数（好ましくは１〜４の整数、より好ましくは２，３又は４）である。）The component (D) preferably contains a compound represented by the following formula (31) from the viewpoint of achieving both sensitivity and resolution.

In formula (31), R ₆₁ independently has an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a heteroaryl having 5 to 18 atoms. It is a group or a halogen atom (preferably a fluorine atom), and n10 is an integer of 0 to 8 (preferably an integer of 1 to 4, more preferably 2, 3 or 4).

Examples of the alkyl group having 1 to 10 carbon atoms (preferably 1 to 6, more preferably 2 to 5) include a methyl group, an ethyl group, a t-butyl group, an n-butyl group and the like.
Examples of the alkoxy group having 1 to 10 carbon atoms (preferably 1 to 6, more preferably 2 to 5) include a butoxy group (for example, n-butoxy group), a methoxy group, an ethoxy group and the like.

Examples of the aryl group having 6 to 18 carbon atoms (preferably 6 to 12, more preferably 6 to 10) include a phenyl group and a naphthyl group.
Examples of the heteroaryl group having 5 to 18 atoms (preferably 5 to 12, more preferably 5 to 10) include a pyridyl group, a quinolinyl group, a carbazolyl group and the like.

Further, the component (D) is preferably dialkoxyanthracene (for example, 9,10 dialkoxyanthracene) which may have a substituent from the viewpoint of achieving both solubility in the photosensitive resin composition and photosensitive characteristics. Butoxyanthracene (eg 9,10 dibutoxyanthracene), dimethoxyanthracene (eg 9,10 dimethoxyanthracene), diethoxyanthracene (eg 9,10 diethoxyanthracene), and diethoxyethyl anthracene (eg 9,10 dimethoxy-2 ethyl) It is preferably 1 or more selected from the group consisting of anthracene).
Examples of the substituent include a methyl group, an ethyl group, a t-butyl group, an n-butyl group and the like.

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

The content of the component (D) is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, and further preferably 0.3 to 20 parts by mass with respect to 100 parts by mass of the component (A). 5 parts by mass.
When it is within the above range, it is possible to achieve both solubility in the photosensitive resin composition and improvement of the photosensitive characteristics.

The photosensitive resin composition of the present invention contains (E) a solvent.
As the component (E), N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, Examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, cyclohexanone, cyclopentanone, diethylketone, diisobutylketone, methylamylketone, N-dimethylmorpholin and the like. Usually, there is no particular limitation as long as other components can be sufficiently dissolved.
Among these, N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, N, N-dimethylformamide from the viewpoint of excellent solubility of each component and coating property at the time of 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。）Further, as the component (E), a compound represented by the following formula (21) may be used.

(In the formula, R _{41 to} R ₄₃ are independently alkyl groups having 1 to 10 carbon atoms.)

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

The component (E) may be used alone or in combination of two or more.
The content of the component (E) is not particularly limited, but is generally 50 to 1000 parts by mass with respect to 100 parts by mass of the component (A).

From the viewpoint of accelerating the polymerization reaction, the photosensitive resin composition of the present invention may further contain (F) a thermal polymerization initiator (hereinafter, also referred to as “component (F)”).
As the component (F), it is not decomposed by heating (drying) for removing the solvent at the time of film formation, but is decomposed by heating at the time of curing to generate radicals, and the components (B) or (A) and A compound that promotes the polymerization reaction of the component (B) is preferable.
The component (F) preferably has a decomposition point of 110 ° C. or higher and 200 ° C. or lower, and more preferably 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-hexyl peroxide) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 1, Peroxyketal such as 1-di (t-butylperoxy) cyclohexane, hydroperoxides such as 1,1,3,3-tetramethylbutylhydroperoxide, cumenehydroperoxide, p-mentan hydroperoxide, dicumylperoxide, di. Dialkyl peroxides such as -t-butyl peroxide, diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide, peroxy such as di (4-t-butylcyclohexyl) peroxydicarbonate and di (2-ethylhexyl) peroxydicarbonate. Dicarbonate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxybenzoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexa Peroxyesters such as Noate, bis (1-phenyl-1-methylethyl) peroxide and the like can be mentioned. Examples of commercially available products include trade names "Park Mill D", "Park Mill P", "Park Mill H" (all manufactured by NOF CORPORATION) and the like.

When the component (F) is contained, the content of the component (F) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (A), and is 0 to ensure good flux resistance. .2 to 20 parts by mass is more preferable, and 0.3 to 10 parts by mass is further preferable from the viewpoint of suppressing a decrease in solubility due to decomposition during drying.

The photosensitive resin composition of the present invention further contains a coupling agent (adhesive aid), a surfactant or a leveling agent, a rust preventive, a cross-linking agent other than the component (B), a sensitizer, a polymerization inhibitor and the like. It may be contained.

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

（式（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, the adhesiveness to the substrate can be further improved even when the curing is performed at a low temperature of 200 ° C. or lower.
The compound represented by the following formula (13) is more preferable because it is excellent in the development of adhesiveness when cured at a low temperature.

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

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

As the silane coupling agent, a silane coupling agent having a hydroxy group or a glycidyl group may be used. When a silane coupling agent having a hydroxy group or a glycidyl group and a silane coupling agent having a urea bond in the molecule are used in combination, the adhesiveness of the cured product during low temperature curing to the substrate can be further improved.
Examples of the silane coupling agent having a hydroxy group or a glycidyl group include methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, and tert-. 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, Examples thereof include 4-bis (dipropylhydroxysilyl) benzene, 1,4-bis (dibutylhydroxysilyl) benzene, and a compound represented by the following formula (14). Of these, 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 the formula (14), R ₃₃ is a monovalent organic group having a hydroxy group or a glycidyl group, R ₃₄ and R ₃₅ are independently alkyl groups having 1 to 5 carbon atoms, and c is 1 to 1. It is an integer of 10, and d is an integer of 1 to 3.)

Examples of the compound represented by the formula (14) include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-. Hydroxypropyltriethoxysilane, 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2- Glycydoxyethyl triethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybutyltriethoxysilane, etc. Be done.

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

Still silane coupling agent having an amide _{bond, R 36 - (CH 2)} e -CO-NH- (CH 2) f -Si (OR 37) 3 (R 36 is a hydroxy group or a glycidyl group, e And f are independently integers of 1 to 3 and R ₃₇ is a methyl group, an ethyl group or a propyl group).

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

When a silane coupling agent is used, the content of the silane coupling agent is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 10 parts by mass, based on 100 parts by mass of the component (A). 10 parts by mass is more preferable.

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

Examples of the surfactant or leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether and the like, and commercially available products include the trade name "Megafuck F171". , "F173", "R-08" (above, manufactured by DIC Co., Ltd.), product name "Florard FC430", "FC431" (above, manufactured by Sumitomo 3M Co., Ltd.), trade name "Organosiloxane Polymer KP341", " Examples thereof include "KBM303", "KBM403", and "KBM803" (all manufactured by Shin-Etsu Chemical Industry Co., Ltd.).

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

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

By containing a rust preventive, it is possible to suppress corrosion and prevent discoloration of copper and copper alloys.
Examples of the rust preventive include a triazole derivative and a tetrazole derivative.
Examples of the rust preventive include 5-aminotetrazole (for example, 5-amino-1H-tetrazole), benzotriazole, 1-hydroxybenzotriazole, 1H-benzotriazole-1-acetoform, benzotriazole-5-carboxylic acid, and 1H-benzo. Examples thereof include triazole-1-methanol, carboxybenzotriazole, and mercaptobenzotriazole. Among these, 5-aminotetrazole, benzotriazole or 1-hydroxybenzotriazole is preferable.
The rust preventive may be used alone 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, and 0.5 to 5 parts by mass with respect to 100 parts by mass of the component (A). 3 parts by mass is more preferable.

By including a cross-linking agent other than the component (B), the photosensitive characteristics, the cured product characteristics, and the like can be flexibly adjusted, and in particular, the cured product characteristics can be greatly changed.

Examples of the cross-linking agent other than the component (B) include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and 1,4-butane. Didiol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, tri Methylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate,
Tetramethylolmethane Tetraacrylate, Tetramethylolmethane Tetramethacrylate, Dipentaerythritol Hexaacrylate, Dipentaerythritol Hexamethacrylate, Pentaerythritol Tetraacrylate, Triacrylate ethoxylated isocyanuric acid, Trimethacrylate ethoxylated isocyanuric acid, Acryloyloxyethyl isocyanurate , Methacryloyloxyethyl isocyanurate and the like.

The cross-linking agent other than the component (B) may be used alone or in combination of two or more.

When a cross-linking agent other than the component (B) is contained, the content of the cross-linking agent other than the component (B) is preferably 0.01 to 20 parts by mass, and 0.05 to 15 parts by mass with respect to 100 parts by mass of the component (A). Parts by mass are more preferable, and parts by mass of 1 to 12 are even more preferable.

As sensitizers, Michler's ketone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-t-butyl anthraquinone, 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-propanol, diacetylbenzyl, benzyldimethylketal, benzyldiethylketal, diphenyldisulfide, anthracene, phenanthrenequinone, riboflavintetrabutyrate, aclysine orange, erythrosin, phenance Renquinone, 2-isopropylthioxanthone, 2,6-bis (p-diethylaminobenzylene) -4-methyl-4-azacyclohexanone, 6-bis (p-dimethylaminobenzylene) -cyclopentanone, 2,6-bis ( p-diethylaminobenzylene) -4-phenylcyclohexanone, aminostyryl ketone, 3-ketocoumarin compound, biscumarin compound, N-phenylglycine, N-phenyldiethanolamine, and 3,3', 4,4'-tetra (t-butyl) Peroxycarbonyl) benzophenone, compounds represented by the following formulas and the like can be mentioned.

As the sensitizer, one type may be used alone, or two or more types may be used in combination.

When a sensitizer is contained, the blending amount of the sensitizer is preferably 0.1 to 1.5 parts by mass, more preferably 0.2 to 1.2 parts by mass with respect to 100 parts by mass of the component (A). preferable.

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

Examples of the polymerization inhibitor include 1,4,4-trimethyl-2,3-diazabicyclo [3.2.2] -none-2-ene-2,3-dixoid, p-methoxyphenol, and diphenyl-p-. Benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N-phenyl-2-naphthylamine, cuperon, 2,5-torquinone, tannic acid, parabenzylaminophenol , Nitrosoamines and the like.

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

When a polymerization inhibitor is contained, the content of the polymerization inhibitor is 0 with respect to 100 parts by mass of the component (A) from the viewpoint of storage stability of the photosensitive resin composition and heat resistance of the obtained cured product. It is 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.

The photosensitive resin composition of the present invention essentially contains components (A) to (E), and optionally components (F), a coupling agent, a surfactant, a leveling agent, a rust preventive, and a component (B). It is composed of a cross-linking agent, a sensitizer and a polymerization inhibitor other than the above, and may contain other unavoidable impurities as long as the effects of the present invention are not impaired.
For example, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 100% by mass of the photosensitive resin composition of the present invention.
Ingredients (A) to (E),
A cross-linking agent other than the components (A) to (F), or the components (A) to (E), and optionally the component (F), a coupling agent, a surfactant, a leveling agent, a rust preventive agent, and a component (B). , A sensitizer and a polymerization inhibitor.

The cured product of the present invention can be obtained by curing the above-mentioned photosensitive resin composition.
The cured product of the present invention may be used as a patterned cured product or as a cured product without a pattern.
The film thickness of the cured product of the present invention is preferably 5 to 20 μm.

In the method for producing a cured pattern of the present invention, the above-mentioned photosensitive resin composition is applied onto a substrate and dried to form a photosensitive resin film, and the photosensitive resin film is pattern-exposed to form a resin film. It includes a step of obtaining, a step of developing the resin film after pattern exposure with an organic solvent to obtain a pattern resin film, and a step of heat-treating the pattern resin film.
Thereby, a pattern cured product can be obtained.

A method for producing a cured product without a pattern includes, for example, a step of forming the above-mentioned photosensitive resin film and a step of heat treatment. Further, an exposure step may be provided.

Examples of the substrate include a glass substrate, a semiconductor substrate such as a Si substrate (silicon wafer), _{a metal oxide insulator substrate such as a TiO 2} substrate and a SiO ₂ substrate, a silicon nitride substrate, a copper substrate, and a copper alloy substrate.

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

Drying can be performed using a hot plate, an oven, or the like.
The drying temperature is preferably 90 to 150 ° C., and more preferably 90 to 120 ° C. from the viewpoint of ensuring the dissolution contrast.
The drying time is preferably 30 seconds to 5 minutes.
Drying may be performed twice or more.
As a result, a photosensitive resin film obtained by forming the above-mentioned 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, and even more preferably 7 to 30 μm.

The pattern exposure exposes a predetermined pattern through, for example, a photomask.
Examples of the active light beam to be irradiated include ultraviolet rays such as i-ray and h-ray, visible light, and radiation, and i-ray is preferable.
As the exposure apparatus, a parallel exposure machine, a projection exposure machine, a stepper, a scanner exposure machine and the like can be used.

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

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

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

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

A cured pattern can be obtained by heat-treating the pattern resin film.
The polyimide precursor of the component (A) undergoes a dehydration ring closure reaction by a heat treatment step to become a normally 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 the substrate and the device can be suppressed to a small extent, the device can be produced with a high yield, and energy saving of the process can be realized.

The heat treatment time is preferably 5 hours or less, more preferably 30 minutes to 3 hours.
Within the above range, the cross-linking reaction or the dehydration ring closure reaction can be sufficiently proceeded.
The atmosphere of the heat treatment may be the atmosphere or an inert atmosphere such as nitrogen, but a nitrogen atmosphere is preferable from the viewpoint of preventing oxidation of the patterned resin film.

Examples of the apparatus used for the heat treatment include a quartz tube furnace, a hot plate, a rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, a microwave curing furnace and the like.

The cured product of the present invention can be used as a passivation film, a buffer coat film, an interlayer insulating film, a cover coat layer, a surface protective film, or the like.
Highly reliable semiconductor devices, multilayer wiring boards, various electronic devices, and 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, and the like. It is possible to manufacture electronic parts such as devices (multi-die fan out wafer level package, etc.).

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

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

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

Further, using a known photographic etching technique, the second conductor layer 7 is formed and electrically connected to the first conductor layer 3.
When forming a multi-layer wiring structure having three or more layers, the above steps can be repeated to form each layer.

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

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

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

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

Measuring device: Detector L4000UV manufactured by Hitachi, Ltd.
Pump: L6000 manufactured by Hitachi, Ltd.
C-R4A Chromatopac manufactured by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5 x 2 Eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.03 mol / L), H ₃ PO ₄ (0.06 mol / L)
Flow rate: 1.0 mL / min, Detector: UV270 nm

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

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

Examples 1-9 and Comparative Examples 1-3
(Preparation of photosensitive resin composition)
The photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 3 were prepared with the components and blending amounts shown in Tables 1 and 2. The blending amounts in Tables 1 and 2 are parts by mass of each component with respect to 100 parts by mass of A1.

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

(B) Component: Polymerizable monomer having an aliphatic cyclic skeleton B1: A-DCP (manufactured by Shin Nakamura Chemical Industry Co., Ltd., tricyclodecanedimethanol diacrylate, compound represented by the following formula B1)

(C) Ingredient: Photopolymerization Initiator C1: IRUGCURE OXE 02 (manufactured by BASF Japan Ltd., Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1 -(O-acetyloxime))
C2: G-1820 (PDO) (1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, manufactured by Rambson Co., Ltd.)

(D) Ingredient D1: 9,10 Dibutoxyanthracene (manufactured by Kawasaki Kasei Chemicals Co., Ltd.)

(E) Component: Solvent E1: N-Methyl-2-pyrrolidone E2: KJCMPA-100 (manufactured by KJ Chemicals Co., Ltd., compound represented by the following formula E2)

Component (F): Thermal polymerization initiator F1: Parkmill D (manufactured by NOF CORPORATION, bis (1-phenyl-1-methylethyl) peroxide, compound represented by the following formula)

Cross-linking agent other than the component (B) ATM-4E: Pentaerythritol tetraacrylate ethoxylated (manufactured by Shin Nakamura Chemical Industry Co., Ltd., a compound represented by the following formula (n11 + n12 + n13 + n14 is 4))

Sensitizer BCIM: 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole (manufactured by Hampford Research, compound represented by the following formula)

Leuco dye LCV: Leuco crystal violet (manufactured by Yamada Chemical Co., Ltd., compound represented by the following formula)

EMK: 4,4'-bis (diethylamino) benzophenone

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

Rust inhibitor 5Atz: 5-amino-1H-tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

Adhesive aid UCT-801: 3-Ureidopropyltriethoxysilane (manufactured by United Chemical Technologies)

(Measurement of residual film ratio after development 1)
The obtained photosensitive resin composition was spin-coated on a silicon wafer using a coating device Act8 (manufactured by Tokyo Electron Limited), dried at 100 ° C. for 2 minutes, and then dried at 110 ° C. for 2 minutes to form a dry film. A photosensitive resin film having a thickness of 7 to 15 μm was formed.
The development time was set to twice the time required for the obtained photosensitive resin film to be immersed in cyclopentanone and completely dissolved.
Further, a photosensitive resin film was prepared in the same manner as described above, and the obtained photosensitive resin film was irradiated with i-rays of ^{200 mJ / cm 2 using an i-line stepper FPA-3000iW (manufactured by Canon Inc.).} , Exposure was performed.
The exposed resin film was paddle-developed with cyclopentanone using Act8 for the above-mentioned development time, and then rinse-washed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a resin film.
Regarding the film thickness after heating for 2 minutes on a hot plate at 110 ° C. and the film thickness after development, the silicon wafer is exposed by scratching a part of the film, and the height from the exposed silicon wafer surface to the film surface is determined. The measurement was performed using a needle-contact type profiler Dektak 150 (manufactured by Bruker) (the film thickness is measured in the same manner below).
The film thickness of 10 μm after development was divided by the film thickness after heating for 2 minutes on a hot plate at 110 ° C., and then made into a percentage to determine the residual film ratio after development. The case where the residual film ratio after development was 55 to 100% was designated as A, the case where it was 40% or more and less than 55% was designated as B, and the case where it was 0% or more and less than 40% was designated as C. The results are shown in Tables 1 and 2.

(Manufacturing of cured product 1)
In Examples 1 to 9, the resin film obtained in the measurement 1 of the residual film ratio after development was subjected to a vertical diffusion furnace μ-TF (manufactured by Koyo Thermo System Co., Ltd.) at 175 ° C. in a nitrogen atmosphere. The mixture was heated for 1 hour to obtain a cured product (thickness 7 to 10 μm after curing).
Good cured products were obtained for Examples 1-9.

(Measurement of residual film ratio after development 2)
The above-mentioned photosensitive resin composition is spin-coated on a silicon wafer using a coating device Act8, dried at 100 ° C. for 2 minutes, and then dried at 110 ° C. for 2 minutes to have a dry film thickness of 7 to 15 μm. A resin film was formed.
The development time was set to twice the time required for the obtained photosensitive resin film to be immersed in cyclopentanone and completely dissolved.
Further, a photosensitive resin film was prepared in the same manner as described above, and the obtained photosensitive resin film was 200 mJ / cm using a mask aligner MA-8 (manufactured by Susu Microtech) and an h-line bandpass filter. ^The exposure was performed by irradiating the h line of No. 2.
The exposed resin film was paddle-developed with cyclopentanone using Act8 for the above-mentioned development time, and then rinse-washed with PGMEA to obtain a resin film.
The film thickness after heating for 2 minutes on a hot plate at 110 ° C. and the film thickness after development were measured in the same manner as in Measurement 1 of the residual film ratio after development.
The film thickness of 10 μm after development was divided by the film thickness after heating for 2 minutes on a hot plate at 110 ° C., and then made into a percentage to determine the residual film ratio after development. The case where the residual film ratio after development was 55 to 100% was designated as A, the case where it was 40% or more and less than 55% was designated as B, and the case where it was 0% or more and less than 40% was designated as C. The results are shown in Tables 1 and 2.

(Manufacturing of cured product 2)
In Examples 1 to 9, the resin film obtained in the measurement 2 of the residual film thickness after development was heated in a nitrogen atmosphere at 175 ° C. for 1 hour using a vertical diffusion furnace μ-TF to obtain a cured product (a cured product (). After curing, a film thickness of 7 to 10 μm) was obtained.
Good cured products were obtained for Examples 1-9.

(Patterning evaluation)
The above-mentioned photosensitive resin composition is spin-coated on a silicon wafer using a coating device Act8, dried at 100 ° C. for 2 minutes, and then dried at 110 ° C. for 2 minutes to have a dry film thickness of 7 to 15 μm. A resin film was formed.
The development time was set to twice the time required for the obtained photosensitive resin film to be immersed in cyclopentanone and completely dissolved.
Further, a photosensitive resin film was prepared in the same manner as described above, and the obtained photosensitive resin film was used with a mask aligner MA-8 (manufactured by Susu Microtech) using an h-line bandpass filter at 500 mJ / cm. ^A predetermined pattern (10 μm line-and-space pattern) was irradiated with h-line No. 2 to perform exposure.
The exposed resin film was paddle-developed with cyclopentanone using Act8 for the above-mentioned development time, and then rinse-washed with PGMEA to obtain a patterned resin film.
The obtained pattern resin film was observed with an optical microscope, and the case where the line pattern was not peeled off was designated as A, the case where even one line pattern was peeled off was designated as B, and the case where patterning could not be performed was designated as C. The results are shown in Tables 1 and 2.

(Manufacturing of cured pattern)
The obtained pattern resin film was heated at 175 ° C. for 1 hour in a nitrogen atmosphere using a vertical diffusion furnace μ-TF to obtain a pattern cured product (thickness after curing 10 μm).
Good cured products were obtained for Examples 1-9.

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

Although some embodiments and / or embodiments of the present invention have been described above in detail, those skilled in the art will be able to demonstrate these embodiments and / or embodiments without substantial departure from the novel teachings and effects of the present invention. It is easy to make many changes to the examples. Therefore, many of these modifications are within the scope of the invention.
All the documents described in this specification and the contents of the application on which the priority under the Paris Convention of the present application is based are incorporated.

Claims (17)

(A) Polyimide precursor having a polymerizable unsaturated bond,
(B) Polymerizable monomer having an aliphatic cyclic skeleton,
(C) Photopolymerization initiator,
A photosensitive resin composition containing (D) a compound containing an anthracene structure and (E) a solvent. The photosensitive resin composition according to claim 1, wherein the component (A) is a polyimide precursor having a structural unit represented by the following formula (1).

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

(In the formula (2), R _{3 to} R ₅ are independently hydrogen atoms or aliphatic hydrocarbon groups having 1 to 3 carbon atoms, and m is an integer of 1 to 10.) The photosensitive resin composition according to claim 1 or 2, wherein the component (B) contains a polymerizable monomer having a group containing a polymerizable unsaturated double bond and having an aliphatic cyclic skeleton. The photosensitive resin composition according to claim 3, wherein the component (B) is a polymerizable monomer having a group containing two or more polymerizable unsaturated double bonds and having 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 the formula (3), R ₆ and R ₇ are independently aliphatic hydrocarbon groups having 1 to 4 carbon atoms or groups represented by the following formula (4). N1 is 0 or 1. , n2 is an integer of 0 to 2, n1 + n2 is at least one of .n1 one of _{R 6} and n2 amino _{R 7} is 1 or more, a group represented by the following formula (4).)

(In the formula (4), R _{9 to} R ₁₁ are independently hydrogen atoms or aliphatic hydrocarbon groups having 1 to 3 carbon atoms, and l is an integer of 0 to 10.) 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 (B) contains a polymerizable monomer represented by the following formula (5).

The photosensitive resin composition according to any one of claims 1 to 7, wherein the component (D) contains a compound represented by the following formula (31).

In formula (31), R ₆₁ independently has an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a heteroaryl having 5 to 18 atoms. It is a group or a halogen atom, and n10 is an integer of 0 to 8.) The photosensitive resin composition according to any one of claims 1 to 7, wherein the component (D) is one or more selected from the group consisting of dibutoxyanthracene, dimethoxyanthracene, diethoxyanthracene and diethoxyethyl anthracene. The photosensitive resin composition according to any one of claims 1 to 9, further comprising (F) a thermal polymerization initiator. The photosensitive resin composition according to any one of claims 1 to 10, which is for a panel level package. A step of applying the photosensitive resin composition according to any one of claims 1 to 11 onto 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, and
A step of developing the resin film after the pattern exposure using an organic solvent to obtain a pattern resin film, and
A method for producing a cured pattern product, which comprises a step of heat-treating the pattern resin film. The method for producing a patterned cured product according to claim 12, wherein the temperature of the heat treatment is 200 ° C. or lower. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 11. The cured product according to claim 14, which is a pattern cured product. An interlayer insulating film, a cover coat layer or a surface protective film produced by using the cured product according to claim 14 or 15. An electronic component including the interlayer insulating film, cover coat layer or surface protective film according to claim 16.

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