JP5504735B2 - Positive photosensitive resin composition, pattern cured film manufacturing method, and electronic component - Google Patents

Description

  The present invention relates to a positive photosensitive resin composition, a method for producing a patterned cured film, and an electronic component. More specifically, for example, the present invention relates to a positive photosensitive resin composition capable of forming a surface protective film and / or an interlayer insulating film of a semiconductor element, and a method for producing a heat resistant pattern cured film using the composition.

Conventionally, polyimide resins and polybenzoxazole resins having excellent heat resistance, electrical characteristics, and mechanical characteristics have been used for interlayer insulating films and surface protective films of semiconductor elements.
In recent years, as semiconductor devices are further highly integrated and enlarged, sealing resin packages are required to be thinner and smaller. Also, methods such as surface mounting by LOC (lead-on-chip) or solder reflow have been taken, and polyimide resins having better mechanical properties and heat resistance are required more than ever. It was.

  In response to these demands, a photosensitive polyimide having a polyimide resin itself imparted with photosensitivity has been used. By using the photosensitive polyimide, the pattern production process can be simplified, and complicated manufacturing processes can be shortened. A heat-resistant photoresist using a conventional photosensitive polyimide or its precursor and its application are well known.

  As a development of these technologies, a positive photosensitive resin composition that can be developed with an alkaline aqueous solution has been recently proposed. For positive photosensitive polyimide, a method of introducing a 2-nitrobenzyl group into the polyimide precursor via an ester bond (for example, Non-Patent Document 1), a naphthoquinone diazide compound is mixed with a soluble dihydroxylimide or polybenzoxazole precursor Examples thereof include a method (for example, Patent Documents 1 and 2), a method for mixing naphthoquinonediazide with a polyimide precursor (for example, Patent Document 3), and the like.

  Due to further integration in recent years and an increase in wafer size, materials with higher productivity are desired. In order to improve the productivity, for example, a highly sensitive photosensitive material capable of shortening the exposure time is desired. However, in the photosensitive resin composition mixed with naphthoquinone diazide, it is naturally high due to the limit of photodegradability of naphthoquinone diazide. There was a limit to sensitivity. Further, in the case of a chemically amplified photosensitive resin compound, generally, film properties such as stretchability tend to be lowered.

Japanese Examined Patent Publication No. 64-60630 US Pat. No. 4,395,482 JP 52-13315 A

J. Macromol. Sci. Chem., A24, 12, 1407, 1987.

  The objective of this invention is providing the highly sensitive positive type photosensitive resin composition which can shorten exposure time.

（式中、Ｘ_１は２〜８価の有機基である。Ｙ_１は２〜８価の有機基である。Ｒ_１はそれぞれ水素原子又は炭素数１〜２０の有機基である。Ｒ_２はそれぞれ水素又は１価の有機基である。ｐ及びｑはそれぞれ０〜４の整数である。ｌ及びｍはそれぞれ０〜２の整数である。ｌ＋ｍ＋ｐ＋ｑは１以上である。ｎは重合体中の構造単位の数を示す２以上の整数である。）
（ｂ）ナフトキノンジアジド化合物、
（ｃ）溶剤、及び
（ｄ）ヨードニウム化合物
を含み、下記条件i)及び条件ii)から選択されるいずれかの条件：
i）前記（ｄ）ヨードニウム化合物が、２つ以上の単環式の芳香環が縮合した形の多環式の芳香環の骨格を有するを有すること、
ii）前記（ｄ）ヨードニウム化合物と共に（ｅ）２つ以上の単環式の芳香環が縮合した形の多環式の芳香環の骨格を有する光励起促進剤を含むこと
を満足することを特徴とするポジ型感光性樹脂組成物。
２．前記（ｂ）ナフトキノンジアジド化合物が、ｏ−ナフトキノンジアジド化合物である１に記載のポジ型感光性樹脂組成物。
３．前記（ｄ）ヨードニウム化合物が、下記式（II）で表されるヨードニウム塩である１又は２に記載のポジ型感光性樹脂組成物。

（式中、Ｘは、対陰イオンである。Ｒ_３は、アルキル基、アルケニル基、アルコキシ基、トリアルキルシリル基、前記各基の水素原子の一部又は全部がフッ素原子に置換された基、塩素原子、臭素原子又はフッ素原子である。Ｚは１価の有機基である。ａは、０〜５の整数である。）
４．前記式（II）のＺが、下記式（III）で表される置換基のいずれかである３に記載のポジ型感光性樹脂組成物。

（Ｒ_３は、前記式（II）と同様の定義である。Ｒ_４〜Ｒ_７は、それぞれ、水素原子、アルキル基、アルコキシ基、トリフロロメタンスルホニル基又はトリアルキルシリル基である。ａは、０〜５の整数である。）
５．前記条件i)を満足するものである１〜４のいずれかに記載のポジ型感光性樹脂組成物。
６．前記条件ii）を満足するものである１〜５のいずれかに記載のポジ型感光性樹脂組成物。
７．（ｄ）成分又は（ｅ）成分における多環式の芳香環の骨格が、ナフタレン骨格又はアントラセン骨格である１〜６のいずれかに記載のポジ型感光性樹脂組成物。
８．前記（ｅ）光励起促進剤が下記式（IV）で表されるアントラセン化合物である１〜７のいずれかに記載のポジ型感光性樹脂組成物。

（Ｒ_８〜Ｒ_１０は、それぞれアルキル基、アルコキシ基又はアルケニル基である。）
９．（ａ）式（Ｉ）で表される構造を有する重合体１００重量部に対し、（ｂ）ナフトキノンジアジド化合物を０．０１〜５０重量部、及び（ｄ）ヨードニウム化合物を１〜５０重量部それぞれ含有する１〜８のいずれかに記載のポジ型感光性樹脂組成物。
１０．（ａ）式（Ｉ）で表される構造を有する重合体１００重量部に対し、（ｂ）ナフトキノンジアジド化合物を０．０１〜５０重量部、（ｄ）ヨードニウム化合物を１〜５０重量部、及び（ｅ）光励起促進剤を０．０１〜５０重量部それぞれ含有する１〜８のいずれかに記載のポジ型感光性樹脂組成物。
１１．１〜１０のいずれかに記載のポジ型感光性樹脂組成物を支持基板上に塗布し乾燥して感光性樹脂膜を形成する感光性樹脂膜形成工程と、
前記感光性樹脂膜を所定のパターンに露光する露光工程と、
前記露光後の感光性樹脂膜をアルカリ水溶液を用いて現像してパターン樹脂膜を得る現像工程と、
前記パターン樹脂膜を加熱処理してパターン硬化膜を得る加熱処理工程を含むパターン硬化膜の製造方法。
１２．１１に記載のパターン硬化膜の製造方法により得られるパターン硬化膜を、層間絶縁膜層又は表面保護膜層として有する電子部品。 According to the present invention, the following positive photosensitive resin composition and the like are provided.
1. (A) a polymer having a structure represented by the following formula (I):

(In the formula, X ₁ is a divalent to octavalent organic group. Y ₁ is a divalent to octavalent organic group. R ₁ is a hydrogen atom or an organic group having 1 to 20 carbon atoms. R _2. Are each hydrogen or a monovalent organic group, p and q are each an integer of 0 to 4. l and m are each an integer of 0 to 2. l + m + p + q is 1 or more, and n is in the polymer. (It is an integer of 2 or more indicating the number of structural units.)
(B) a naphthoquinonediazide compound,
(C) a solvent, and (d) any condition selected from the following conditions i) and ii) including an iodonium compound:
i) The (d) iodonium compound has a polycyclic aromatic ring skeleton in which two or more monocyclic aromatic rings are condensed,
and (ii) comprising (d) an iodonium compound and (e) a photoexcitation accelerator having a polycyclic aromatic ring skeleton in which two or more monocyclic aromatic rings are condensed. A positive photosensitive resin composition.
2. 2. The positive photosensitive resin composition according to 1, wherein the (b) naphthoquinonediazide compound is an o-naphthoquinonediazide compound.
3. The positive photosensitive resin composition according to 1 or 2, wherein the (d) iodonium compound is an iodonium salt represented by the following formula (II).

(In the formula, X is a counter anion. R ₃ is an alkyl group, an alkenyl group, an alkoxy group, a trialkylsilyl group, or a group in which part or all of the hydrogen atoms in each of the above groups are substituted with fluorine atoms. , A chlorine atom, a bromine atom or a fluorine atom, Z is a monovalent organic group, and a is an integer of 0 to 5.)
4). 4. The positive photosensitive resin composition according to 3, wherein Z in the formula (II) is any one of substituents represented by the following formula (III).

(R ₃ has the same definition as in formula (II) above. R _{4 to} R ₇ are each a hydrogen atom, an alkyl group, an alkoxy group, a trifluoromethanesulfonyl group, or a trialkylsilyl group. , An integer from 0 to 5.)
5. The positive photosensitive resin composition according to any one of 1 to 4, which satisfies the condition i).
6). The positive photosensitive resin composition according to any one of 1 to 5, which satisfies the condition ii).
7). The positive photosensitive resin composition according to any one of 1 to 6, wherein the skeleton of the polycyclic aromatic ring in the component (d) or the component (e) is a naphthalene skeleton or an anthracene skeleton.
8). The positive photosensitive resin composition according to any one of 1 to 7, wherein (e) the photoexcitation accelerator is an anthracene compound represented by the following formula (IV).

(R _{8 to} R ₁₀ are each an alkyl group, an alkoxy group, or an alkenyl group.)
9. (A) 0.01 to 50 parts by weight of (b) naphthoquinonediazide compound and (d) 1 to 50 parts by weight of iodonium compound with respect to 100 parts by weight of the polymer having the structure represented by formula (I). The positive photosensitive resin composition in any one of 1-8 containing.
10. (A) 0.01 to 50 parts by weight of (b) naphthoquinonediazide compound, (d) 1 to 50 parts by weight of iodonium compound, and 100 parts by weight of the polymer having the structure represented by formula (I), and (E) The positive photosensitive resin composition according to any one of 1 to 8, which contains 0.01 to 50 parts by weight of a photoexcitation accelerator.
A photosensitive resin film forming step of applying the positive photosensitive resin composition according to any one of 11.1 to 10 onto a support substrate and drying to form a photosensitive resin film;
An exposure step of exposing the photosensitive resin film to a predetermined pattern;
A development step of developing the exposed photosensitive resin film using an alkaline aqueous solution to obtain a patterned resin film;
The manufacturing method of the pattern cured film including the heat processing process which heat-processes the said pattern resin film and obtains a pattern cured film.
An electronic component having a patterned cured film obtained by the method for producing a patterned cured film described in 12.11 as an interlayer insulating film layer or a surface protective film layer.

  ADVANTAGE OF THE INVENTION According to this invention, the highly sensitive positive photosensitive resin composition which can shorten exposure time can be provided.

It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure concerning one Embodiment of this invention, Comprising: It is a figure which shows a 1st process. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure concerning one Embodiment of this invention, Comprising: It is a figure which shows a 2nd process. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure concerning one Embodiment of this invention, Comprising: It is a figure which shows a 3rd process. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure concerning one Embodiment of this invention, Comprising: It is a figure which shows a 4th process. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure concerning one Embodiment of this invention, Comprising: It is a figure which shows a 5th process.

（式中、Ｘ_１は２〜８価の有機基である。Ｙ_１は２〜８価の有機基である。Ｒ_１はそれぞれ水素原子又は炭素数１〜２０の有機基である。Ｒ_２はそれぞれ水素又は１価の有機基である。ｐ及びｑはそれぞれ０〜４の整数である。ｌ及びｍはそれぞれ０〜２の整数である。ｌ＋ｍ＋ｐ＋ｑは１以上である。ｎは重合体中の構造単位の数を示す２以上の整数である。）
（ｂ）ナフトキノンジアジド化合物、
（ｃ）溶剤、及び
（ｄ）ヨードニウム化合物。
加えて、本発明のポジ型感光性樹脂組成物は、下記条件i)及び条件ii)から選択される、いずれかの条件を満足するものである。
i）前記（ｄ）ヨードニウム化合物が、２つ以上の単環式の芳香環が縮合した形の多環式の芳香環の骨格を有するを有すること、
ii）前記（ｄ）ヨードニウム化合物と共に（ｅ）２つ以上の単環式の芳香環が縮合した形の多環式の芳香環の骨格を有する光励起促進剤を含むこと。 The positive photosensitive resin composition of the present invention is a composition comprising the following component (a), component (b), component (c) and component (d).
(A) a polymer having a structure represented by the following formula (I):

(In the formula, X ₁ is a divalent to octavalent organic group. Y ₁ is a divalent to octavalent organic group. R ₁ is a hydrogen atom or an organic group having 1 to 20 carbon atoms. R _2. Are each hydrogen or a monovalent organic group, p and q are each an integer of 0 to 4. l and m are each an integer of 0 to 2. l + m + p + q is 1 or more, and n is in the polymer. (It is an integer of 2 or more indicating the number of structural units.)
(B) a naphthoquinonediazide compound,
(C) a solvent, and (d) an iodonium compound.
In addition, the positive photosensitive resin composition of the present invention satisfies any one of conditions selected from the following conditions i) and ii).
i) The (d) iodonium compound has a polycyclic aromatic ring skeleton in which two or more monocyclic aromatic rings are condensed,
ii) It includes (d) an iodonium compound and (e) a photoexcitation accelerator having a polycyclic aromatic ring skeleton in which two or more monocyclic aromatic rings are condensed.

  The positive photosensitive resin composition of the present invention has high sensitivity. Therefore, for example, the exposure time in the semiconductor manufacturing process can be shortened, and the productivity of the semiconductor device can be improved.

  The component (a) contained in the composition of the present invention is a polymer having a structure represented by the formula (I), and generally has heat resistance.

The component (a) in the present invention contains two amide bonds in one structural unit as shown in the structural unit of the formula (I). This is generally formed by the reaction of a carboxylic acid (di-, tri-, tetra-, etc.), its anhydride or its derivative with a diamine.
Accordingly, the divalent to octavalent organic group of X ₁ in formula (I) includes a carboxyl group in which an amide bond is formed by reaction with an amine in the structure of the carboxylic acid, and other acid functional groups (that is, carboxyl An organic group having a structure other than a group or a group esterified with it and a phenolic hydroxyl group or a group in which the hydrogen atom is substituted with a substituent. For example, an organic group corresponding to a structure other than the carboxyl group and acid functional group of tetracarboxylic dianhydride or dicarboxylic acid. X ₁ generally preferably contains an aromatic ring, and the carboxyl group and other acid functional groups are preferably directly bonded to the aromatic ring.

  Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 2,3,3 ′, 4′-biphenyltetracarboxylic acid. Dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′- Benzophenone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1- Bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3- Carboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,3,4-cyclopentanetetracarboxylic Acid dianhydride, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic Acid dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilane Examples include tetracarboxylic dianhydride and 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, which are used alone or in combination of two or more. It is. Moreover, it is not necessarily limited to what was mentioned here.

  Among the above-mentioned tetracarboxylic dianhydrides, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid Dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′- Benzophenone tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, N- (trimellitic acid The dianhydride) -2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is preferred for obtaining good film properties with high heat resistance.

  Examples of the dicarboxylic acid include 3-fluoroisophthalic acid, 2-fluoroisophthalic acid, 3-fluorophthalic acid, 2-fluorophthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, 3,4,5, 6-tetrafluorophthalic acid, 4,4′-hexafluoroisopropylidenediphenyl-1,1′-dicarboxylic acid, perfluorosuberic acid, 2,2′-bis (trifluoromethyl) -4,4′-biphenylenedicarboxylic acid Examples include acids, terephthalic acid, isophthalic acid, 4,4′-oxydiphenyl-1,1′-dicarboxylic acid, and these are used alone or in combination of two or more. Moreover, it is not necessarily limited to what was mentioned here.

  Of the above-mentioned dicarboxylic acids, terephthalic acid, isophthalic acid, and 4,4′-oxydiphenyl-1,1′-dicarboxylic acid are preferable for obtaining good film properties with high heat resistance.

Moreover, in order to adjust alkali solubility, the said dicarboxylic acid may have an acid functional group which shows alkali solubility.
Examples of the dicarboxylic acid having an acid functional group include N- (trimellitic dianhydride) -2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, N- (trimellitic dianhydride). Product) -2,2′-bis (3-amino-4-hydroxyphenyl) propane, N- (trimellitic dianhydride) -4,4′-diamino-3,3′-dihydroxybiphenyl, N- ( Trimellitic dianhydride) -2,2′-bis (3-amino-4-hydroxyphenyl) sulfone, N- (trimellitic dianhydride) -2,2′-bis (3-amino-4-) Hydroxyphenyl) ether, N- (trimellitic dianhydride) -2,2'-bis (3-amino-4-hydroxyphenyl) propane, N- (trimellitic dianhydride) -2,4-diamino Phenol, N -(Trimellitic dianhydride) -2,5-diaminophenol, N- (trimellitic dianhydride) -1,4-diamino-2,5-dihydroxybenzene, etc. Two or more types are used in combination. Moreover, it is not necessarily limited to what was mentioned here.

Among the dicarboxylic acids having an acid functional group described above, N- (trimellitic dianhydride) -2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, N- (trimellitic acid 2 Anhydride) -2,2'-bis (3-amino-4-hydroxyphenyl) propane, N- (trimellitic dianhydride) -4,4'-diamino-3,3'-dihydroxybiphenyl, N- (Trimellitic dianhydride) -2,2′-bis (3-amino-4-hydroxyphenyl) sulfone, N- (trimellitic dianhydride) -2,2′-bis (3-amino-4) -Hydroxyphenyl) ether and N- (trimellitic dianhydride) -2,2'-bis (3-amino-4-hydroxyphenyl) propane are preferred for obtaining good film properties with high heat resistance.
Further, a tricarboxylic acid such as trimellitic acid or its anhydride can be used.

The divalent to octavalent organic group of Y ₁ in formula (I) is, for example, an organic group corresponding to the structure of a diamine and / or a diamine having an acid functional group, excluding two amino groups and an acid functional group. is there.

  Examples of the diamine include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl sulfide, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4- (4- Aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenoxy) benzene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-diethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, , 3′-diethyl-4,4′-diaminobiphenyl, 2,2 ′, 3,3′-tetramethyl-4,4′-diaminobiphenyl, 2,2 ′, 3,3′-tetraethyl-4,4 '-Diaminobiphenyl, 2,2'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2'-dihydroxy-4,4'-diaminobiphenyl, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 2,2′-di (trifluoromethyl) -4,4′-diaminobiphenyl and the like may be mentioned, and these may be used alone or in combination of two or more. used. Moreover, it is not necessarily limited to what was mentioned here.

  Among the above diamines, 4,4′-diaminodiphenyl ether, m-phenylenediamine, p-phenylenediamine, bis (4-aminophenoxy) biphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3, 3'-dimethyl-4,4'-diaminobiphenyl is preferred for obtaining good film properties with high heat resistance.

Moreover, in order to adjust alkali solubility, the said diamine may have an acid functional group which shows alkali solubility.
Examples of the diamine having an acid functional group include 2,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 3,3′-diaminobiphenyl-5,5′-dicarboxylic acid, and 4,4′-diaminodiphenyl ether. 5,5′-dicarboxylic acid, 4,4′-diaminodiphenylmethane-5,5′-dicarboxylic acid, 4,4′-diaminodiphenylsulfone-5,5′-dicarboxylic acid, 4,4′-diaminodiphenyl sulfide It has one or more carboxyl groups such as 5,5′-dicarboxylic acid or isomers thereof, or 4,4′-diamino-3,3′-dihydroxybiphenyl, 2,2′-bis (3-amino -4-hydroxyphenyl) propane, 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, oxybis (3-amino-4-hydro) Siphenyl), bis (3-amino-4-hydroxyphenyl) sulfone, 2,4-diaminophenol, 1,4-diamino-2,5-dihydroxybenzene, N, N ′-(4-aminophenylcarbonyl) -3 , 3′-dihydroxybiphenyl, N, N ′-(3-aminophenylcarbonyl) -3,3′-dihydroxybiphenyl, N, N ′-(4-aminophenylcarbonyl) 2,2′-bis (3-amino -4-hydroxyphenyl) hexafluoropropane, N, N '-(3-aminophenylcarbonyl) 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, N, N'-(4- Aminophenylcarbonyl) 2,2′-bis (3-amino-4-hydroxyphenyl) propane, N, N ′-(3-aminophenylcarbonyl) , 2′-bis (3-amino-4-hydroxyphenyl) propane, N, N ′-(4-aminophenylcarbonyl) -oxybis (3-amino-4-hydroxyphenyl), N, N ′-(3- Aminophenylcarbonyl) -oxybis (3-amino-4-hydroxyphenyl), N, N ′-(4-aminophenylcarbonyl) -bis (3-amino-4-hydroxyphenyl) sulfone, N, N ′-(3 -Aminophenylcarbonyl) -bis (3-amino-4-hydroxyphenyl) sulfone, N, N '-(4-aminophenylcarbonyl) -2,4-diaminophenol, N, N'-(3-aminophenylcarbonyl ) -2,4-diaminophenol, N, N ′-(4-aminophenylcarbonyl) -1,4-diamino-2,5-dihydroxybenzene, Examples thereof include those having a phenol group such as N, N ′-(3-aminophenylcarbonyl) -1,4-diamino-2,5-dihydroxybenzene, and these are used alone or in combination of two or more. Is done. Moreover, it is not necessarily limited to what was mentioned here.

  Among the diamines having acid functional groups described above, 3,5-diaminobenzoic acid, and 4,4′-diamino-3,3′-dihydroxybiphenyl, 2,2′-bis (3- Amino-4-hydroxyphenyl) propane, 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, oxybis (3-amino-4-hydroxyphenyl), bis (3-amino-4-hydroxy) Phenyl) sulfone, 2,4-diaminophenol, 1,4-diamino-2,5-dihydroxybenzene, N, N ′-(4-aminophenylcarbonyl) -3,3′-dihydroxybiphenyl, N, N′- (3-aminophenylcarbonyl) -3,3′-dihydroxybiphenyl, N, N ′-(4-aminophenylcarbonyl) 2, '-Bis (3-amino-4-hydroxyphenyl) hexafluoropropane, N, N'-(3-aminophenylcarbonyl) 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, N , N ′-(4-aminophenylcarbonyl) 2,2′-bis (3-amino-4-hydroxyphenyl) propane, N, N ′-(3-aminophenylcarbonyl) 2,2′-bis (3- Amino-4-hydroxyphenyl) propane, N, N ′-(4-aminophenylcarbonyl) -oxybis (3-amino-4-hydroxyphenyl), N, N ′-(3-aminophenylcarbonyl) -oxybis (3 -Amino-4-hydroxyphenyl), N, N '-(4-aminophenylcarbonyl) -bis (3-amino-4-hydroxyphenyl) (I) Sulfone and N, N '-(3-aminophenylcarbonyl) -bis (3-amino-4-hydroxyphenyl) sulfone are preferred for obtaining good alkali development characteristics.

In addition, component (a) is capable of controlling the solubility during development and / or pattern processing utilizing photoreaction by introducing a functional group as a monovalent organic group other than a hydrogen atom into R _1. It becomes. Moreover, alkali solubility can also be controlled by having these functional groups partially and leaving a hydrogen atom as R ₁ .
Examples of the method of introducing a functional group as a monovalent organic group into R ₁ in formula (I) include a method of introducing via an ether bond or an ester bond. As a specific introduction method, a halogen compound or acid halide compound having R ¹ as a substituent is reacted with a group in which R ₁ is a hydrogen atom, an addition reaction using a deoxidation halogen reaction, or an addition with vinyl ether. Reaction etc. are mentioned.

Examples of the organic group having 1 to 20 carbon atoms of R ₁ include methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, cyclopropenyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, and cyclohexenyl. , Norbornyl, norbornenyl, adamantyl, benzyl, p-nitrobenzyl, trifluoromethyl, methoxyethyl, ethoxyethyl, methoxymethyl, ethoxymethyl, methoxyethoxymethyl, benzoxymethyl, tetrahydropyranyl, ethoxytetrahydropyranyl, tetrahydrofuranyl, And organic groups such as 2-trimethylsilylethoxymethyl, trimethylsilyl, t-butyldimethylsilyl, 3-oxocyclohexyl, 9-fluorenylmethyl, and methylthiomethyl. .

Examples of the organic group having 1 to 20 carbon atoms of R ₁ include allyl alcohol, 2-methyl-2-propen-1-ol, crotyl alcohol, 3-buten-1-ol, 3-buten-2-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-1-ol, 3-methyl-3-buten-1-ol, 2-methyl-3-buten-2-ol, 2- Penten-1-ol, 4-penten-1-ol, 3-penten-2-ol, 4-penten-2-ol, 1-penten-3-ol, 4-methyl-3-penten-1-ol, 3-methyl-1-penten-3-ol, 2-hexen-1-ol, 3-hexen-1-ol, 4-hexen-1-ol, 5-hexen-1-ol, 1-hexene-3 -Ol, 1-heptane-3-ol, 6-methyl-5-heptan-2-ol 1-octane-3-ol, citronellol, 3-nonen-1-ol, 5-decan-1-ol, 9-decan-1-ol, 7-decan-1-ol, 1,4-pentadiene-3 -Ol, 2,4-hexadien-1-ol, 1,5-hexadien-3-ol, 1,6-heptadiene-4-ol, 2,4-dimethyl-2,6-heptadien-1-ol, nerol , Geraniol, linalool, 2-cyclohexen-1-ol, 3-cyclohexene-1-methanol, isopulegol, 5-norbornen-2-ol, 5-norbornene-2-methanol, ethylene glycol vinyl ether, 1,4-butanediol vinyl ether 1,6-hexanediol vinyl ether, diethylene glycol vinyl ether, 2-hydroxyethyl acrylate 3-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, pentaerythritol diacrylate monostearate, pentaerythritol triacrylate, caprolactone 2- (methacryloyl) Roxy) A carboxyl group that binds a compound such as ethyl ester, dicaprolactone 2- (methacryloyloxy) ethyl ester, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate to X ₁ or Y ₁ And a functional group obtained by reacting with. Moreover, it is not necessarily limited to what was mentioned here. Moreover, when the terminal of a polymer has an acidic functional group, it is also possible to introduce these functional groups.

  Among the organic groups having 1 to 20 carbon atoms, methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, methoxyethyl, ethoxyethyl, methoxymethyl, ethoxymethyl, methoxyethoxymethyl, tetrahydro Pyranyl, ethoxytetrahydropyranyl, and tetrahydrofuranyl are preferred for controlling the solubility well.

In the formula (I), when R ₂ is the same functional group as R ₁ , the composition of the present invention can be controlled in solubility during development and / or patterned using a photoreaction. Moreover, alkali solubility can also be controlled by having these functional groups partially. Moreover, when the terminal of the polymer of (a) component has an acidic functional group, it is also possible to introduce these functional groups.

  The component (a) has both the amine functional group and / or its derived substituent, the acidic functional group and / or its derived substituent, or one of both functional groups at one end, One of the combinations.

  When the amine functional group at the terminal is a primary amine, the stability of the photosensitive resin composition deteriorates due to side reactions, so at least one of the two hydrogen atoms on the amine functional group is another atom or other atom. Substitution with a functional group is preferred for obtaining stability as a photosensitive resin composition. Further, the substitution ratio of the other atom or other functional group is more preferably in the range of 30% to 100% in order to obtain sufficient stability.

  Regarding the derivative substituent of the amine functional group at the end of the component (a), examples of the substituent on nitrogen derived from the amine functional group include amide, imide, carbamate, sulfonyl, sulfenyl, phosphinyl, and alkylsilyl. Of these, amide, imide, carbamate, and sulfonyl are preferable in terms of obtaining more excellent cured resin properties.

（式中、Ｒ_１１〜Ｒ_１３は、それぞれ１価の有機基であり、好ましくは炭素数１〜２０の有機基である。Ｒ_１４は２価の有機基である。Ｘ_２は酸素原子、硫黄原子又は窒素原子であり、Ｘ_２が酸素原子又は硫黄原子である場合、ｎ＝１であり、Ｘ_２が窒素原子の場合、ｎ＝２である。） Preferably, it is either a hydrogen atom or a substituent represented by the following formula (V) as a substituent on nitrogen derived from the amine functional group.

(In the formula, R _{11 to} R ₁₃ are each a monovalent organic group, preferably an organic group having 1 to 20 carbon atoms. R ₁₄ is a divalent organic group. X ₂ is an oxygen atom, When it is a sulfur atom or a nitrogen atom, and X ₂ is an oxygen atom or a sulfur atom, n = 1, and when X ₂ is a nitrogen atom, n = 2.)

Examples of the monovalent organic group represented by R _{11 to} R ₁₃ include methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, cyclopropenyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, and cyclohexenyl. , Norbornyl, norbornenyl, adamantyl, benzyl, p-nitrobenzyl, trifluoromethyl, methoxyethyl, ethoxyethyl, methoxymethyl, ethoxymethyl, methoxyethoxymethyl, benzoxymethyl, ethoxytetrahydropyranyl, tetrahydrofuranyl, 2-trimethylsilylethoxy Methyl, trimethylsilyl, t-butyldimethylsilyl, 3-oxocyclohexyl, 9-fluorenylmethyl, phenyl, toluyl, xylyl, 9,10-dihydroanthrani , Trimethylphenyl, pentamethylphenyl, biphenyl, terphenyl, quarterphenyl, dimethylbiphenyl, naphthalenyl, methylnaphthalenyl, fluorenyl, fluorophenyl, fluorobiphenyl, isopropylidenebiphenyl, tetrafluoroisopropylidenebiphenyl, benzylphenyl ether, phenyl ether Phenoxytoluyl, methoxybiphenyl, dimethoxybiphenyl, methoxynaphthalenyl, dimethoxynaphthalenyl and nitrophenyl.

Examples of the divalent organic group represented by R ₁₄ include methane, ethane, propane, isopropane, dimethylmethane, butane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, methylcyclohexane, norbornane, adamantane, isopropylidenedicyclohexane, and methoxymethane. , Methoxyethane, ethoxyethane, methoxyethoxymethane, benzoxymethane, tetrahydrofuran, benzene, toluene, cumene, diphenylmethane, xylene, 9,10-dihydroanthracene, mesitylene, hexamethylbenzene, biphenyl, terphenyl, triphenylbenzene, Quarterphenyl, dimethylbiphenyl, azulene, naphthalene, methylnaphthalene, anthracene, fluorene, fluorobenzene, fluorobiphenyl Divalent organic groups corresponding to benzene, isopropylidenebiphenyl, tetrafluoroisopropylidenebiphenyl, anisole, benzylphenyl ether, phenyl ether, phenoxytoluene, tolyl ether, methoxybiphenyl, dimethoxybiphenyl, methoxynaphthalene, dimethoxynaphthalene, nitrobenzene, etc. Can be mentioned. Moreover, it is not necessarily limited to what was mentioned here.

Examples of the acidic functional groups and / or their derived substituent at the end portion of the component (a), there are substituents represented by -COOR ₁ or -OR ₂ of the formula (I).

The component (a) is preferably a polymer that is soluble in an alkaline aqueous solution.
The alkaline aqueous solution is, for example, an alkaline aqueous solution such as a tetramethylammonium hydroxide aqueous solution, a metal hydroxide aqueous solution, or an organic amine aqueous solution. Since a tetrabutylammonium aqueous solution having a concentration of 2.38 parts by weight is generally used, it is more preferable that the component (a) is soluble in this aqueous solution.

The molecular weight of the component (a) is not particularly limited, but is a polystyrene standard weight average molecular weight, preferably 5,000 to 80,000.
The molecular weight can be measured by gel permeation chromatography and calculated using a standard polystyrene calibration curve.

  Component (a) is, for example, tetracarboxylic dianhydride, dicarboxylic acid, a compound further having an acid functional group or a derivative thereof, and a diamine or a compound further having an acid functional group as a main raw material of the polymer. A polyimide precursor, a polybenzoxazole precursor, a copolymer thereof, and a mixture thereof obtained as follows are preferable.

The component (a) can be prepared by polymerizing a tetracarboxylic dianhydride, a dicarboxylic acid and / or a dicarboxylic acid having an acid functional group and a diamine and / or a diamine having an acid functional group.
For example, the polyimide precursor which is a component (a) can be prepared by polymerizing a tetracarboxylic dianhydride and a diamine and / or a diamine having an acid functional group. Similarly, a polybenzoxazole precursor as component (a) can be prepared by polymerizing an activated esterified dicarboxylic acid and / or a dicarboxylic acid having an acid functional group and a diamine having a phenolic acid functional group. Moreover, it is (a) component by copolymerizing tetracarboxylic dianhydride, dicarboxylic acid and / or dicarboxylic acid having an active esterified acid functional group and diamine and / or diamine having an acid functional group. A copolymer of polyimide / polybenzoxazole precursor can be prepared.

  The naphthoquinone diazide compound which is the component (b) contained in the composition of the present invention is a photosensitizer and has a function of generating an acid upon irradiation with actinic light. By including the component (b), it is possible to increase the solubility of the light irradiated portion of the resin film obtained from the composition of the present invention in an alkaline aqueous solution. The naphthoquinone diazide compound is preferably an o-naphthoquinone diazide compound.

  The naphthoquinonediazide compound is obtained by subjecting naphthoquinonediazidosulfenyl chloride and a polyhydroxy compound to a condensation reaction according to a conventional method, for example, a polyhydroxy compound and 1,2-naphthoquinonediazide-4-sulfonyl chloride, or 1,2-naphtho It can be obtained by reacting quinonediazide-5-sulfonyl chloride in the presence of a basic catalyst such as triethylamine.

  Examples of the polyhydroxy compounds that serve as ballasts for the photosensitizer include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (2-hydroxyphenyl) methane, bis (4-hydroxyphenyl) methane, and 2-hydroxyphenyl-4′-hydroxyphenyl. Methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′- Tetrahydroxybenzophenone, 2,3,4,2 ′, 3′-pentahydroxybenzophenone, 2,3,4,3 ′, 4 ′, 5′-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) ) Methane, bis (2,3,4-trihydroxyphenyl) Lopan, 2- (4-hydroxyphenyl) -2- [4- [1,1-bis (4-hydroxyphenyl) ethyl] phenyl] propane, 4b, 5,9b, 10-tetrahydro-1,3,6 Examples include 8-tetrahydroxy-5,10-dimethylindeno [2,1-a] indene, tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxyphenyl) ethane, and the like. Moreover, it is not necessarily limited to what was mentioned here.

The solvent which is the component (c) contained in the composition of the present invention dissolves the components (a) and (b) described above, the components (d) and (e) described later, and the varnish. Shape.
Solvents used include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, 2-methoxyethanol, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether , Propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol acetate, cyclohexanone, cyclopentanone, tetrahydrofuran and the like. May be used.

  The iodonium compound which is the component (d) contained in the composition of the present invention has a function as a dissolution inhibitor in the unexposed portion of the resin film obtained from the composition of the present invention, and is irradiated with active light. It is a co-photosensitive agent having a function of generating an acid and increasing the solubility of an exposed area in an alkaline aqueous solution.

（式中、Ｘは、対陰イオンである。Ｒ_３は、アルキル基、アルケニル基、アルコキシ基、トリアルキルシリル基、前記各基の水素原子の一部又は全部がフッ素原子に置換された基（例えばパーフルオロアルキル基等）、塩素原子、臭素原子又はフッ素原子である。Ｚは、１価の有機基である。ａは、０〜５の整数である。） The iodonium compound is preferably an iodonium salt represented by the following formula (II).

(In the formula, X is a counter anion. R ₃ is an alkyl group, an alkenyl group, an alkoxy group, a trialkylsilyl group, or a group in which part or all of the hydrogen atoms in each of the above groups are substituted with fluorine atoms. (For example, a perfluoroalkyl group, etc.), a chlorine atom, a bromine atom or a fluorine atom. Z is a monovalent organic group, and a is an integer of 0 to 5.)

  Examples of the counter anion of X include p-toluenesulfonate ion, trifluoromethanesulfonate ion, hexafluoroborate ion, 9,10-dimethoxyanthracene-2-sulfonate ion, and 8-anilinonaphthalene-1 -Sulfonate ion, methyl sulfonate ion, sulfate ion, nitrate ion, trichloroacetate ion, chloride ion and the like.

（Ｒ_３は、前記式（II）と同様の定義である。Ｒ_４〜Ｒ_７は、それぞれ、水素原子、アルキル基、アルコキシ基、トリフロロメタンスルホニル基又はトリアルキルシリル基である。ａは、０〜５の整数である。） In the iodonium salt represented by the formula (II), Z is preferably any of the substituents represented by the following formula (III).

(R ₃ has the same definition as in formula (II) above. R _{4 to} R ₇ are each a hydrogen atom, an alkyl group, an alkoxy group, a trifluoromethanesulfonyl group, or a trialkylsilyl group. , An integer from 0 to 5.)

Examples of the alkyl group of R _{3 to} R ₇ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an isobutyl group, a pentyl group, a hexyl group, and an octyl group. .
Examples of the alkoxy group of R _{3 to} R ₇ include a methoxy group, an ethoxy group, and a propoxy group.
Examples of the trialkylsilyl group for R _{3 to} R ₇ include a trimethylsilyl group and a triethylsilyl group.
Examples of the alkenyl group for R ₃ include vinyl group, allyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, and 3-butenyl group.

  Specific examples of the component (d) include diphenyliodonium, 9,10-dimethoxyanthracene-2-sulfonate, diphenyliodonium-8-anilinonanaphthalene-1-sulfonate, diphenyliodoniumsulfonate, diphenyltrifluoromethylsulfonate, diphenyl. Iodonium nanofluorobutanesulfonate, diphenyliodonium toluenesulfonate, diphenyliodonium chloride, diphenyliodonium bromide, diphenyliodonium iodide, diphenyliodonium hexafluorophosphate, 4-methoxyphenyliodoniumnitrate, 4-methoxyphenyliodoniumtrifluoromethylsulfonate 4,4'-di-t-butyldiphenyliodonium trifluoromethylsulfonate Phenyl (5-trifluoromethylsulfonyl-4-octen-4-yl) iodonium hexafluoroborate, phenyl (5-trifluoromethylsulfonyl-4-octen-4-yl) trifluoromethylsulfonate, phenyl (4- Examples thereof include trifluoromethylsulfonyl 3-hexen-3-yl) hexafluoroborate, phenyl (4-trifluoromethylsulfonyl-hexen-3-yl) trifluoromethyl sulfonate, and the like.

In the present invention, as described above, any one of conditions selected from the following conditions i) and ii) must be satisfied.
i) The (d) iodonium compound has a polycyclic aromatic ring skeleton in which two or more monocyclic aromatic rings are condensed,
ii) containing (d) an iodonium compound and (e) a photoexcitation accelerator having a polycyclic aromatic ring skeleton in which two or more monocyclic aromatic rings are condensed.

Here, the polycyclic aromatic ring in which two or more monocyclic aromatic rings are condensed includes a condensed polycyclic hydrocarbon ring such as a naphthalene ring, an anthracene ring, a phenanthrene ring, a naphthacene ring, and a pyrene ring. , Quinoline ring, isoquinoline ring, condensed heterocyclic ring such as quinazoline ring, and the like, and naphthalene ring or anthracene ring is preferable from various properties such as solubility.
Accordingly, specific examples of the component (d) satisfying the condition i) include diphenyliodonium-9,10-dimethoxyanthracene-2-sulfonate, diphenyliodonium-8-anilinonanaphthalene-1-sulfonate, phenyl [(3- Trimethylsilyl) -2-naphthyl] iodonium triflate, naphthyl (phenyl) iodonium tetrafluoroborate, and the like.
In addition, the composition of the present invention is a photoexcitation accelerator having a polycyclic aromatic ring skeleton in which (e) two or more monocyclic aromatic rings are condensed as a case satisfying the condition ii) including.
(E) The photoexcitation accelerator is a function that is excited by irradiation with actinic light and decomposes the component (d) by one electron transfer to the component (d) to generate an acid, thereby increasing the dissolution rate of the light irradiation part. Have The component (e) is particularly preferably used when the component (d) is a compound that does not absorb active light.

（Ｒ_８〜Ｒ_１０は、それぞれアルキル基、アルコキシ基又はアルケニル基であり、これらはそれぞれ０〜１０有することができ、Ｒ_８〜Ｒ_１０の総計は０〜１０である。） Examples of the component (e) include those having various condensed polycyclic aromatic ring skeletons, and examples include anthracene compounds, tetracene compounds, and phenanthrene compounds. Preferably, anthracene represented by the following formula (IV): A compound.

_(R 8 _{to R 10} each represent an alkyl group, an alkoxy group or an alkenyl group, each of may have _0, total R 8 _{to R 10} is 0-10.)

Here, examples of the alkyl group, alkoxy group and alkenyl group of R _{8 to} R ₁₀ include the same exemplified groups as those exemplified in the description of R ₃ .

  The anthracene compound represented by the formula (IV) is preferably an anthracene compound having an alkoxy group at the 9,10-position, and more preferably an anthracene compound further having an alkyl group at the 2-position for the purpose of preventing precipitation. .

  Specific examples of the component (e) include 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethoxyanthracene, 9-methylanthracene, 9,10-dimethylanthracene, and 9,10-dipropoxyanthracene. Although it is mentioned as a thing, it is not limited to these.

The composition of the present invention preferably contains 0.01 to 50 parts by weight of component (b) and 1 to 50 parts by weight of component (d) with respect to 100 parts by weight of component (a).
Moreover, when the composition of this invention further contains a component (e), the composition of this invention is preferably 0.01-50 weight part of (b) component with respect to 100 weight part of component (a), The component (d) contains 1 to 50 parts by weight, and the component (e) contains 0.01 to 50 parts by weight.

The amount of the solvent of component (c) is not particularly limited, but is usually 100 parts by weight of component (a).
150 to 230 parts by weight are used.
The composition of the present invention may contain an adhesion-imparting agent, a surfactant or leveling agent, a crosslinking agent, and the like in addition to the components (a) to (e) described above.

The adhesion-imparting agent can enhance the adhesion with the base of the cured film obtained from the composition of the present invention.
Examples of the adhesion imparting agent include organic silane compounds and aluminum chelate compounds.

  Examples of the organic silane compound include vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, ureapropyltriethoxysilane, methylphenylsilanediol, ethylphenylsilanediol, n- Propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol , Ethyl n-propylphenylsilanol, 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 (butyldi) Droxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, 1,4-bis (dipropylhydroxysilyl) benzene, 1,4-bis (dibutylhydroxysilyl) ) Benzene and the like.

  Examples of the aluminum chelate compound include tris (acetylacetonate) aluminum and acetylacetate aluminum diisopropylate.

  The content of the adhesion-imparting agent is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of component (a).

The surfactant or the leveling agent can prevent, for example, striation (film thickness unevenness) or improve the developability of the composition of the present invention.
Examples of the surfactant or leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like. Commercially available surfactants or leveling agents include Megafac F171, F173, R-08 (Dainippon Ink Chemical Co., Ltd.), Florard FC430, FC431 (Sumitomo 3M Limited), organosiloxane polymer KP341. , KBM303, KBM403, KBM803 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

The crosslinking agent can improve the stretchability, elastic modulus, and thermal characteristics of the thermosetting film obtained from the composition of the present invention.
The crosslinking agent is, for example, a methylol compound, and examples of the methylol compound include 3,3′-methylenebis (2-hydroxy-5-methylbenzenemethanol), 4,4 ′-(1-methylethylidene) bis [2 -Methyl-6-hydroxymethylphenol], 4,4 '-(1,1,1,3,3,3-hexafluoroisopropylidene) bis [2,6-bis (hydroxymethyl) phenol], 3,3 ', 5,5'-tetrakis (hydroxymethyl) [(1,1'-biphenyl) -4,4'-diol], 4,4'-(1-methylethylidene) bis [2,6-bis (hydroxy Methyl) phenol], 2,2′-methylenebis (4,6-bishydroxymethylphenol), 2,6-bis [(2-hydroxy-3-hydroxymethyl-5-methylpheny) ) Include methyl] -4-methylphenol and the like. Moreover, it is not necessarily limited to what was mentioned here.

  A pattern cured film can be formed by applying the composition of the present invention. In particular, the cured film obtained from the composition of the present invention is excellent in heat resistance and mechanical properties.

  The pattern cured film manufacturing method of the present invention includes a photosensitive resin film forming step in which the composition of the present invention is applied to a support substrate and dried to form a photosensitive resin film, and the formed photosensitive resin film is predetermined. An exposure process for exposing the pattern, a development process for developing the exposed photosensitive resin film using an alkaline aqueous solution to obtain a pattern resin film, and a heat treatment process for obtaining a pattern cured film by heat-treating the pattern resin film including.

Examples of the support substrate to which the composition of the present invention is applied include a silicon wafer, a metal substrate, and a ceramic substrate. Examples of the coating method include a dipping method, a spray method, a screen printing method, and a spin coating method.
A photosensitive resin coating film is obtained by appropriately heating and drying the composition of the present invention applied on a support substrate.

On the obtained photosensitive resin coating film, an exposure treatment is performed in which actinic rays or actinic rays are irradiated through a mask on which a desired pattern is drawn.
As the actinic ray or actinic ray to be irradiated, a contact / proximity exposure machine using an ultra-high pressure mercury lamp, a mirror projection exposure machine, an i-line stepper, a g-line stepper, other ultraviolet rays, a visible light source, an X-ray or an electron beam is used. be able to.
After the exposure, a post exposure bake (PEB) treatment may be performed as necessary.

A desired positive pattern (pattern resin film) can be obtained by dissolving and removing the exposed portion of the exposed resin film using an alkaline aqueous solution.
Examples of the alkaline aqueous solution as a developer include aqueous solutions of alkali metal hydroxides such as caustic potash and caustic soda; quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline; ethanolamine, propylamine and ethylenediamine. An aqueous amine solution such as can be used.

After development, it may be rinsed with water or a poor solvent as necessary.
Examples of the rinsing liquid to be used include methanol, ethanol, isopropyl alcohol, benzene, toluene, xylene, methyl cellosolve, and water.

By heating the obtained pattern resin film, the solvent or the solvent and the photosensitizer can be removed to obtain a stable high heat resistant pattern cured film.
The said heating temperature becomes like this. Preferably it is 150-500 degreeC, More preferably, it is 200-400 degreeC. When the heating temperature is less than 150 ° C., the mechanical properties and thermal properties of the film may be deteriorated. On the other hand, when the heating temperature exceeds 500 ° C., the mechanical properties and thermal properties of the film may be deteriorated.
The heating time is preferably 0.05 to 10 hours. When the heating time is less than 0.05 hours, the mechanical properties and thermal properties of the film may be deteriorated. On the other hand, when the heating time exceeds 10 hours, the mechanical properties and thermal properties of the film may be deteriorated.

  The cured pattern film made of the composition of the present invention can be used for electronic parts such as semiconductor devices and multilayer wiring boards. Specifically, it can be used as a surface protective film layer, an interlayer insulating film layer of a semiconductor device, an interlayer insulating film layer of a multilayer wiring board, or the like.

  The electronic component of the present invention is not particularly limited except that it has a surface protective film layer and / or an interlayer insulating film layer formed using the composition of the present invention, and can have various structures. Moreover, as an electronic component, a semiconductor device, a multilayer wiring board, various electronic devices, etc. are included.

A manufacturing method of a patterned cured film of the present invention and an electronic component provided with the patterned cured film of the present invention will be described based on the drawings with an example of a manufacturing process of a semiconductor device having a patterned cured film.
1 to 5 are schematic cross-sectional views for explaining a manufacturing process of a semiconductor device having a multilayer wiring structure, and represent a series of processes from a first process to a fifth process.

1 to 5, a semiconductor substrate 1 such as a Si substrate having a circuit element (not shown) is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element, and on the exposed circuit element. A first conductor layer 3 is formed. An interlayer insulating film layer 4 is formed on the semiconductor substrate 1 by a spin coating method or the like (first step, FIG. 1).
The interlayer insulating film layer 4 can be formed using the resin composition of the present invention.

  Next, a photosensitive resin layer 5 such as chlorinated rubber or phenol novolac is formed on the interlayer insulating film layer 4 as a mask by a spin coating method, and a predetermined portion of the interlayer insulating film layer 4 is formed by a known photolithography technique. A window 6A is provided so as to be exposed (second step, FIG. 2).

  The interlayer insulating film layer 4 exposed to the window 6A is selectively etched by a dry etching means using a gas such as oxygen or carbon tetrafluoride to open the 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 (third step, FIG. 3).

  Further, the second conductor layer 7 is formed by using a known photolithography technique, and the electrical connection with the first conductor layer 3 is completely performed (fourth step, FIG. 4). When a multilayer wiring structure having three or more layers is formed, each layer can be formed by repeating the above steps.

Next, the surface protective film 8 is formed. In FIG. 5, the resin composition of the present invention is applied and dried by a spin coating method, irradiated with light from a mask on which a pattern for forming a window 6C is formed at a predetermined portion, and then developed with an alkaline aqueous solution. A resin film is formed. Thereafter, the patterned resin film is heated to form a patterned cured film of a photosensitive resin as the surface protective film layer 8 (fifth step, FIG. 5).
This surface protective film layer (patterned cured film) 8 protects the conductor layer from external stress, α rays, etc., and the resulting semiconductor device is excellent in reliability.

Synthesis example 1
In a flask which is a closed reaction vessel equipped with a stirrer, a thermometer and a nitrogen introduction tube, 6495 g of dry N-methylpyrrolidone and 1831.3 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (5 mol) ) And 218.3 g (2 mol) of m-aminophenol were added and stirred until dissolved at 15 to 25 ° C. Next, 1771 g (6 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride was added over 30 minutes, followed by stirring at 20 to 35 ° C. for 3 hours. The reaction mixture was treated with 2.0 l of ion exchange water with vigorous stirring. The precipitated solid was further washed with warm ion-exchanged water at 70 ° C., sucked and dried on a filtration filter, and further dried under reduced pressure to obtain polymer A.
The obtained polymer A had a water content of 0.8% by weight, a weight average molecular weight of 19,200, and a dispersity of 1.5.

In addition, the weight average molecular weight of the polymer A was measured by a GPC method using a sample diluted with 1 mL of a solvent with respect to 0.5 mg of the polymer. The measurement conditions are shown below.
Measuring device: Detector L4000 UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
C-R4A Chromatopac made by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5 × 2 eluent: THF / DMF = 1/1 (volume ratio)
LiBr · H ₂ O (0.03 mol / L), H ₃ PO ₄ (0.06 mol / L)
Flow rate: 1.0 mL / min, detector: UV 270 nm

Example 1
In a three-necked flask equipped with a stirrer, a nitrogen inlet tube, and a thermometer, 170 g of γ-butyrolactone, 17 g of propylene glycol monobutyl ether acetate, 100 g of the polymer A obtained in Synthesis Example 1, 4,4 ′-(1, 1,1,3,3,3-hexafluoroisopropylidene) bis [2,6-bis (hydroxymethyl) phenol] 10.0 g, 2- (4-hydroxyphenyl) -2- [4- [1,1 -Bis (4-hydroxyphenyl) ethyl] phenyl] propane and 13.0 g of a compound obtained by reacting naphthoquinone-1,2-diazide-5-sulfonyl chloride in a molar ratio of 1 / 2.5, bis (2-hydroxy Ethyl) -3-aminopropyltriethoxysilane (62% ethanol solution) 3.5 g, trimethoxy (phenyl) silane 0.5 g, diphenyl Le iodonium nitrate 3.0 g, for one day after stirring and dissolved at room temperature by addition of 2-ethyl-9,10-dimethoxy anthracene 3.0 g, to obtain a positive photosensitive resin composition solution was filtered.
This solution was spin-coated on a 6-inch silicon wafer and then dried to form a coating film having a film thickness of 9.0 ± 1.0 μm, followed by pattern masking using an i-line stepper and an exposure amount of 100 to 800 mJ. / Cm ² for exposure. When the coated film after exposure was subjected to paddle development using a 2.38% tetramethylammonium hydroxide aqueous solution, a good relief pattern was obtained at 270 mJ / cm ² .

Example 2
A positive photosensitive resin composition solution was prepared in the same manner as in Example 1 except that 9,10-dimethoxyanthracene was used instead of 2-ethyl-9,10-dimethoxyanthracene to produce a patterned resin film. As a result, a good relief pattern was obtained at 270 mJ / cm ² or more.

Example 3
Positive photosensitive resin composition in the same manner as in Example 1 except that diphenyliodonium and 9,10-dimethoxyanthracene-2-sulfonate were used instead of diphenyliodonium nitrate and 2-ethyl-9,10-dimethoxyanthracene. A solution was prepared to produce a patterned resin film. As a result, a good relief pattern was obtained at 270 mJ / cm ² or more.

Example 4
A positive photosensitive resin composition solution was prepared in the same manner as in Example 3 except that diphenyliodonium-8-anilinonanaphthalene-1-sulfonate was used in place of diphenyliodonium and 9,10-dimethoxyanthracene-2-sulfonate. Then, a patterned resin film was manufactured. As a result, a good relief pattern was obtained at 270 mJ / cm ² or more.

Comparative Example 1
In a three-necked flask equipped with a stirrer, a nitrogen inlet tube, and a thermometer, 170 g of γ-butyrolactone, 17 g of propylene glycol monobutyl ether acetate, 100 g of the polymer A obtained in Synthesis Example 1, 4,4 ′-(1, 1,1,3,3,3-hexafluoroisopropylidene) bis [2,6-bis (hydroxymethyl) phenol] 10.0 g, 2- (4-hydroxyphenyl) -2- [4- [1,1 -Bis (4-hydroxyphenyl) ethyl] phenyl] propane and 13.0 g of a compound obtained by reacting naphthoquinone-1,2-diazide-5-sulfonyl chloride in a molar ratio of 1 / 2.5, bis (2-hydroxy Ethyl) -3-aminopropyltriethoxysilane (62% ethanol solution) 3.5 g, trimethoxy (phenyl) silane 0.5 g, diphenyl After overnight stirring and dissolved at room temperature was added Le iodonium nitrate 3.0 g, to obtain a positive photosensitive resin composition solution was filtered.
A patterned resin film was produced in the same manner as in Example 1 using the obtained solution. As a result, a good relief pattern was obtained at 310 mJ / cm ² or more.

The combinations of the components included in the compositions prepared in Examples 1 to 4 and Comparative Example 1 and the results of the minimum exposure that the patterns obtained from the compositions of Examples 1 to 4 and Comparative Example 1 are opened are shown below. .

(A) to (F) in Table 1 are the following compounds, respectively.

  From the results of Examples and Comparative Examples, it can be seen that the positive photosensitive resin composition of the present invention can form a pattern with a low exposure amount and is a highly sensitive positive photosensitive resin composition.

  Since the positive photosensitive resin composition of the present invention is excellent in sensitivity, a relief pattern having a good shape can be obtained with a low exposure amount. Therefore, the positive photosensitive resin composition of the present invention has excellent reliability and is particularly suitable for the production of electronic parts.

DESCRIPTION OF SYMBOLS 1 Semiconductor substrate 2 Protective film 3 1st conductor layer 4 Interlayer insulating film layer 5 Photosensitive resin layer 6A, 6B, 6C Window 7 2nd conductor layer 8 Surface protective film layer

Claims (9)

(A) a polymer having a structure represented by the following formula (I):

(In the formula, X ₁ is a divalent to octavalent organic group. Y ₁ is a divalent to octavalent organic group. R ₁ is a hydrogen atom or an organic group having 1 to 20 carbon atoms. R _2. Are each hydrogen or a monovalent organic group, p and q are each an integer of 0 to 4. l and m are each an integer of 0 to 2. l + m + p + q is 1 or more, and n is in the polymer. (It is an integer of 2 or more indicating the number of structural units.)
(B) a naphthoquinonediazide compound,
(C) solvent ,
(D) an iodonium compound , and
(E) A positive photosensitive resin composition comprising a photoexcitation accelerator having a polycyclic aromatic ring skeleton in which two or more monocyclic aromatic rings are condensed.   The positive photosensitive resin composition according to claim 1, wherein the (b) naphthoquinone diazide compound is an o-naphthoquinone diazide compound. The positive photosensitive resin composition according to claim 1 or 2, wherein the (d) iodonium compound is an iodonium salt represented by the following formula (II).

(In the formula, X is a counter anion. R ₃ is an alkyl group, an alkenyl group, an alkoxy group, a trialkylsilyl group, or a group in which part or all of the hydrogen atoms in each of the above groups are substituted with fluorine atoms. , A chlorine atom, a bromine atom or a fluorine atom, Z is a monovalent organic group, and a is an integer of 0 to 5.) The positive photosensitive resin composition according to claim 3, wherein Z in the formula (II) is any one of substituents represented by the following formula (III).

(R ₃ has the same definition as in formula (II) above. R _{4 to} R ₇ are each a hydrogen atom, an alkyl group, an alkoxy group, a trifluoromethanesulfonyl group, or a trialkylsilyl group. , An integer from 0 to 5.) Wherein (e) the backbone of the polycyclic aromatic rings in component, positive photosensitive resin composition according to any one of claims 1 to 4, which is a naphthalene skeleton or anthracene skeleton. Wherein (e) photoexcitation accelerator positive photosensitive resin composition according to any one of claims 1 to 5, an anthracene compound represented by the following formula (IV).

(R _{8 to} R ₁₀ are each an alkyl group, an alkoxy group, or an alkenyl group.) (A) 0.01 to 50 parts by weight of (b) naphthoquinonediazide compound, (d) 1 to 50 parts by weight of iodonium compound, and 100 parts by weight of the polymer having the structure represented by formula (I), and (E) The positive photosensitive resin composition in any one of Claims 1-6 which contains 0.01-50 weight part of photoexcitation promoters, respectively. A photosensitive resin film forming step of forming a photosensitive resin layer of the positive photosensitive resin composition is coated on a supporting substrate and dried to according to any one of claims 1 to 7
An exposure step of exposing the photosensitive resin film to a predetermined pattern;
A development step of developing the exposed photosensitive resin film using an alkaline aqueous solution to obtain a patterned resin film;
The manufacturing method of the pattern cured film including the heat processing process which heat-processes the said pattern resin film and obtains a pattern cured film. The electronic component which has a pattern cured film obtained by the manufacturing method of the pattern cured film of Claim 8 as an interlayer insulation film layer or a surface protective film layer.

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