JP2013190697A - Photosensitive resin composition, cured relief pattern-manufacturing method, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which can be cured at low-temperature and gives a cured film excellent in chemical resistance; a cured relief pattern-manufacturing method to form a pattern using the photosensitive resin composition; and a semiconductor device and a display device having the cured relief pattern.SOLUTION: A photosensitive resin composition contains a phenol resin (A) having a repeating unit represented by the general formula (1) [in the formula, a is an integer of 1 to 3; b is an integer of 0 to 3; 1≤(a+b)≤4 is satisfied; Rrepresents a monovalent substituent selected from a monovalent organic group having a carbon number of 1 to 20, a halogen atom, a nitro group and a cyano group; and X represents divalent organic group selected from a divalent chain aliphatic group having a carbon number of 2 to 10, a divalent alicyclic group having a carbon number of 3 to 20, an alkylene oxide group having a carbon number of 1 to 10 and a divalent organic group having an aromatic ring], a photoacid-generating agent (B), solvent (C) and a nonionic surfactant (D).

Description

  The present invention relates to a photosensitive resin composition. The present invention also relates to a semiconductor device and a display device having a cured relief pattern obtained by curing the photosensitive resin composition.

  Conventionally, polyimide resins and polybenzoxazole resins having excellent heat resistance, electrical characteristics, and mechanical characteristics have been widely used for permanent films used in semiconductor devices, such as surface protective films and interlayer insulating films. Since these resins have a cyclic structure and have low solubility in various solvents as they are, a composition in which a precursor obtained by ring-opening the cyclic structure is dissolved in a solvent is generally used. Therefore, in order to manufacture a semiconductor device, a step of closing the precursor is necessary after the step of applying the composition on the semiconductor element. This ring closing step is usually performed by thermosetting in which the coating film is heated to 300 ° C. or higher.

  However, in recent years, semiconductor devices that are inferior in heat resistance compared to conventional products have been developed, and a lowering of the thermosetting temperature has been required for the material for forming the surface protective film and the interlayer insulating film. Increasingly, curability is required.

  In response to this requirement, Patent Document 1 discloses a composition using a phenol resin obtained by condensing phenols and aldehydes, and crosslinkable fine particles for improving the thermal shock resistance of the phenol resin. Has been proposed. Phenolic resin is a resin that is widely used as a base resin for resists that are temporarily used as a mask in the etching or film formation process when manufacturing semiconductor devices, and does not require the above-described ring closing process, and can be cured at low temperatures. It is excellent in cost and photosensitivity.

  Further, in Patent Document 2, in order to improve the thermal shock resistance of a phenol resin, when synthesizing a phenol resin, an α, α′-dihaloxylene compound, an α, α′-dihydroxyxylene compound, And a composition obtained by condensing a phenolic compound with at least one substituted xylene compound selected from the group consisting of α, α′-dialkoxyxylene compounds.

  Patent Document 3 discloses a negative photosensitive resin composition used as an interlayer insulating resin used for silicon wafers and the like, comprising an epoxy-containing substance, a vinylphenol resin, a biphenylphenol resin, and a specific urea-based crosslinking agent. Have been described.

JP 2003-215789 A JP 2007-057595 A JP 2006-243161 A

  When a resin film is applied as a permanent film to a semiconductor device, chemical resistance to chemicals used in the semiconductor process is one of the important film properties of the cured resin film. However, Patent Documents 1 to 3 mentioned above do not describe chemical resistance of the cured film. When this inventor examined, compared with the cured relief pattern which consists of a polyimide resin or polybenzoxazole resin currently utilized, these phenol resins had room to improve about chemical resistance.

  Accordingly, the present invention provides a photosensitive resin composition that can be cured at low temperature and provides a cured film with excellent chemical resistance, and a method for producing a cured relief pattern that forms a pattern using the photosensitive resin composition It is another object of the present invention to provide a semiconductor device and a display device having the cured relief pattern.

  As a result of intensive studies and repeated experiments, the present inventor is able to solve the above problems by using a phenol resin having a specific structure in combination with a nonionic surfactant. The present invention has been found and the present invention has been accomplished. That is, the present invention is as follows.

｛式（１）中、ａは、１〜３の整数であり、ｂは、０〜３の整数であり、１≦（ａ＋ｂ）≦４であり、Ｒ₁は、炭素数１〜２０の１価の有機基、ハロゲン原子、ニトロ基及びシアノ基から成る群から選ばれる１価の置換基を表し、ｂが２又は３である場合の複数のＲ₁は、それぞれ同じでも異なっていてもよく、Ｘは、不飽和結合を有していてもよい炭素数２〜１０の２価の鎖状脂肪族基、炭素数３〜２０の２価の脂環式基、下記一般式（２）：

（式（２）中、ｐは、１〜１０の整数である。）で表される２価のアルキレンオキシド基、及び芳香族環を有する２価の有機基から成る群から選ばれる２価の有機基を表す。｝で表される繰り返し単位を有するフェノール樹脂（Ａ）、
光酸発生剤（Ｂ）、
溶剤（Ｃ）、及び
非イオン性界面活性剤（Ｄ）
を含有する、感光性樹脂組成物。
［２］ 前記一般式（１）中の、Ｘが、下記一般式（３）：

｛式（３）中、Ｒ₂、Ｒ₃、Ｒ₄及びＲ₅は、それぞれ独立に、水素原子、炭素数１〜１０の１価の脂肪族基、又は水素原子の一部若しくは全部がフッ素原子で置換されてなる炭素数１〜１０の１価の脂肪族基であり、ｎ₁は０〜４の整数であって、ｎ₁が１〜４の整数である場合のＲ₆は、ハロゲン原子、水酸基、又は１価の有機基であり、少なくとも１つのＲ₆は水酸基であり、ｎ₁が２〜４の整数である場合の複数のＲ₆はそれぞれ同じでも異なっていてもよい。｝で表される２価の基、及び下記一般式（４）：

｛式（４）中、Ｒ₇、Ｒ₈、Ｒ₉及びＲ₁₀は、それぞれ独立に、水素原子、炭素数１〜１０の１価の脂肪族基、又は水素原子の一部若しくは全部がフッ素原子で置換されてなる炭素数１〜１０の１価の脂肪族基を表し、Ｗは、単結合、フッ素原子で置換されていてもよい炭素数１〜１０の鎖状脂肪族基、フッ素原子で置換されていてもよい炭素数３〜２０の脂環式基、下記一般式（２）：

（式（２）中、ｐは、１〜１０の整数である。）で表される２価のアルキレンオキシド基、及び下記式（５）：

で表される２価の基から成る群から選ばれる２価の有機基である。｝で表される２価の基から成る群から選ばれる２価の有機基である、上記［１］に記載の感光性樹脂組成物。
［３］ 前記一般式（１）中の、Ｘが、下記式（６）：

で表される２価の有機基である、上記［１］又は［２］に記載の感光性樹脂組成物。
［４］ 前記一般式（１）中の、Ｘが、下記式（７）：

で表される２価の有機基である、上記［１］〜［３］のいずれかに記載の感光性樹脂組成物。
［５］ 前記フェノール樹脂（Ａ）が、下記一般式（８）：

｛式（８）中、Ｒ₁₁は炭化水素基及びアルコキシ基から成る群から選ばれる炭素数１〜１０の１価の基であり、ｎ₂は１〜３の整数であり、ｎ₃は０〜２の整数であり、ｍ₁は１〜５００の整数であり、２≦（ｎ₂＋ｎ₃）≦４であり、ｎ₃が２である場合のＲ₁₁はそれぞれ同じでも異なっていてもよい。｝で表される繰り返し単位、及び下記一般式（９）：

｛式（９）中、Ｒ₁₂及びＲ₁₃はそれぞれ独立に炭化水素基及びアルコキシ基から成る群から選ばれる炭素数１〜１０の１価の基であり、ｎ₄は１〜３の整数であり、ｎ₅は０〜２の整数であり、ｎ₆は０〜３の整数であり、ｍ₂は１〜５００の整数であり、２≦（ｎ₄＋ｎ₅）≦４であり、ｎ₅が２である場合のＲ₁₂はそれぞれ同じでも異なっていてもよく、ｎ₆が２又は３である場合のＲ₁₃はそれぞれ同じでも異なっていてもよい。｝で表される繰り返し単位の両方を同一樹脂骨格内に有するフェノール樹脂である、上記［１］〜［４］のいずれかに記載の感光性樹脂組成物。
［６］ 前記非イオン性界面活性剤（Ｄ）が、（Ｄ−１）シリコーン型界面活性剤、（Ｄ−２）エーテル型及びエステル型の一方又は両方である界面活性剤、並びに（Ｄ−３）フッ素型界面活性剤、から成る群から選ばれる少なくとも１種の非イオン性界面活性剤である、上記［１］〜［５］のいずれかに記載の感光性樹脂組成物。
［７］ 更に架橋剤（Ｅ）を含む、上記［１］〜［６］のいずれかに記載の感光性樹脂組成物。
［８］ 以下の工程：
（１）上記［１］〜［７］のいずれかに記載の感光性樹脂組成物を含む感光性樹脂層を基板上に形成する工程、
（２）該感光性樹脂層を露光する工程、
（３）該露光の後の感光性樹脂層を現像してレリーフパターンを得る工程、
（４）該レリーフパターンを加熱処理する工程、
を含む、硬化レリーフパターンの製造方法。
［９］ 上記［８］に記載の方法により製造された、硬化レリーフパターン。
［１０］ 半導体素子と、該半導体素子の上部に設けられた硬化膜とを備える半導体装置であって、該硬化膜は、上記［９］に記載の硬化レリーフパターンである、半導体装置。
［１１］ 表示体素子と、該表示体素子の上部に設けられた硬化膜とを備える表示体装置であって、該硬化膜は、上記［９］に記載の硬化レリーフパターンである、表示体装置。 [1] The following general formula (1):

{Wherein (1), a is an integer of 1 to 3, b is an integer of 0 to 3, a 1 ≦ (a + b) ≦ 4, R 1 is 1 1 to 20 carbon atoms Represents a monovalent substituent selected from the group consisting of a valent organic group, a halogen atom, a nitro group and a cyano group, and when b is 2 or 3, a plurality of R ₁ may be the same or different from each other , X is a divalent chain aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic group having 3 to 20 carbon atoms, and the following general formula (2):

(In formula (2), p is an integer of 1 to 10.) A divalent alkylene oxide group represented by the formula (2) and a divalent organic group selected from the group consisting of divalent organic groups having an aromatic ring. Represents an organic group. } A phenol resin (A) having a repeating unit represented by:
Photoacid generator (B),
Solvent (C) and nonionic surfactant (D)
The photosensitive resin composition containing this.
[2] In the general formula (1), X represents the following general formula (3):

{In Formula (3), R ₂ , R ₃ , R ₄ and R ₅ are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a part or all of the hydrogen atoms are fluorine. R ₆ is a monovalent aliphatic group having 1 to 10 carbon atoms substituted with an atom, n ₁ is an integer of 0 to 4, and n ₁ is an integer of ₁ to 4; An atom, a hydroxyl group, or a monovalent organic group, at least one R ₆ is a hydroxyl group, and when n ₁ is an integer of 2 to 4, a plurality of R ₆ may be the same or different. }, And the following general formula (4):

{In Formula (4), R ₇ , R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a part or all of the hydrogen atoms are fluorine. Represents a monovalent aliphatic group having 1 to 10 carbon atoms that is substituted with an atom, and W is a single bond, a chain aliphatic group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, or a fluorine atom. An alicyclic group having 3 to 20 carbon atoms which may be substituted with the following general formula (2):

(In formula (2), p is an integer of 1 to 10) and a divalent alkylene oxide group represented by the following formula (5):

A divalent organic group selected from the group consisting of divalent groups represented by the formula: } The photosensitive resin composition as described in [1] above, which is a divalent organic group selected from the group consisting of divalent groups represented by:
[3] In the general formula (1), X represents the following formula (6):

The photosensitive resin composition according to the above [1] or [2], which is a divalent organic group represented by the formula:
[4] In the general formula (1), X represents the following formula (7):

The photosensitive resin composition in any one of said [1]-[3] which is a bivalent organic group represented by these.
[5] The phenol resin (A) is represented by the following general formula (8):

{In Formula (8), R ₁₁ is a monovalent group having 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, n ₂ is an integer of 1 to 3, and n ₃ is 0 Is an integer of ˜2, m ₁ is an integer of ₁ to 500, 2 ≦ (n ₂ + n ₃ ) ≦ 4, and when n ₃ is 2, R ₁₁ may be the same or different. . } And the following general formula (9):

{In Formula (9), R ₁₂ and R ₁₃ are each independently a monovalent group having 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, and n ₄ is an integer of 1 to 3. N ₅ is an integer of 0 to 2, n ₆ is an integer of 0 to 3, m ₂ is an integer of ₁ to 500, 2 ≦ (n ₄ + n ₅ ) ≦ 4, and n ₅ R ₁₂ when n is 2 may be the same or different, and R ₁₃ when n ₆ is 2 or 3 may be the same or different. } The photosensitive resin composition in any one of said [1]-[4] which is a phenol resin which has both the repeating units represented by} in the same resin frame | skeleton.
[6] The nonionic surfactant (D) is (D-1) a silicone-type surfactant, (D-2) a surfactant that is one or both of an ether type and an ester type, and (D- 3) The photosensitive resin composition according to any one of the above [1] to [5], which is at least one nonionic surfactant selected from the group consisting of fluorine type surfactants.
[7] The photosensitive resin composition according to any one of [1] to [6], further including a crosslinking agent (E).
[8] The following steps:
(1) The process of forming the photosensitive resin layer containing the photosensitive resin composition in any one of said [1]-[7] on a board | substrate,
(2) a step of exposing the photosensitive resin layer;
(3) A step of developing the photosensitive resin layer after the exposure to obtain a relief pattern;
(4) a step of heat-treating the relief pattern;
A method for producing a cured relief pattern.
[9] A cured relief pattern produced by the method according to [8] above.
[10] A semiconductor device comprising a semiconductor element and a cured film provided on the semiconductor element, wherein the cured film is the cured relief pattern according to the above [9].
[11] A display device comprising a display element and a cured film provided on the display element, wherein the cured film is the cured relief pattern according to [9]. apparatus.

  According to the present invention, a photosensitive resin composition that can be cured at a low temperature and provides a cured film having excellent chemical resistance, a method for producing a cured relief pattern that forms a pattern using the photosensitive resin composition, and A semiconductor device and a display device having the cured relief pattern can be provided.

  Hereinafter, modes for carrying out the present invention (hereinafter abbreviated as “embodiments”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary. Throughout the present specification, when a plurality of structures represented by the same symbol in the general formula are present in a molecule, they may be the same as or different from each other.

  The photosensitive resin composition provided by one embodiment of the present invention has the following general formula (1):

{Wherein (1), a is an integer of 1 to 3, b is an integer of 0 to 3, a 1 ≦ (a + b) ≦ 4, R 1 is 1 1 to 20 carbon atoms Represents a monovalent substituent selected from the group consisting of a valent organic group, a halogen atom, a nitro group and a cyano group, and when b is 2 or 3, a plurality of R ₁ may be the same or different from each other , X is a divalent chain aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic group having 3 to 20 carbon atoms, and the following general formula (2):

(In formula (2), p is an integer of 1 to 10.) A divalent alkylene oxide group represented by the formula (2) and a divalent organic group selected from the group consisting of divalent organic groups having an aromatic ring. Represents an organic group. } A phenol resin (A) having a repeating unit represented by:
Photoacid generator (B),
Solvent (C) and nonionic surfactant (D)
Containing. Hereinafter, each component will be described in order.

[Phenolic resin (A)]
In this embodiment, the phenol resin (A) is represented by the following general formula (1):

{Wherein (1), a is an integer of 1 to 3, b is an integer of 0 to 3, a 1 ≦ (a + b) ≦ 4, R 1 is 1 1 to 20 carbon atoms Represents a monovalent substituent selected from the group consisting of a valent organic group, a halogen atom, a nitro group and a cyano group, and when b is 2 or 3, a plurality of R ₁ may be the same or different from each other , X is a divalent chain aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic group having 3 to 20 carbon atoms, and the following general formula (2):

(In formula (2), p is an integer of 1 to 10.) A divalent alkylene oxide group represented by the formula (2) and a divalent organic group selected from the group consisting of divalent organic groups having an aromatic ring. Represents an organic group. } Has a repeating unit represented by: The phenol resin (A) having the above repeating unit can be cured at a low temperature as compared with, for example, conventionally used polyimide resins and polybenzoxazole resins, and can form a cured film having good elongation. to enable.

In the general formula (1), R ₁ is not limited as long as it is a monovalent substituent selected from the group consisting of a monovalent organic group having 1 to 20 carbon atoms, a halogen atom, a nitro group, and a cyano group. From the viewpoint of alkali solubility, a halogen atom, a nitro group, a cyano group, an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, an aromatic group having 6 to 20 carbon atoms, and the following general formula (10):

{In Formula (10), R ₁₄ , R ₁₅ and R ₁₆ are each independently a hydrogen atom, a C1-C10 chain aliphatic group optionally having an unsaturated bond, C3-C3 20 represents an alicyclic group or an aromatic group having 6 to 20 carbon atoms, and R ₁₇ is a divalent chain aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, A divalent alicyclic group having 3 to 20 carbon atoms or a divalent aromatic group having 6 to 20 carbon atoms is represented. } Is preferably a monovalent substituent selected from the group consisting of four groups represented by:

  In this embodiment, in the general formula (1), a is not limited as long as it is an integer of 1 to 3, but 2 is preferable from the viewpoint of alkali solubility and elongation. Moreover, when a is 2, the substitution position of hydroxyl groups may be any of ortho, meta, and para positions. When a is 3, the substitution position between the hydroxyl groups may be any of 1,2,3-position, 1,2,4-position, 1,3,5-position, and the like.

In the present embodiment, in the general formula (1), b is not limited as long as it is an integer of 0 to 3, but is preferably 0 or 1 from the viewpoint of alkali solubility and elongation. When b is 2 or 3, the plurality of R ₁ may be the same or different.

  Further, in the present embodiment, in the general formula (1), a and b satisfy the relationship of 1 ≦ (a + b) ≦ 4.

  In the present embodiment, in the general formula (1), X is a divalent chain aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond, or a divalent chain having 3 to 20 carbon atoms. A divalent organic group selected from the group consisting of an alicyclic group, an alkylene oxide group represented by the general formula (2), and a divalent organic group having an aromatic ring. Among these divalent organic groups, X represents the following general formula (3) from the viewpoint of the toughness of the cured film.

{In Formula (3), R ₂ , R ₃ , R ₄ and R ₅ are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a part or all of the hydrogen atoms are fluorine. R ₆ is a monovalent aliphatic group having 1 to 10 carbon atoms substituted with an atom, n ₁ is an integer of 0 to 4, and n ₁ is an integer of ₁ to 4; In the case of an atom, a hydroxyl group, or a monovalent organic group, at least one R ₆ is a hydroxyl group, and n ₁ is an integer of 2 to 4, a plurality of R ₆ may be the same or different. } And the following general formula (4):

{In Formula (4), R ₇ , R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a part or all of the hydrogen atoms are fluorine. Represents a monovalent aliphatic group having 1 to 10 carbon atoms that is substituted with an atom, and W is a single bond, a chain aliphatic group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, or a fluorine atom. An alicyclic group having 3 to 20 carbon atoms which may be substituted with the following general formula (2):

(In formula (2), p is an integer of 1 to 10) and a divalent alkylene oxide group represented by the following formula (5):

A divalent organic group selected from the group consisting of divalent groups represented by the formula: } Is preferably an organic group selected from the group consisting of groups represented by:
W is a single bond, an alkylene oxide group represented by the above general formula (2), or a group consisting of an ester group, an amide group, and a sulfonyl group in the above formula (5) from the viewpoint of the elongation of the cured film. Preferred are divalent organic groups selected.

  In the present embodiment, in the general formula (1), X is preferably a divalent organic group represented by the general formula (3) or (4), and is represented by the general formula (4). The divalent organic group to be formed is represented by the following formula (6) from the viewpoint that the pattern forming property of the resin composition is good and the degree of elongation of the cured film after curing:

It is more preferable that it is a divalent organic group represented by the following formula (7):

The divalent organic group represented by the formula is particularly preferred.

  Regarding the ratio between the portion containing the phenolic hydroxyl group and the portion represented by X in the general formula (1), particularly from the viewpoint of elongation, the portion represented by X in the structure represented by the general formula (1) The ratio is preferably 20% by mass or more, and more preferably 30% by mass or more. The ratio is preferably 80% by mass or less, more preferably 70% by mass or less, from the viewpoint of alkali solubility.

  The phenol resin (A) is represented by the following general formula (8):

{In Formula (8), R ₁₁ is a monovalent group having 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, n ₂ is an integer of 1 to 3, and n ₃ is 0 Is an integer of ˜2, m ₁ is an integer of ₁ to 500, 2 ≦ (n ₂ + n ₃ ) ≦ 4, and when n ₃ is 2, R ₁₁ is the same or different. Also good. } And the following general formula (9):

{In Formula (9), R ₁₂ and R ₁₃ are each independently a monovalent group having 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, and n ₄ is an integer of 1 to 3. N ₅ is an integer of 0 to 2, n ₆ is an integer of 0 to 3, m ₂ is an integer of ₁ to 500, 2 ≦ (n ₄ + n ₅ ) ≦ 4, and n ₅ R ₁₂ when n is 2 may be the same or different, and R ₁₃ when n ₆ is 2 or 3 may be the same or different. } It is particularly preferable to have both of the structures represented by

M _{1 in the} general formula (8) and m _{2 in the} general formula (9) represent the total number of each repeating unit in the main chain of the phenol resin (A). That is, in the phenol resin (A), the repeating unit in parentheses in the structure represented by the general formula (8) and the repeating unit in parentheses in the structure represented by the general formula (9) are random, block Or they can be arranged in combination. m ₁ and m ₂ are each independently an integer of 1 to 500 from the viewpoint of alkali solubility and the elongation of the cured product, and the lower limit is preferably 2, more preferably 3, and the upper limit is Preferably it is 450, More preferably, it is 400, More preferably, it is 350. m ₁ and m ₂ are each independently preferably 2 or more from the viewpoint of the toughness of the film after curing, and preferably 450 or less from the viewpoint of solubility in an alkaline aqueous solution.

In the phenol resin (A) having both the structure represented by the general formula (8) and the structure represented by the general formula (9) in the same resin skeleton, the structure represented by the general formula (8) The higher the molar ratio, the better the film physical properties after curing, the better the heat resistance, and the higher the molar ratio of the structure represented by the general formula (9), the better the alkali solubility and the curing. Excellent pattern shape later. Therefore, m ₁ : m ₂ = 90: 10 to 20:80 is a film after curing as the range of the ratio between the structure represented by the general formula (8) and the structure represented by the general formula (9). From the viewpoint of physical properties, m ₁ : m ₂ = 80: 20 to 40:60 is more preferable from the viewpoint of film physical properties after curing and alkali solubility, and m ₁ : m ₂ = 70: 30 to 50:50 is preferable. It is particularly preferred from the viewpoints of film properties after curing, pattern shape, and alkali solubility.

The phenol resin (A) typically includes a phenol compound, a copolymer component (specifically, a compound having an aldehyde group (including a compound that decomposes to form an aldehyde compound like trioxane), a ketone group, and the like. One or more compounds selected from the group consisting of a compound having a methylol group, a compound having two methylol groups in the molecule, a compound having two alkoxymethyl groups in the molecule, and a compound having two haloalkyl groups in the molecule) More typically, monomer components composed of these can be synthesized by a polymerization reaction. For example, an aldehyde compound, a ketone compound, a methylol compound, an alkoxymethyl compound, a diene compound, a haloalkyl compound, etc. with respect to phenol and / or a phenol derivative (hereinafter also collectively referred to as “phenol compound”) as shown below A phenol resin (A) can be obtained by polymerizing the copolymer component. In this case, in the above general formula (1), the moiety represented by the structure in which the OH group and any R ₁ group are bonded to the aromatic ring is derived from the phenol compound, and the moiety represented by X is the above-mentioned common group. It comes from the polymerization component. From the viewpoint of reaction control and the stability of the obtained phenolic resin (A) and the photosensitive resin composition, the charging molar ratio of the phenolic compound and the copolymerization component is 5: 1 to 1 .01: 1 is preferable, and 2.5: 1 to 1.1: 1 is more preferable.

  In the present embodiment, the weight average molecular weight of the phenol resin (A) is preferably 700 to 100,000, more preferably 1,500 to 80,000, still more preferably 2,000 to 50,000. is there. The weight average molecular weight is preferably 700 or more from the viewpoint of the elongation of the cured film, while it is preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition.

  The weight average molecular weight is measured by gel permeation chromatography (GPC), and can be calculated from a calibration curve created using standard polystyrene.

  In this embodiment, examples of the phenol compound that can be used to obtain the phenol resin (A) include cresol, ethylphenol, propylphenol, butylphenol, amylphenol, cyclohexylphenol, hydroxybiphenyl, benzylphenol, nitrobenzylphenol, and cyano. Benzylphenol, adamantanephenol, nitrophenol, fluorophenol, chlorophenol, bromophenol, trifluoromethylphenol, N- (hydroxyphenyl) -5-norbornene-2,3-dicarboximide, N- (hydroxyphenyl) -5 -Methyl-5-norbornene-2,3-dicarboximide, trifluoromethylphenol, hydroxybenzoic acid, methyl hydroxybenzoate, hydride Ethyl xylbenzoate, benzyl hydroxybenzoate, hydroxybenzamide, hydroxybenzaldehyde, hydroxyacetophenone, hydroxybenzophenone, hydroxybenzonitrile, resorcinol, xylenol, catechol, methylcatechol, ethylcatechol, hexylcatechol, benzylcatechol, nitrobenzylcatechol, methylresorcinol , Ethyl resorcinol, hexyl resorcinol, benzyl resorcinol, nitrobenzyl resorcinol, hydroquinone, caffeic acid, dihydroxybenzoic acid, methyl dihydroxybenzoate, ethyl dihydroxybenzoate, butyl dihydroxybenzoate, propyl dihydroxybenzoate, benzyl dihydroxybenzoate, dihydroxy Benzamide Dihydroxybenzaldehyde, dihydroxyacetophenone, dihydroxybenzophenone, dihydroxybenzonitrile, N- (dihydroxyphenyl) -5-norbornene-2,3-dicarboximide, N- (dihydroxyphenyl) -5-methyl-5-norbornene-2,3 -Dicarboximide, nitrocatechol, fluorocatechol, chlorocatechol, bromocatechol, trifluoromethylcatechol, nitroresorcinol, fluororesorcinol, chlororesorcinol, bromoresorcinol, trifluoromethylresorcinol, pyrogallol, phloroglucinol, 1,2,4 -Trihydroxybenzene, trihydroxybenzoic acid, methyl trihydroxybenzoate, ethyl trihydroxybenzoate, Examples include butyl droxybenzoate, propyl trihydroxybenzoate, benzyl trihydroxybenzoate, trihydroxybenzamide, trihydroxybenzaldehyde, trihydroxyacetophenone, trihydroxybenzophenone, and trihydroxybenzonitrile.

  Examples of the aldehyde compound include acetaldehyde, propionaldehyde, pivalaldehyde, butyraldehyde, pentanal, hexanal, trioxane, glyoxal, cyclohexylaldehyde, diphenylacetaldehyde, ethylbutyraldehyde, benzaldehyde, glyoxylic acid, 5-norbornene-2-carboxyl Examples include aldehyde, malondialdehyde, succindialdehyde, glutaraldehyde, salicylaldehyde, naphthaldehyde, terephthalaldehyde, and the like.

  Examples of the ketone compound include acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, dicyclohexyl ketone, dibenzyl ketone, cyclopentanone, cyclohexanone, bicyclohexanone, cyclohexanedione, 3-butyn-2-one, 2-norbornanone, Adamantanone, 2,2-bis (4-oxocyclohexyl) propane, and the like.

  Examples of the methylol compound include 2,6-bis (hydroxymethyl) -p-cresol, 2,6-bis (hydroxymethyl) -4-ethylphenol, and 2,6-bis (hydroxymethyl) -4-propyl. Phenol, 2,6-bis (hydroxymethyl) -4-n-butylphenol, 2,6-bis (hydroxymethyl) -4-t-butylphenol, 2,6-bis (hydroxymethyl) -4-methoxyphenol, 2 , 6-bis (hydroxymethyl) -4-ethoxyphenol, 2,6-bis (hydroxymethyl) -4-propoxyphenol, 2,6-bis (hydroxymethyl) -4-n-butoxyphenol, 2,6- Bis (hydroxymethyl) -4-t-butoxyphenol, 1,3-bis (hydroxymethyl) urea, libito Arabitol, allitol, 2,2-bis (hydroxymethyl) butyric acid, 2-benzyloxy-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1, 3-propanediol, monoacetin, 2-methyl-2-nitro-1,3-propanediol, 5-norbornene-2,2-dimethanol, 5-norbornene-2,3-dimethanol, pentaerythritol, 2-phenyl -1,3-propanediol, trimethylolethane, trimethylolpropane, 3,6-bis (hydroxymethyl) durene, 2-nitro-p-xylylene glycol, 1,10-dihydroxydecane, 1,12-dihydroxydodecane 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydro Cymethyl) cyclohexene, 1,6-bis (hydroxymethyl) adamantane, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 2,6-bis (hydroxymethyl) -1,4-dimethoxybenzene, 2, 3-bis (hydroxymethyl) naphthalene, 2,6-bis (hydroxymethyl) naphthalene, 1,8-bis (hydroxymethyl) anthracene, 2,2′-bis (hydroxymethyl) diphenyl ether, 4,4′-bis ( Hydroxymethyl) diphenyl ether, 4,4′-bis (hydroxymethyl) diphenylthioether, 4,4′-bis (hydroxymethyl) benzophenone, 4-hydroxymethylbenzoic acid-4′-hydroxymethylphenyl, 4-hydroxymethylbenzoic acid -4'-hydroxymethylanilide 4,4′-bis (hydroxymethyl) phenylurea, 4,4′-bis (hydroxymethyl) phenylurethane, 1,8-bis (hydroxymethyl) anthracene, 4,4′-bis (hydroxymethyl) biphenyl, 2,2′-dimethyl-4,4′-bis (hydroxymethyl) biphenyl, 2,2-bis (4-hydroxymethylphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, di Examples include propylene glycol, tripropylene glycol, and tetrapropylene glycol.

  Examples of the alkoxymethyl compound include 2,6-bis (methoxymethyl) -p-cresol, 2,6-bis (methoxymethyl) -4-ethylphenol, and 2,6-bis (methoxymethyl) -4-. Propylphenol, 2,6-bis (methoxymethyl) -4-n-butylphenol, 2,6-bis (methoxymethyl) -4-t-butylphenol, 2,6-bis (methoxymethyl) -4-methoxyphenol, 2,6-bis (methoxymethyl) -4-ethoxyphenol, 2,6-bis (methoxymethyl) -4-propoxyphenol, 2,6-bis (methoxymethyl) -4-n-butoxyphenol, 2,6 -Bis (methoxymethyl) -4-t-butoxyphenol, 1,3-bis (methoxymethyl) urea, 2,2-bis (methoxy) Til) butyric acid, 2,2-bis (methoxymethyl) -5-norbornene, 2,3-bis (methoxymethyl) -5-norbornene, 1,4-bis (methoxymethyl) cyclohexane, 1,4-bis (methoxy) Methyl) cyclohexene, 1,6-bis (methoxymethyl) adamantane, 1,4-bis (methoxymethyl) benzene, 1,3-bis (methoxymethyl) benzene, 2,6-bis (methoxymethyl) -1,4 -Dimethoxybenzene, 2,3-bis (methoxymethyl) naphthalene, 2,6-bis (methoxymethyl) naphthalene, 1,8-bis (methoxymethyl) anthracene, 2,2'-bis (methoxymethyl) diphenyl ether, 4 , 4′-bis (methoxymethyl) diphenyl ether, 4,4′-bis (methoxymethyl) diphenylthio Ether, 4,4′-bis (methoxymethyl) benzophenone, 4-methoxymethylbenzoic acid-4′-methoxymethylphenyl, 4-methoxymethylbenzoic acid-4′-methoxymethylanilide, 4,4′-bis (methoxy) Methyl) phenylurea, 4,4′-bis (methoxymethyl) phenylurethane, 1,8-bis (methoxymethyl) anthracene, 4,4′-bis (methoxymethyl) biphenyl, 2,2′-dimethyl-4, 4'-bis (methoxymethyl) biphenyl, 2,2-bis (4-methoxymethylphenyl) propane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether And dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, and tetrapropylene glycol dimethyl ether.

  Examples of the diene compound include butadiene, pentadiene, hexadiene, heptadiene, octadiene, 3-methyl-1,3-butadiene, 1,3-butanediol-dimethacrylate, 2,4-hexadien-1-ol, and methyl. Cyclohexadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene, dicyclopentadiene, 1-hydroxydicyclopentadiene, 1-methylcyclopentadiene, methyldicyclopentadiene, diallyl ether, diallyl sulfide, diallyl adipate, 2 , 5-norbornadiene, tetrahydroindene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, triallyl cyanurate, diallyl isocyanurate, triisocyanurate Lil, diallyl propyl etc. isocyanuric acid.

  Examples of the haloalkyl compound include xylene dichloride, bischloromethyldimethoxybenzene, bischloromethyldurene, bischloromethylbiphenyl, bischloromethyl-biphenylcarboxylic acid, bischloromethyl-biphenyldicarboxylic acid, bischloromethyl-methylbiphenyl, Examples include bischloromethyl-dimethylbiphenyl, bischloromethylanthracene, ethylene glycol bis (chloroethyl) ether, diethylene glycol bis (chloroethyl) ether, triethylene glycol bis (chloroethyl) ether, tetraethylene glycol bis (chloroethyl) ether, and the like.

  A phenol resin (A) can be obtained by condensing the above-described phenolic compound and the copolymerization component by dehydration, dehydrohalogenation, or dealcoholization, or by polymerizing while cleaving the unsaturated bond. A catalyst may be used during the polymerization. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, methanesulfonic acid, p-toluenesulfonic acid, dimethyl sulfuric acid, diethyl sulfuric acid, acetic acid, oxalic acid, 1-hydroxyethylidene-1,1. Examples include '-diphosphonic acid, zinc acetate, boron trifluoride, boron trifluoride / phenol complex, boron trifluoride / ether complex, and the like. On the other hand, examples of the alkaline catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, triethylamine, pyridine, 4-N, N-dimethylaminopyridine, piperidine, Piperazine, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, Ammonia, hexamethylenetetramine and the like can be mentioned.

  In this embodiment, the amount of the catalyst used to obtain the phenol resin (A) is the total number of moles of copolymerization components, preferably aldehyde compounds, ketone compounds, methylol compounds, alkoxymethyl compounds, diene compounds and haloalkyls. It is preferably in the range of 0.01 mol% to 100 mol% with respect to 100 mol% of the total number of moles of the compound.

  When performing the synthesis reaction of a phenol resin (A), an organic solvent can be used as needed. Specific examples of organic solvents that can be used include bis (2-methoxyethyl) ether, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, Examples include toluene, xylene, γ-butyrolactone, N-methyl-2-pyrrolidone, but are not limited thereto. The amount of these organic solvents to be used is usually 10 parts by mass to 1000 parts by mass, preferably 20 parts by mass to 500 parts by mass, when the total mass of the charged raw materials is 100 parts by mass. In the synthesis reaction of the phenol resin (A), the reaction temperature is usually preferably 40 ° C. to 250 ° C., more preferably 100 ° C. to 200 ° C., and the reaction time is approximately 1 hour. 10 hours is preferable.

  In addition, the phenol resin (A) may be obtained by polymerizing a phenol compound that does not become a raw material having the structure of the general formula (1) as long as the effects of the present invention are not impaired. The range not impairing the effects of the present invention is, for example, 30% or less of the total number of moles of the phenol compound that is a raw material of the phenol resin (A).

  In the present embodiment, in the general formula (1), when a is 1, a phenol resin selected from a novolac resin and a polyhydroxystyrene resin (hereinafter referred to as a phenol resin (A ′) in order to improve alkali solubility. )) Can be mixed with the phenolic resin (A).

  The mixing ratio of the phenol resin (A) and the phenol resin (A ′) is preferably in the range of (A) / (A ′) = 10/90 to 90/10 in mass ratio. This mixing ratio is preferably (A) / (A ′) = 10/90 to 90/10 from the viewpoints of solubility in an alkaline aqueous solution and elongation of the cured film, and (A) / ( A ′) is more preferably 20/80 to 80/20, and further preferably (A) / (A ′) = 30/70 to 70/30.

  The novolak resin can be obtained by condensing phenols and formaldehyde in the presence of an acidic catalyst. Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2 , 3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5- Examples include trimethylphenol, catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol and the like. Specific examples of the novolak resin include phenol / formaldehyde condensed novolak resin, cresol / formaldehyde condensed novolak resin, phenol-naphthol / formaldehyde condensed novolak resin, and the like.

  As the polyhydroxystyrene resin, polyparavinylphenol is preferable. The polyparavinylphenol is not particularly limited as long as it is a polymer containing paravinylphenol as a polymerization unit. As the polymerization unit other than paravinylphenol, which can constitute polyparavinylphenol, any compound copolymerizable with paravinylphenol is possible unless it is contrary to the object of the present invention, for example, methyl acrylate, methyl Methacrylate, hydroxyethyl acrylate, butyl methacrylate, octyl acrylate, 2-ethoxyethyl acrylate, t-butyl acrylate, 1,5-pentanediol diacrylate, N, N-diethylaminoethyl acrylate, ethylene glycol diacrylate, 1, 3-propanediol diacrylate, decamethylene glycol diacrylate, decamethylene glycol dimethacrylate, 1,4-cyclohexanediol diacrylate, 2,2-dimethylolpropane Acrylate, glycerol diacrylate, tripropylene glycol diacrylate, glycerol triacrylate, 2,2-di (p-hydroxyphenyl) -propane dimethacrylate, triethylene glycol diacrylate, polyoxyethyl-2--2-di (p -Hydroxyphenyl) -propane dimethacrylate, triethylene glycol dimethacrylate, polyoxypropyltrimethylolpropane triacrylate, ethylene glycol dimethacrylate, butylene glycol dimethacrylate, 1,3-propanediol dimethacrylate, butylene glycol Dimethacrylate, 1,3-propanediol dimethacrylate, 1,2,4-butanetriol trimethacrylate, 2,2,4- Limethyl-1,3-pentanediol dimethacrylate, pentaerythritol trimethacrylate, 1-phenylethylene-1,2-dimethacrylate, pentaerythritol tetramethacrylate, trimethylolpropane trimethacrylate, 1,5-pentanediol Esters of acrylic acid, such as dimethacrylate and 1,4-benzenediol dimethacrylate; styrene, and substituted styrenes such as 2-methylstyrene and vinyltoluene; such as vinyl acrylate and vinyl methacrylate Monomers such as, but not limited to, vinyl esters; vinyl phenols other than para vinyl phenol, such as ortho vinyl phenol and meta vinyl phenol;

  The weight average molecular weight of the phenol resin (A ′) (that is, a phenol resin selected from a novolak resin and a polyhydroxystyrene resin) is preferably 700 to 100,000, more preferably 1,500 to 80,000. More preferably, it is 2,000 to 50,000. The weight average molecular weight is preferably 700 or more from the viewpoint of the elongation of the cured film, while it is preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition.

  In addition, the phenol resin selected from novolak resin and polyhydroxystyrene resin may be used individually by 1 type, and may be used in mixture of 2 or more types.

[Photoacid generator (B)]
In the present embodiment, the photosensitive resin composition is a composition that can form a resin pattern in response to actinic rays (that is, radiation) represented by ultraviolet rays, electron beams, X-rays, and the like. The photosensitive resin composition may be either a negative type (that is, a non-irradiated part is eluted by development) or a positive type (that is, an irradiated part is eluted by development).

  In this embodiment, when the photosensitive resin composition is used as a negative photosensitive resin composition, the photoacid generator (B) is irradiated with radiation to generate an acid, and the generated acid is the phenol resin. By causing a crosslinking reaction between (A) and the crosslinking agent, the radiation irradiated portion becomes insoluble in the developer. Examples of the photoacid generator (B) that can be used in the negative type include the following compounds:

(I) Trichloromethyl-s-triazines Tris (2,4,6-trichloromethyl) -s-triazine, 2-phenyl-bis (4,6-trichloromethyl) -s-triazine, 2- (3-chlorophenyl) ) -Bis (4,6-trichloromethyl) -s-triazine, 2- (2-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -bis (4 , 6-Trichloromethyl) -s-triazine, 2- (3-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxyphenyl) -bis (4,6-trichloro Methyl) -s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methylthiophenyl) ) Bis (4,6-trichloromethyl-s-triazine, 2- (2-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -bis (4 6-trichloromethyl) -s-triazine, 2- (3-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxynaphthyl) -bis (4,6-trichloromethyl) ) -S-triazine, 2- (3,4,5-trimethoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methylthio-β-styryl) -bis ( 4,6-trichloromethyl) -s-triazine, 2- (3-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methylthio- - styryl) - bis (4,6-trichloromethyl) -s-triazine and the like;

(Ii) Diaryliodonium salts Diphenyliodonium tetrafluoroborate, diphenyliodonium tetrafluorophosphate, diphenyliodonium tetrafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, 4-methoxy Phenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, 4 -Methoxyphenylphenyl iodonium-p-toluenesulfonate, bis (4-ter-butylphenyl) iodonium tetrafluoroborate, bis (4-ter-butylphenyl) iodonium hexafluoroarsenate, bis (4-ter-butylphenyl) Iodonium trifluoromethanesulfonate, bis (4-ter-butylphenyl) iodonium trifluoroacetate, bis (4-ter-butylphenyl) iodonium-p-toluenesulfonate, etc .;

(Iii) Triarylsulfonium salts Triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluene Sulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenylsulfonium Trifluoroacetate 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoroarsenate, 4-phenylthiophenyl Diphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate, 4-phenylthiophenyldiphenyl-p-toluenesulfonate, and the like.

  Among these compounds, trichloromethyl-s-triazines include 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-chlorophenyl) -bis (4, 6-trichloromethyl) -s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy-β-styryl) -bis (4,6 -Trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, and the like as diaryl iodonium salts include diphenyl iodonium trifluoroacetate, diphenyl iodonium trifluoromethane Sulfonate, 4-methoxyphenylphenyliodonium trifluoromethane For example, sulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, and triarylsulfonium salts include triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyl. Diphenylsulfonium trifluoroacetate, 4-phenylthiophenyl diphenyl trifluoromethanesulfonate, 4-phenylthiophenyl diphenyl trifluoroacetate and the like can be mentioned as suitable ones.

  In addition, the following compounds can also be used as the photoacid generator (B).

(1) Diazoketone compound Examples of the diazoketone compound include 1,3-diketo-2-diazo compound, diazobenzoquinone compound, diazonaphthoquinone compound, and the like. Specific examples include 1,2-naphthoquinonediazide of phenols. A 4-sulfonic acid ester compound can be mentioned.

(2) Sulfone compounds Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds and α-diazo compounds of these compounds. Specific examples include 4-trisphenacylsulfone, mesitylphena. Examples include silsulfone and bis (phenacylsulfonyl) methane.

(3) Sulfonic acid compound Examples of the sulfonic acid compound include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Preferred examples include benzoin tosylate, pyrogallol tris trifluoromethane sulfonate, o-nitrobenzyl trifluoromethane sulfonate, o-nitrobenzyl-p-toluene sulfonate, and the like.

(4) Sulfonimide compound Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- ( (Trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide and the like.

(5) Oxime ester compound As an oxime ester compound, specifically, 2- [2- (4-methylphenylsulfonyloxyimino)]-2,3-dihydrothiophene-3-ylidene] -2- (2-methyl Phenyl) acetonitrile (trade name “Irgacure PAG121” manufactured by Ciba Specialty Chemicals), [2- (propylsulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (Ciba Specialty) Chemicals trade name “Irgacure PAG103”), [2- (n-octanesulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (Ciba Specialty Chemicals trade name) "Irgacure PAG 108 ”), α- (n-octanesulfonyloxyimino) -4-methoxybenzyl cyanide (trade name“ CGI725 ”manufactured by Ciba Specialty Chemicals) and the like.

(6) Diazomethane compound Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and bis (phenylsulfonyl) diazomethane.

  From the viewpoint of sensitivity, the above (5) oxime ester compound is particularly preferable.

  In this embodiment, when the photosensitive resin composition is a negative type, the blending amount of the photoacid generator (B) with respect to 100 parts by mass of the phenol resin (A) is 0.1 to 50 parts by mass. Preferably, it is 1-40 mass parts. If the blending amount is 0.1 parts by mass or more, a sensitivity improvement effect can be obtained satisfactorily. If the blending amount is 50 parts by mass or less, the mechanical properties of the cured film are good.

  In this embodiment, the photosensitive resin composition can also be used as a positive photosensitive resin composition. In this case, the photoacid generators and / or quinonediazide compounds represented by the above (i) to (iii) and (1) to (6) are preferably used. Among these, a quinonediazide compound is preferable from the viewpoint of physical properties after curing. This is because the quinonediazide compound is thermally decomposed during curing and the amount remaining in the cured film is extremely low.

  The positive photoacid generator (B) is preferably a quinonediazide compound. Examples of the quinonediazide compound include compounds having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure (a compound having the latter structure is hereinafter also referred to as “NQD compound”). The compounds are known, for example, from US Pat. No. 2,772,972, US Pat. No. 2,797,213, US Pat. No. 3,669,658 and the like. The NQD compound is a 1,2-naphthoquinonediazide-4-sulfonic acid ester of a compound having a plurality of phenolic hydroxyl groups (hereinafter also referred to as “polyhydroxy compound”) described in detail below, and 1, It is at least one compound selected from the group consisting of 2-naphthoquinonediazide-5-sulfonic acid ester.

  The NQD compound is obtained by subjecting naphthoquinone diazide sulfonic acid to sulfonyl chloride with chlorosulfonic acid or thionyl chloride according to a conventional method, and subjecting the obtained naphthoquinone diazide sulfonyl chloride to a polyhydroxy compound. For example, a polyhydroxy compound and a predetermined amount of 1,2-naphthoquinonediazide-5-sulfonyl chloride or 1,2-naphthoquinonediazide-4-sulfonyl chloride in a solvent such as dioxane, acetone, or tetrahydrofuran, triethylamine, etc. The reaction can be carried out in the presence of a basic catalyst for esterification, and the resulting product can be obtained by washing with water and drying.

  Examples of preferable NQD compounds from the viewpoint of cured film properties such as sensitivity and elongation include those represented by the following general formula group.

{Wherein Q is a hydrogen atom or the following group of formulas:

The naphthoquinone diazide sulfonate group represented by any of the above, but not all Q are hydrogen atoms at the same time. }.

  Further, as the NQD compound, a naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule can be used, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl group. A mixture with an ester compound can also be used.

  The NQD compounds may be used alone or in combination of two or more.

  In the present embodiment, the amount of the photoacid generator (B) used when the photosensitive resin composition is positive is preferably 0.1 with respect to 100 parts by mass of the phenol resin (A) of the composition. It is -70 mass parts, More preferably, it is 1-40 mass parts, More preferably, it is 5-30 mass parts. If this amount used is 0.1 parts by mass or more, good sensitivity is obtained, and if it is 70 parts by mass or less, the mechanical properties of the cured film are good.

[Solvent (C)]
Examples of the solvent (C) include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons and the like. For example, N-methyl-2- Pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, Ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, ethylene glycol Use methyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene, etc. be able to. Among them, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene from the viewpoints of resin solubility, resin composition stability, and adhesion to a substrate. Glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenyl glycol, and tetrahydrofurfuryl alcohol are preferred.

  In the photosensitive resin composition of the present invention, the amount of the solvent (C) used is preferably 100 to 1000 parts by mass, more preferably 120 to 700 parts by mass with respect to 100 parts by mass of the phenol resin (A). More preferably, it is the range of 125-500 mass parts.

[Nonionic surfactant (D)]
In the present invention, the chemical resistance of the cured film can be improved by combining the phenol resin (A) and the nonionic surfactant (D).

The surfactant is a compound having both a hydrophilic group and a hydrophobic group in the molecule. There are two types of surfactants: an ionic surfactant that dissociates into ions and a nonionic surfactant that does not dissociate into ions. The ionic surfactant includes hydrophilic groups such as —COO ⁻ and —SO ₃ ^— and hydrophobic groups such as H ⁺ , Na ⁺ , K ⁺ , NH ₄ ⁺ , Ca ⁺⁺ , Cl ⁻ , Br ^{− and the} like. And a group including Nonionic surfactants are hydrophilic groups such as hydroxyl groups, ether groups, ester groups, etc. and hydrophobic groups which may have unsaturated bonds, such as aliphatic groups, aromatic groups, haloalkyl groups, and silicone moieties. And a group containing a group such as a fluorine moiety.

  When these ionic surfactants are added to the photosensitive resin composition of the present invention, there are problems such as defects due to corrosion of the wiring metal by the ionic compound during relief pattern formation, relief pattern curing, and after semiconductor device formation. Get up. Therefore, it is important to add a nonionic surfactant that does not contain these ionic compounds.

  Examples of the nonionic surfactant (D) used in the present invention are shown in the following (D-1) to (D-3). The surfactants (D-1) to (D-3) are advantageous from the viewpoints of the coating properties of the composition varnish and the prevention of residues and pattern lift during development.

(D-1) Silicone type surfactant The silicone type nonionic surfactant is a surfactant having a siloxane bond and a silicon-carbon bond in the molecule. Examples thereof include dimethylsiloxane ethyleneoxy graft compound, dimethylsiloxane propyleneoxy graft compound, (hydroxyethyleneoxypropyl) methylsiloxane-dimethylsiloxane compound, and the like.

  Specific examples include organosiloxane polymers KF-640, 642, 643, KP341, X-70-092, X-70-093 (above, trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (above, trade name, manufactured by Toray Dow Corning Silicone), SILWET L-77, L-7001, FZ-2105, FZ- 2120, FZ-2154, FZ-2164, FZ-2166, L-7604 (trade name, manufactured by Nihon Unicar), DBE-814, DBE-224, DBE-621, CMS-626, CMS-222, KF -352A, KF-354L, KF-355A, KF-6020, DBE-821, DBE-712 (Gelest) BYK-307, BYK-310, BYK-378, BYK-333 (trade names, manufactured by BYK Japan), Granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), and the like. Among these, a dimethylsiloxane ethyleneoxy graft compound and a dimethylsiloxane propyleneoxy graft compound are preferable from the viewpoint of applicability of the composition varnish.

(D-2) Ether-type and / or ester-type surfactants Ether-type and / or ester-type nonionic surfactants are surfactants containing ether bonds and / or ester groups in the molecule. It is an agent.

  For example, polyoxyethylene alkyl ethers include polyoxyethylene lauryl ether, polyoxyethylene steryl ether, polyoxyethylene cetyl ether, polyoxyethylene olein ether, and the like. Polyoxyethylene dialkyl esters include polyoxyethylene dialkyl esters. Examples include polyoxyethylene dilaurate and polyoxyethylene distearate. Examples of polyoxyethylene aryl ethers include polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether. Examples include polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and polyoxyethylene ether ester As polyoxyethylene glyceryl ether fatty acid ester, polyoxyethylene hydrogenated castor oil fatty acid ester and the like, polyoxyethylene sorbitan fatty acid esters include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, Examples include polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate. Examples of sorbitan fatty acid esters include sorbitan monolaurate, sorbitan monopalmitate, and sorbitan monostearate. Others include polyethylene glycol fatty acid ester, polyoxyethylene trimethylolpropane fatty acid ester, etc.

  Specifically, span 20, 80, 83, 85, sucrose fatty acid ester, polyethylene glycol monooleyl ether, polyglycol 200, 600, 4000 (manufactured by Tokyo Chemical Industry Co., Ltd.) and the like can be mentioned.

  Among these, from the viewpoint of applicability of the composition varnish, polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene sorbitan fatty acid esters, and sorbitan fatty acid esters are preferable.

(D-3) Fluorine-type surfactant A fluorine-type nonionic surfactant is a surfactant containing a fluorine atom in the molecule. Specific examples include perfluoroalkyl carboxylic acid, perfluoroalkyl sulfonic acid, perfluoroalkyl group-containing oligomer (manufactured by Dainippon Ink Chemical Co., Ltd., trade name: Mega-Fac product number R-08), and the following general formula (11). Compound

{Wherein R ₁₈ represents a trifluoromethyl group or a pentafluoroethyl group, and m ₃ represents an integer of 1 to 25. } Etc. are mentioned.

  Specifically, F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), MegaFuck F171, F172, F173 (above, manufactured by Dainippon Ink and Chemicals), Florard FC430, FC431 (above, manufactured by Sumitomo 3M) , Asahi Guard AG710, Surflon S-381, S-382, SC101, SC102, SC103, SC104, SC105, SC106, Surfinol E1004, KH-10, KH-20, KH-30, KH-40 (above, manufactured by Asahi Glass ), 250, 251, 222F, FTX-218 (manufactured by Neos) and the like.

  Among these nonionic surfactants described in (D-1) to (D-3), from the viewpoint of chemical resistance, (D-1) silicone type surfactants and (D-2) ethers Type and / or ester type surfactants are preferred.

  Although it is not clear why the effect of improving the chemical resistance is obtained by adding the nonionic surfactant (D), the addition of the nonionic surfactant (D) The change in wettability is considered to be affected.

  The amount of the nonionic surfactant (D) used is 0.01 with respect to 100 parts by mass of the phenol resin (A) from the viewpoints of the coating properties of the composition varnish and the prevention of residue and pattern lift during development. It is preferable that it is -50 mass parts, and it is more preferable that it is 0.1-10 mass parts.

[Other ingredients]
If necessary, the photosensitive resin composition of the present invention may contain a crosslinking agent (E), a thermal acid generator, a silane coupling agent, a dye, a dissolution accelerator, and the like.

  The crosslinking agent (E) can be crosslinked with the phenol resin (A) when the relief pattern formed using the photosensitive resin composition of the present invention is heat-cured, or the crosslinking agent itself forms a crosslinked network. Such a compound. The crosslinking agent has two or more crosslinking groups in the molecule, and can further improve the thermal properties, mechanical properties, and chemical resistance of the cured film formed from the photosensitive resin composition.

  Examples of the crosslinking agent (E) include Cymel (registered trademark) 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, which are compounds containing a methylol group and / or an alkoxymethyl group. 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR 65, 300, My Coat 102, 105 (Mitsui Cytec Co., Ltd.), Nicalac (registered trademark) MX-270, -280, -290, Nicalac MS-11, Nikarak MW-30, -100, -300, -390, -750 (manufactured by Sanwa Chemical Co., Ltd.), DML-OCHP, DML-MBPC, DML-BPC, DML-PEP, DML-34X, DML-PSBP, DML-PTBP, DML-PCHP, DML-POP, D L-PFP, DML-MBOC, BisCMP-F, DML-BisOC-Z, DML-BisOCHP-Z, DML-BisOC-P, DMOM-PTBT, TMOM-BP, TMOM-BPA, TML-BPAF-MF (above, Honshu Chemical Industry Co., Ltd.), benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis ( Hydroxymethyl) biphenyl, dimethylbis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxy) Methyl) diphenyl ether, bis (methoxymethyl) benzophenone, methoxymethyl benzoate methoxymethyl, bis (methoxymethyl) biphenyl, dimethyl bis (methoxymethyl) biphenyl, and the like.

  Also, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol type epoxy resin, trisphenol type epoxy resin, tetraphenol type epoxy resin, phenol-xylylene type epoxy resin, naphthol-xylylene type epoxy resin, phenol, which are oxirane compounds -Naphthol type epoxy resin, phenol-dicyclopentadiene type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, diethylene glycol diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, 1 , 1,2,2-tetra (p-hydroxyphenyl) ethanetetraglycidyl ether, glycerol triglycidyl Ether, ortho-secondary butylphenyl glycidyl ether, 1,6-bis (2,3-epoxypropoxy) naphthalene, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, YDB-340, YDB-412, YDF-2001, YDF-2004 (Above, trade name, manufactured by Nippon Steel Chemical Co., Ltd.), NC-3000-H, EPPN-501H, EOCN-1020, NC-7000L, EPPN-201L, XD-1000, EOCN-4600 (above, trade name) Manufactured by Nippon Kayaku Co., Ltd.), Epicoat (registered trademark) 1001, Epicoat 1007, Epicoat 1009, Epicoat 5050, Epicoat 5051, Epicoat 1031S, Epicoat 180S65, Epicoat 157H70, YX-315- 75 (above, trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EHPE3150, Plaxel G402, PUE101, PUE105 (above, trade name, manufactured by Daicel Chemical Industries, Ltd.), Epicron (registered trademark) 830, 850, 1050, N-680, N-690, N-695, N-770, HP-7200, HP-820, EXA-4850-1000 (trade name, manufactured by DIC), Denacol (registered trademark) EX-201, EX -251, EX-203, EX-313, EX-314, EX-321, EX-411, EX-511, EX-512, EX-612, EX-614, EX-614B, EX-711, EX-731 , EX-810, EX-911, EM-150 (above, trade name, manufactured by Nagase ChemteX Corporation), Epolite (registered trader) ) 70P, Epolight 100MF (trade names, manufactured by Kyoeisha Chemical Co., Ltd.), and the like.

  Further, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, 1,3-phenylenebismethylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, takenate (isocyanate group-containing compounds). (Registered trademark) 500, 600, Cosmonate (registered trademark) NBDI, ND (trade name, manufactured by Mitsui Chemicals) Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402- B80T (above, trade name, manufactured by Asahi Kasei Chemicals Corporation) and the like.

  Further, 4,4′-diphenylmethane bismaleimide, phenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4, which are bismaleimide compounds. '-Diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, 4,4'-diphenyl ether bismaleimide, 4,4' -Diphenylsulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene, BMI-1000, BMI-1100, BMI-2000, BMI-2300, BMI- 3000, BMI-400 , BMI-5100, BMI-7000, BMI-TMH, BMI-6000, BMI-8000 (trade names, Daiwa Kasei Kogyo Co., Ltd.), and the like. However, the crosslinking agent (E) is not limited to these as long as it is a compound that can be thermally crosslinked.

  As a compounding quantity in the case of using a crosslinking agent (E), 0.1-40 mass parts is preferable with respect to 100 mass parts of phenol resins (A), and 1-30 mass parts is more preferable. If the blending amount is 0.1 parts by mass or more, the thermophysical properties and mechanical strength of the thermosetting film are good, and if it is 40 parts by mass or less, the stability of the composition in the varnish state and the elongation of the thermosetting film. Is good.

  The thermal acid generator is preferably blended from the viewpoint of exhibiting good thermal and mechanical properties of the cured product even when the curing temperature is lowered.

  Thermal acid generators include allyl chloroacetate, n-butyl chloroacetate, t-butyl chloroacetate, ethyl chloroacetate, methyl chloroacetate, benzyl chloroacetate, isopropyl chloroacetate, 2-methoxyethyl chloroacetate, methyl dichloroacetate, Methyl trichloroacetate, ethyl trichloroacetate, 2-ethoxyethyl trichloroacetate, t-butyl cyanoacetate, t-butyl methacrylate, ethyl trifluoroacetate, methyl trifluoroacetate, phenyl trifluoroacetate, vinyl trifluoroacetate, trifluoroacetic acid Isopropyl, allyl trifluoroacetate, ethyl benzoate, methyl benzoate, t-butyl benzoate, methyl 2-chlorobenzoate, ethyl 2-chlorobenzoate, ethyl 4-chlorobenzoate, ethyl 2,5-dichlorobenzoate 2,4-dichloro Carboxylic acid esters such as methyl benzoate, ethyl p-fluorobenzoate, methyl p-fluorobenzoate, t-butyl pentachlorophenylcarboxylate, methyl pentafluoropropionate, ethyl pentafluoropropionate, t-butyl crotonate Cyclic carboxylic acid esters such as phenolphthalein and thymolphthalein; ethyl methanesulfonate, methyl methanesulfonate, 2-methoxyethyl methanesulfonate, 2-isopropoxyethyl methanesulfonate, phenyl p-toluenesulfonate, ethyl p-toluenesulfonate, methyl p-toluenesulfonate, 2-phenylethyl p-toluenesulfonate, n-propyl p-toluenesulfonate, n-butyl p-toluenesulfonate, t-butyl p-toluenesulfonate , P- N-hexyl ruene sulfonate, n-heptyl p-toluenesulfonate, n-octyl p-toluenesulfonate, 2-methoxyethyl p-toluenesulfonate, propargyl p-toluenesulfonate, 3-butynyl p-toluenesulfonate , Ethyl trifluoromethanesulfonate, n-butyl trifluoromethanesulfonate, ethyl perfluorobutanesulfonate, methyl perfluorobutanesulfonate, benzyl (4-hydroxyphenyl) methylsulfonium hexafluoroantimonate, benzyl (4-hydroxyphenyl) Methylsulfonium hexafluorophosphate, trimethylsulfonium methylsulfate, tri-p-sulfonium trifluoromethanesulfonate, trimethylsulfonium trifluoromethanesulfate Sulfonates such as honate, pyridinium-p-toluenesulfonate, ethyl perfluorooctanesulfonate; 1,4-butane sultone, 2,4-butane sultone, 1,3-propane sultone, phenol red, bromocresol green, bromo Cyclic sulfonic acid esters such as cresol purple; aromatic carboxylic acid anhydrides such as 2-sulfobenzoic acid anhydride, p-toluenesulfonic acid anhydride, phthalic acid anhydride, etc. are generated by heat. If it is a compound to be, it will not be limited.

  As a compounding quantity in the case of using a thermal acid generator, 0.1-30 mass parts is preferable with respect to 100 mass parts of (A) phenol resin, 0.5-10 mass parts is more preferable, 1-5 mass More preferably, it is a part. If the blending amount is 0.1 parts by mass or more, the effect of maintaining the pattern shape after thermosetting is good. On the other hand, if the blending amount is 30 parts by mass or less, the lithography performance is not adversely affected, and the composition Good stability.

  As the silane coupling agent, 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name KBM803, manufactured by Chisso Corporation: trade name: Silaace S810), 3-mercaptopropyltriethoxysilane (manufactured by Amax Co., Ltd.): Product name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: product name LS1375, product of Amax Co., Ltd .: product name SIM6474.0), product of mercaptomethyltrimethoxysilane (product of Asmax Co., Ltd .: product) Name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by AMAX Co., Ltd .: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropyl eth Sidimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercapto Ethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercapto Ethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4 -Mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N- (3-triethoxysilylpropyl) urea (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name LS3610, manufactured by Amax Co., Ltd .: trade name SIU9055.0), N- (3-trimethoxysilylpropyl) urea (manufactured by AMAX Co., Ltd .: trade name SIU9058.0), N- (3-diethoxymethoxysilylpropyl) urea, N- (3-ethoxydimethoxysilylpropyl) urea, N -(3-tripropoxysilylpropyl) urea, N- (3-diethoxypropoxysilylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N- (3-dimethoxypropoxysilylpropyl) urea, N -(3-Methoxydipropoxy Silylpropyl) urea, N- (3-trimethoxysilylethyl) urea, N- (3-ethoxydimethoxysilylethyl) urea, N- (3-tripropoxysilylethyl) urea, N- (3-tripropoxysilylethyl) ) Urea, N- (3-ethoxydipropoxysilylethyl) urea, N- (3-dimethoxypropoxysilylethyl) urea, N- (3-methoxydipropoxysilylethyl) urea, N- (3-trimethoxysilylbutyl) ) Urea, N- (3-triethoxysilylbutyl) urea, N- (3-tripropoxysilylbutyl) urea, 3- (m-aminophenoxy) propyltrimethoxysilane (manufactured by Amax Co., Ltd .: trade name SLA0598.0 ), M-aminophenyltrimethoxysilane (Amax Co., Ltd.) Product name: SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Amax Co .: product name SLA0599.1) Aminophenyltrimethoxysilane (product name: SLA0599.2), 2- ( Trimethoxysilylethyl) pyridine (manufactured by AMAX Co., Ltd .: trade name SIT83396), 2- (triethoxysilylethyl) pyridine, 2- (dimethoxysilylmethylethyl) pyridine, 2- (diethoxysilylmethylethyl) pyridine, (3-triethoxysilylpropyl) -t-butylcarbamate, (3-glycidoxypropyl) triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra- n- Toxisilane, tetra-i-butoxysilane, tetra-t-butoxysilane, tetrakis (methoxyethoxysilane), tetrakis (methoxy-n-propoxysilane), tetrakis (ethoxyethoxysilane), tetrakis (methoxyethoxyethoxysilane), bis ( Trimethoxysilyl) ethane, bis (trimethoxysilyl) hexane, bis (triethoxysilyl) methane, bis (triethoxysilyl) ethane, bis (triethoxysilyl) ethylene, bis (triethoxysilyl) octane, bis (triethoxy Silyl) octadiene, bis [3- (triethoxysilyl) propyl] disulfide, bis [3- (triethoxysilyl) propyl] tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxy Citriethoxysilane, bis (pentadionate) titanium-O, O'-bis (oxyethyl) -aminopropyltriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropyl Phenylsilanediol, n-butylsiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n- Propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenol Lucilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n- Examples include, but are not limited to, propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol, and the like. These may be used alone or in combination.

  As the silane coupling agent, among the above-mentioned silane coupling agents, from the viewpoint of storage stability, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy (p-tolyl) silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxy Diphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and a silane coupling agent represented by the following structure are preferable.

  As a compounding quantity in the case of using a silane coupling agent, 0.01-20 mass parts is preferable with respect to 100 mass parts of phenol resins (A).

  Examples of the dye include methyl violet, crystal violet, and malachite green. As a compounding quantity of dye, 0.1-30 mass parts is preferable with respect to 100 mass parts of phenol resin (A).

  As the dissolution accelerator, a compound having a hydroxyl group or a carboxyl group is preferable. Examples of the compound having a hydroxyl group include the ballast agent used in the above-mentioned naphthoquinone diazide compound, paracumylphenol, bisphenols, resorcinol, and linear phenol compounds such as MtrisPC and MtetraPC, TrisP-HAP, TrisP -Non-linear phenolic compounds such as PHBA and TrisP-PA (all manufactured by Honshu Chemical Industry Co., Ltd.), 2 to 5 phenol substitutes of diphenylmethane, 1 to 5 phenol substitutes of 3,3-diphenylpropane, A compound obtained by reacting 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane with 5-norbornene-2,3-dicarboxylic anhydride in a molar ratio of 1: 2, bis- ( 3-amino-4-hydroxyphenyl) sulfone and 1,2-cyclo Compounds obtained by reacting xyldicarboxylic anhydride with a molar ratio of 1: 2, N-hydroxysuccinimide, N-hydroxyphthalimide, N-hydroxy 5-norbornene-2,3-dicarboxylic imide, etc. Can be mentioned. Examples of the compound having a carboxyl group include 3-phenyl lactic acid, 4-hydroxyphenyl lactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid, 2-methoxy-2. Examples include-(1-naphthyl) propionic acid, mandelic acid, atrolactic acid, α-methoxyphenylacetic acid, O-acetylmandelic acid, itaconic acid, and the like.

  As a compounding quantity in the case of using a solubility promoter, 0.1-30 mass parts is preferable with respect to 100 mass parts of (A) phenol resin.

<Method for producing cured relief pattern>
Another aspect of the present embodiment includes (1) a step of forming a photosensitive resin layer containing the above-described photosensitive resin composition of the present invention on a substrate, (2) a step of exposing the photosensitive resin layer, (3 A method for producing a cured relief pattern comprising the steps of: developing a photosensitive resin layer after the exposure to obtain a relief pattern; and (4) heat-treating the relief pattern. An example of this method will be described below.

  First, the photosensitive resin composition of the present embodiment is applied to an appropriate support or substrate such as a silicon wafer, a ceramic substrate, an aluminum substrate, or the like. The substrate here includes, in addition to an unprocessed substrate, for example, a substrate on which a semiconductor element or a display element is formed. At this time, in order to ensure water-resistant adhesion between the pattern to be formed and the support, an adhesion assistant such as a silane coupling agent may be applied to the support or the substrate in advance. The photosensitive resin composition is applied by spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, or the like.

  Next, it prebakes at 80-140 degreeC, and dries the coating film of the photosensitive resin composition. As thickness of the photosensitive resin layer after drying, 1-500 micrometers is preferable.

  Next, the photosensitive resin layer is exposed. As the actinic radiation for exposure, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable. From the viewpoint of pattern resolution and handleability, the light source wavelength is preferably in the g-line, h-line or i-line region of the mercury lamp, and may be a single or a mixture of two or more actinic rays. As the exposure apparatus, a contact aligner, a mirror projection, and a stepper are particularly preferable. After exposure, the coating film may be heated again at 80 to 140 ° C. as necessary.

  Next, development can be carried out using a developer by selecting from methods such as dipping, paddle, and rotary spraying. By developing, an exposed portion (in the case of a positive type) or an unexposed portion (in the case of a negative type) can be eluted and removed from the applied photosensitive resin layer to obtain a relief pattern.

  Developers include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide. An aqueous solution such as quaternary ammonium salts such as quaternary ammonium salts, and a water-soluble organic solvent such as methanol and ethanol, or an aqueous solution to which an appropriate amount of a surfactant is added as required can be used. In these, the tetramethylammonium hydroxide aqueous solution is preferable, The density | concentration of this tetramethylammonium hydroxide becomes like this. Preferably, it is 0.5-10 mass%, More preferably, it is 1-5 mass%.

  After development, the substrate on which the relief pattern is formed can be obtained by washing with a rinse solution and removing the developer. As a rinse liquid, distilled water, methanol, ethanol, isopropanol, etc. can be used individually or in combination of 2 or more types.

  Finally, a cured relief pattern can be obtained by heating the relief pattern thus obtained. The heating temperature is preferably 150 ° C. or higher and 300 ° C. or lower, and more preferably 250 ° C. or lower.

  In the method of forming a cured relief pattern using a polyimide or polybenzoxazole precursor composition commonly used for permanent film applications in semiconductor devices, the precursor is heated to 300 ° C or higher for dehydration cyclization. By advancing the reaction, it is necessary to convert it to polyimide or polybenzoxazole. However, in the method for producing a cured relief pattern of the present invention, the photosensitive resin composition can be cured even by heating at a lower temperature. Therefore, it can be suitably used for a semiconductor device and a display device that are vulnerable to heat. For example, the photosensitive resin composition according to the present invention is made of a high-dielectric material or a ferroelectric material having a process temperature restriction, for example, an oxide of a refractory metal such as titanium, tantalum, or hafnium. It is suitably used for a semiconductor device having an insulating layer.

  Of course, if the semiconductor device does not have such heat resistance restrictions, heat treatment may be performed at 300 to 400 ° C. also in this method. Such heat treatment can be performed by using a hot plate, an oven, or a temperature rising oven in which a temperature program can be set. Air may be used as the atmospheric gas when performing the heat treatment, and an inert gas such as nitrogen or argon may be used. Further, when it is necessary to perform heat treatment at a lower temperature, heating may be performed under reduced pressure using a vacuum pump or the like.

  The cured product according to the present embodiment has excellent chemical resistance, and even when the chemical solution that can be used in the semiconductor process is processed under the conditions that can be used in the semiconductor process, the cured film peels off, cracks, and None of the pattern collapse occurs and it has sufficient resistance. The cured product according to this embodiment is more excellent in chemical resistance to PGMEA (propylene glycol monomethyl ether acetate) and GBL (gamma butyrolactone). These solvents are solvents that may come into contact with the cured product according to the present embodiment in the semiconductor process as a solvent such as a photoresist and other photosensitive resin composition for a semiconductor protective film, a reworking agent, and the like. The evaluation method of chemical resistance is as described in the column of chemical resistance evaluation in the examples described later.

<Semiconductor device>
In addition, a semiconductor device having a cured relief pattern manufactured by the above-described method using the photosensitive resin composition of this embodiment is also an aspect of this embodiment. The semiconductor device of this embodiment includes a semiconductor element and a cured film provided on the semiconductor element, and the cured film is the above-described cured relief pattern. Here, the cured relief pattern may be laminated in direct contact with the semiconductor element, or may be laminated with another layer interposed therebetween. Examples of the cured film include a surface protective film, an interlayer insulating film, a rewiring insulating film, a flip-chip device protective film, and a semiconductor device protective film having a bump structure. The semiconductor device of this embodiment can be manufactured by combining the manufacturing method of a well-known semiconductor device and the manufacturing method of the hardening relief pattern of this invention mentioned above.

<Display body device>
The display body device of this embodiment includes a display body element and a cured film provided on the display body element, and the cured film is the above-described cured relief pattern. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer interposed therebetween. Examples of the cured film include surface protective films, insulating films, and planarizing films for TFT liquid crystal display elements and color filter elements, protrusions for MVA liquid crystal display devices, and partition walls for organic EL element cathodes. .

  Similar to the semiconductor device of the present embodiment, the display device of the present embodiment can be manufactured by combining a known display device manufacturing method and the above-described cured relief pattern manufacturing method of the present embodiment. .

  Hereinafter, although this embodiment is concretely demonstrated by a synthesis example, an Example, and a comparative example, this invention is not limited to this.

  The measurement conditions in the examples are as shown below.

<Weight average molecular weight>
About the phenol resin obtained by each synthesis example, molecular weight was measured on condition of the following using gel permeation chromatography (GPC), and the weight average molecular weight in standard polystyrene conversion was calculated | required.
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40 ° C
Column: Shodex KD-806M Two in series Mobile phase: 0.1 mol / l EtBr / NMP
Flow rate: 1 ml / min.

<Chemical resistance evaluation>
The photosensitive resin compositions obtained in Examples and Comparative Examples were spin-coated so that the film thickness after curing was about 10 μm, and pre-baked on a hot plate at 120 ° C. for 180 seconds to form a coating film. . The film thickness was measured with a film thickness measuring device, Lambda Ace (manufactured by Dainippon Screen). This coating film was exposed by irradiating an i-line with an exposure dose of 500 mJ / cm ² through a reticle with a test pattern using a stepper NSR2005i8A (Nikon Corp.) having an exposure wavelength of i-line (365 nm). After the exposure, only Example 26 described later was reheated on a hot plate at 120 ° C. for 180 seconds. Next, it is developed with a developing machine D-SPIN (manufactured by SOKUDO) at 23 ° C. using a 2.38 mass% tetramethylammonium hydroxide aqueous solution AZ-300MIF (manufactured by AZ Electronic Materials) for 100 seconds, and pure water After rinsing, curing was performed at 220 ° C. for 1 hour in a vertical curing furnace VF200B (manufactured by Koyo Thermo System Co., Ltd.) under a nitrogen atmosphere to obtain a cured relief pattern.

About the obtained hardening relief pattern, the chemical resistance with respect to PGMEA and GBL was evaluated. The processing conditions are as follows.
[PGMEA]
Immersion at room temperature for 10 minutes [GBL]
After immersion treatment at 80 ° C for 10 minutes, washed with water, dried in an atmosphere of 23 ° C and 50% RH for 5 hours or longer, appearance of the cured pattern (observed with an optical microscope), and change in film thickness (stylus step meter KLA- Measured with Tencor P-15). The evaluation criteria are as follows. The results are listed in Table 3.

◯: There is no change in pattern cracks, and both film reduction (namely, film thickness reduction) and swelling (namely, film thickness increase) are both less than 5%.
Δ: No pattern crack is generated, but film reduction or swelling of 5% or more and less than 10% is observed.
X: Generation of pattern cracks or film reduction or swelling of 10% or more is observed.

[Synthesis Example 1]
<Synthesis of phenol resin (A-1)>
100.9 g (0.8 mol) of phloroglucinol, 4,4′-bis (methoxymethyl) biphenyl (hereinafter also referred to as “BMMB”) in a separable flask with a Dean-Stark device of 0.5 liter capacity. 121.2 g (0.5 mol), diethyl sulfate 3.9 g (0.025 mol), and diethylene glycol dimethyl ether 140 g were mixed and stirred at 70 ° C. to dissolve the solid matter.

  The mixed solution was heated to 140 ° C. with an oil bath, and generation of methanol was confirmed from the reaction solution. The reaction solution was stirred at 140 ° C. for 2 hours.

  Next, the reaction vessel was cooled in the atmosphere, and 100 g of tetrahydrofuran was separately added thereto and stirred. The reaction dilution is dropped into 4 L of water under high-speed stirring to disperse and precipitate the resin, which is recovered, appropriately washed with water, dehydrated and then vacuum-dried, and a copolymer of phloroglucinol / BMMB (phenol resin) (A-1)) was obtained with a yield of 70%.

[Synthesis Example 2]
<Synthesis of phenol resin (A-2)>
Synthesis was performed in the same manner as in Synthesis Example 1 using 128.3 g (0.76 mol) of methyl 3,5-dihydroxybenzoate instead of phloroglucinol of Synthesis Example 1, and methyl 3,5-dihydroxybenzoate / A copolymer composed of BMMB (phenol resin (A-2)) was obtained with a yield of 65%.
[Synthesis Example 3]
<Synthesis of phenol resin (A-3)>
A separable flask with a Dean-Stark apparatus having a capacity of 1.0 L was purged with nitrogen, and then in the separable flask, 81.3 g (0.738 mol) of resorcinol, 84.8 g (0.35 mol) of BMMB, p-toluenesulfone 3.81 g (0.02 mol) of acid and 116 g of propylene glycol monomethyl ether (hereinafter also referred to as PGME) were mixed and stirred at 50 ° C. to dissolve the solid matter.

  The mixed solution was heated to 120 ° C. with an oil bath, and generation of methanol was confirmed from the reaction solution. The reaction solution was stirred at 120 ° C. for 3 hours.

  Next, 2,6-bis (hydroxymethyl) -p-cresol 24.9 (0.150 mol) g and PGME 249 g were mixed and stirred in a separate container, and the uniformly dissolved solution was added to the solution using a dropping funnel. The mixture was added dropwise to the separable flask in 1 hour, and stirred for another 2 hours after the addition.

  After completion of the reaction, the same treatment as in Synthesis Example 1 was carried out to obtain a copolymer (phenol resin (A-3)) consisting of resorcinol / BMMB / 2,6-bis (hydroxymethyl) -p-cresol in a yield of 77%. Got in.

[Example 1]
As shown in Table 1, phenol resin (A-1) 100 parts by mass, photoacid generator (B-1) 12 parts by mass, surfactant (D-1) 0.1 part by mass, and crosslinking agent (E- 1) 5 parts by mass was dissolved in 217 parts by mass of the solvent (C-1) and filtered through a 0.1 μm filter to prepare a positive photosensitive resin composition. The properties of this composition and its cured film were measured according to the evaluation method described above. The obtained results are shown in Table 3.

[Examples 2 to 27]
A composition comprising the components shown in Table 1 was prepared in the same manner as in Example 1, and the properties of the composition and its cured film were measured in the same manner as in Example 1. The obtained results are shown in Table 3.

[Example 28]
As shown in Table 1, phenol resin (A-1) 100 parts by mass, photoacid generator (B-2) 5 parts by mass, surfactant (D-1) 0.1 part by mass, and crosslinking agent (E- 1) 10 parts by mass was dissolved in 214 parts by mass of the solvent (C-1) and filtered through a 0.1 μm filter to prepare a negative photosensitive resin composition. The properties of this composition were measured according to the evaluation method described above. The obtained results are shown in Table 3.

[Comparative Examples 1-8]
A composition comprising the components shown in Table 2 was prepared in the same manner as in Example 1, and the properties of the composition and its cured film were measured in the same manner as in Example 1. The obtained results are shown in Table 3.

  The compositions described in Tables 1 and 2 are as follows.

<Phenolic resins (A) and (A ′)>
A-1: Copolymer composed of phloroglucinol / BMMB, polystyrene equivalent weight average molecular weight (Mw) = 15,000
A-2: Copolymer composed of methyl 3,5-dihydroxybenzoate / BMMB, polystyrene equivalent weight average molecular weight (Mw) = 21,000
A-3: A copolymer comprising resorcinol / BMMB / 2,6-bis (hydroxymethyl) -p-cresol, polystyrene-reduced weight average molecular weight (Mw) = 9,900
A-4: Phenol / biphenylene resin, polystyrene-reduced weight average molecular weight (Mw) = 2,400 (Maywa Kasei Co., Ltd., product name MEH-7851M)
A-5: Novolak resin, polystyrene-equivalent weight average molecular weight (Mw) = 10,600 (product name: EP-4080G, manufactured by Asahi Organic Materials Co., Ltd.)

（式中、Ｑの内８３％が以下の：

で表される構造であり、残余が水素原子である。）
Ｂ−２：オキシムエステル化合物（ＢＡＳＦ社製、商品名；イルガキュア ＰＡＧ１２１） <Photoacid generator (B)>
B-1: Photoacid generator represented by the following formula:

(Wherein 83% of Q is the following:

The remainder is a hydrogen atom. )
B-2: Oxime ester compound (manufactured by BASF, trade name: Irgacure PAG121)

<Solvent (C)>
C-1: γ-butyrolactone (GBL)

<Nonionic surfactant (D)>
D-1: Silicone type nonionic surfactant DBE821 (trade name, manufactured by Gelest)
D-2: Silicone type nonionic surfactant DBE224 (trade name, manufactured by Gelest)
D-3: Silicone type nonionic surfactant SILWET FZ-2105 (trade name, manufactured by Nihon Unicar)
D-4: Sorbitan lauric acid monoester span 20 (trade name, manufactured by Tokyo Chemical Industry Co., Ltd.)
D-5: Sorbitan oleic acid triester span 85 (trade name, manufactured by Tokyo Chemical Industry Co., Ltd.)
D-6: Fluorine type nonionic surfactant PF-656 (trade name, manufactured by OMNOVA Solutions)
D-7: Fluorine-type nonionic surfactant, Footent 251 (trade name, manufactured by Neos)

<Crosslinking agent (E)>
E-1: 1,3,4,6-tetrakis (methoxymethyl) glycoluril (manufactured by Sanwa Chemical Co., Ltd., trade name: Nicalak MX-270)

  As can be seen from the results shown in Table 3, in each Example, a cured film excellent in chemical resistance of the cured film can be formed. Therefore, according to the present invention, it is possible to provide an interlayer insulating film, a surface protective film, and the like for a semiconductor element having excellent chemical resistance by curing at a low temperature.

  The photosensitive resin composition of the present invention includes a surface protective film for a semiconductor device, a display device and a light emitting device, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, a protective film for a device having a bump structure, It can be suitably used as an interlayer insulating film of a multilayer circuit, a cover coat of a flexible copper-clad plate, a solder resist film, a liquid crystal alignment film, and the like.

Claims (11)

The following general formula (1):

{Wherein (1), a is an integer of 1 to 3, b is an integer of 0 to 3, a 1 ≦ (a + b) ≦ 4, R 1 is 1 1 to 20 carbon atoms Represents a monovalent substituent selected from the group consisting of a valent organic group, a halogen atom, a nitro group and a cyano group, and when b is 2 or 3, a plurality of R ₁ may be the same or different from each other , X is a divalent chain aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic group having 3 to 20 carbon atoms, and the following general formula (2):

(In formula (2), p is an integer of 1 to 10.) A divalent alkylene oxide group represented by the formula (2) and a divalent organic group selected from the group consisting of divalent organic groups having an aromatic ring. Represents an organic group. } A phenol resin (A) having a repeating unit represented by:
Photoacid generator (B),
Solvent (C) and nonionic surfactant (D)
The photosensitive resin composition containing this. In the general formula (1), X represents the following general formula (3):

{In Formula (3), R ₂ , R ₃ , R ₄ and R ₅ are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a part or all of the hydrogen atoms are fluorine. R ₆ is a monovalent aliphatic group having 1 to 10 carbon atoms substituted with an atom, n ₁ is an integer of 0 to 4, and n ₁ is an integer of ₁ to 4; An atom, a hydroxyl group, or a monovalent organic group, at least one R ₆ is a hydroxyl group, and when n ₁ is an integer of 2 to 4, a plurality of R ₆ may be the same or different. }, And the following general formula (4):

{In Formula (4), R ₇ , R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or a part or all of the hydrogen atoms are fluorine. Represents a monovalent aliphatic group having 1 to 10 carbon atoms that is substituted with an atom, and W is a single bond, a chain aliphatic group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, or a fluorine atom. An alicyclic group having 3 to 20 carbon atoms which may be substituted with the following general formula (2):

(In formula (2), p is an integer of 1 to 10) and a divalent alkylene oxide group represented by the following formula (5):

A divalent organic group selected from the group consisting of divalent groups represented by the formula: The photosensitive resin composition according to claim 1, which is a divalent organic group selected from the group consisting of divalent groups represented by: In the general formula (1), X represents the following formula (6):

The photosensitive resin composition of Claim 1 or 2 which is a bivalent organic group represented by these. In the general formula (1), X represents the following formula (7):

The photosensitive resin composition of any one of Claims 1-3 which is a bivalent organic group represented by these. The phenol resin (A) is represented by the following general formula (8):

{In Formula (8), R ₁₁ is a monovalent group having 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, n ₂ is an integer of 1 to 3, and n ₃ is 0 Is an integer of ˜2, m ₁ is an integer of ₁ to 500, 2 ≦ (n ₂ + n ₃ ) ≦ 4, and when n ₃ is 2, R ₁₁ may be the same or different. . } And the following general formula (9):

{In Formula (9), R ₁₂ and R ₁₃ are each independently a monovalent group having 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, and n ₄ is an integer of 1 to 3. N ₅ is an integer of 0 to 2, n ₆ is an integer of 0 to 3, m ₂ is an integer of ₁ to 500, 2 ≦ (n ₄ + n ₅ ) ≦ 4, and n ₅ R ₁₂ when n is 2 may be the same or different, and R ₁₃ when n ₆ is 2 or 3 may be the same or different. } The photosensitive resin composition of any one of Claims 1-4 which is a phenol resin which has both the repeating units represented by} in the same resin frame | skeleton.   The nonionic surfactant (D) is (D-1) a surfactant of a silicone type, (D-2) a surfactant of one or both of an ether type and an ester type, and (D-3) fluorine. The photosensitive resin composition of any one of Claims 1-5 which is at least 1 sort (s) of nonionic surfactant chosen from the group which consists of type | mold surfactant.   Furthermore, the photosensitive resin composition of any one of Claims 1-6 containing a crosslinking agent (E). The following steps:
(1) The process of forming the photosensitive resin layer containing the photosensitive resin composition of any one of Claims 1-7 on a board | substrate,
(2) a step of exposing the photosensitive resin layer;
(3) A step of developing the photosensitive resin layer after the exposure to obtain a relief pattern;
(4) a step of heat-treating the relief pattern;
A method for producing a cured relief pattern.   A cured relief pattern produced by the method according to claim 8.   A semiconductor device comprising a semiconductor element and a cured film provided on the semiconductor element, wherein the cured film is the cured relief pattern according to claim 9.   A display body device comprising a display body element and a cured film provided on the display body element, wherein the cured film is the cured relief pattern according to claim 9.