JP5981738B2 - Photosensitive resin composition and method for producing cured relief pattern - Google Patents

Description

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

  Conventionally, polyimide resins or 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, they are generally used as compositions in which a precursor having a ring structure opened is dissolved in a solvent. Therefore, in order to manufacture a semiconductor device, a step of ring-closing the precursor is required after the step of applying the composition on the semiconductor element. This ring closing step is usually performed by thermosetting which is heated to 300 ° C. or higher.

  However, in recent years, since semiconductor devices having inferior heat resistance compared to conventional products have been developed, a material for forming a surface protective film or an interlayer insulating film is required to have a lower thermosetting temperature, particularly 250 ° C. or less. In many cases, thermosetting properties are 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. Phenol resin is a resin that is widely used as a base resin for resists that are temporarily used as a mask in etching or film formation processes when manufacturing semiconductor devices, and does not require the above-described ring closure process, so it is cured at low temperatures. In addition, it is excellent in cost and photosensitive performance.

  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 and an α, α′-dihydroxyxylene compound are used instead of aldehydes. And a composition obtained by condensing at least one substituted xylene compound selected from the group consisting of an α, α′-dialkoxyxylene compound and a phenol compound.

  Further, Patent Document 3 discloses a negative photosensitive resin composition comprising an epoxy-containing substance, a vinylphenol resin, a biphenylphenol resin, and a specific urea-based cross-linking agent, as an interlayer insulating resin used for a silicon wafer or the like. The negative photosensitive resin composition used is described.

  Patent Document 4 describes a photosensitive resin composition for a surface protective film or an interlayer insulating film, comprising an alkali-soluble phenol resin, polyhydroxystyrene or a polyhydroxystyrene derivative, an organic solvent, and an alkoxysilyl group-containing organic compound. Has been.

  Moreover, when it is necessary to improve the adhesive strength between the cured product of the photosensitive resin composition containing the phenol resin and the silicon wafer, it has been proposed to add a silane coupling agent to the photosensitive resin composition ( (See Patent Document 4).

JP 2003-215789 A JP 2007-057595 A JP 2006-243161 A JP 2008-164816 A

  When the resin film is applied to a semiconductor device as a permanent film, the elongation of the cured resin film is important as one of the film physical properties. However, Patent Documents 1 to 4 do not describe the elongation of the cured relief pattern. Further, when the present inventors examined these cured relief patterns, there was room for improvement in elongation as compared with cured relief patterns made of a polyimide resin or polybenzoxazole resin that have been put into practical use. (See Comparative Examples 4 and 5 described later).

  In addition, when the cured relief pattern described in Patent Documents 1 to 4 is used as an interlayer insulating film necessary for a semiconductor manufacturing process, a process of providing a metal film by sputtering on the cured relief pattern occurs. . However, Patent Documents 1 to 4 do not describe whether or not appearance defects such as wrinkles and blisters that may occur on the cured relief pattern in the sputtering process are generated. When the present inventors examined these cured relief patterns, there was room for improvement in appearance defects during sputtering as compared with cured relief patterns made of polyimide resin or polybenzoxazole resin (described later). (See Comparative Examples 4 and 5).

  Therefore, the present invention provides a cured relief pattern that can be cured at low temperature, has an excellent relief pattern shape after curing, and does not cause appearance defects such as wrinkles when sputtered on the cured relief pattern. It is an object of the present invention to provide a photosensitive resin composition for forming a cured relief pattern for forming a pattern using the photosensitive resin composition, and a semiconductor device and a display device having the cured relief pattern.

  As a result of intensive investigations and repeated experiments in view of the above-described problems of the prior art, the present inventor has solved the above-mentioned problems by using a photosensitive resin composition containing a phenol resin having a specific structure in combination with a silane compound. The inventors have found that this can be solved, and have come to make the present invention. That is, the present invention is as follows.

｛式（１）中、ａは、２又は３の整数であり、ｂは、０〜２の整数であり、２≦（ａ＋ｂ）≦４であり、Ｒ_１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である場合には、２つのＲ_１は、互いに同一であるか、又は異なっていてよく、そして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、及び芳香族基を有する２価の有機基から成る群から選ばれる少なくとも１つの２価の有機基を表す。｝で表される構造を有するフェノール樹脂、
（Ｂ）光酸発生剤、
（Ｃ）溶剤、及び
（Ｄ）下記一般式（３）：

｛式（３）中、Ｘ_１及びＸ_２は、それぞれ独立に、炭素数１〜１０の１価の有機基を表し、ｓは、０〜２の整数であり、そしてＹ_０は、炭素数１〜２０の１価の有機基を表す。｝で表されるシラン化合物、
を含む感光性樹脂組成物。 [1] (A) The following general formula (1):

{In Formula (1), a is an integer of 2 or 3, b is an integer of 0-2, 2 <= (a + b) <= 4, and R < ₁ > is C1-C20 1 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, two R _{1 s} are the same or different from each other And 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, the following general formula (2):

(In formula (2), p is an integer of 1 to 10.) At least one selected from the group consisting of a divalent alkylene oxide group represented by formula (2) and a divalent organic group having an aromatic group. Represents a divalent organic group. }, A phenolic resin having a structure represented by:
(B) a photoacid generator,
(C) solvent, and (D) the following general formula (3):

{In Formula (3), X ₁ and X ₂ each independently represent a monovalent organic group having 1 to 10 carbon atoms, s is an integer of 0 to 2, and Y ₀ is the number of carbon atoms. 1 to 20 monovalent organic groups are represented. } A silane compound represented by
A photosensitive resin composition comprising:

｛式（４）中、Ｒ_２、Ｒ_３、Ｒ_４及びＲ_５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いる炭素数１〜１０の１価の脂肪族基であり、ｎ_１は、０〜４の整数であり、Ｒ_６は、ハロゲン原子、水酸基又は１価の有機基から選択され、ｎ_１が１の整数である場合には、Ｒ_６は、水酸基、又は水酸基を有する１価の有機基であり、そしてｎ_１が２〜４の整数である場合には、Ｒ_６の少なくとも１つは、水酸基、又は水酸基を有する１価の有機基であり、かつ複数のＲ_６は、それぞれ同一であるか、又は異なっていてよい。｝で表される２価の基及び／又は下記一般式（５）：

｛式（５）中、Ｒ_７、Ｒ_８、Ｒ_９及びＲ_１０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いる炭素数１〜１０の１価の脂肪族基を表し、そして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。）で表されるアルキレンオキシド基、及び下記式（６）：

で表される２価の基から成る群から選ばれる少なくとも１つの２価の有機基である。｝で表される２価の基である、［１］に記載の感光性樹脂組成物。 [2] In the general formula (1), X represents the following general formula (4):

{In Formula (4), 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. A monovalent aliphatic group having 1 to 10 carbon atoms substituted with an atom, n ₁ is an integer of 0 to 4, and R ₆ is selected from a halogen atom, a hydroxyl group or a monovalent organic group; , N ₁ is an integer of 1, R ₆ is a hydroxyl group or a monovalent organic group having a hydroxyl group, and when n ₁ is an integer of 2 to 4, at least R ₆ One is a hydroxyl group or a monovalent organic group having a hydroxyl group, and the plurality of R ₆ may be the same or different from each other. } And / or the following general formula (5):

{In Formula (5), 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 substituted with an atom, and W represents a single bond, a chain aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, fluorine C3-C20 alicyclic group which may be substituted by atom, the following general formula (2):

(In formula (2), p is an integer of 1 to 10.) and the following formula (6):

And at least one divalent organic group selected from the group consisting of divalent groups represented by: } The photosensitive resin composition as described in [1] which is a bivalent group represented by these.

で表される２価の有機基である、［１］又は［２］に記載の感光性樹脂組成物。 [3] In the general formula (1), X represents the following general formula (7):

The photosensitive resin composition as described in [1] or [2] which is a bivalent organic group represented by these.

で表される２価の有機基である、［１］〜［３］のいずれか一項に記載の感光性樹脂組成物。 [4] In the general formula (1), X represents the following general formula (8):

The photosensitive resin composition as described in any one of [1]-[3] which is a bivalent organic group represented by these.

｛式（９）中、Ｒ_１１は、炭化水素基又はアルコキシ基から選ばれる炭素数１〜１０の１価の基であり、ｎ_２は、２又は３の整数であり、ｎ_３は、０〜２の整数であり、ｍ_１は、１〜５００の整数であり、２≦（ｎ_２＋ｎ_３）≦４であり、そしてｎ_３が２である場合には、２つのＲ_１１は、互いに同一であるか、又は異なっていてよい。｝で表される構造及び下記一般式（１０）：

｛式（１０）中、Ｒ_１２及びＲ_１３は、それぞれ独立に、炭化水素基又はアルコキシ基から選ばれる炭素数１〜１０の１価の基であり、ｎ_４は、２又は３の整数であり、ｎ_５は、０〜２の整数であり、ｎ_６は、０〜３の整数であり、ｍ_２は、１〜５００の整数であり、２≦（ｎ_４＋ｎ_５）≦４であり、ｎ_５が２である場合には、２つのＲ_１２は、互いに同一であるか、又は異なっていてよく、そしてｎ_６が２〜３である場合には、複数のＲ_１３は、それぞれ同一であるか、又は異なっていてよい。｝で表される構造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、［１］〜［４］のいずれか一項に記載の感光性樹脂組成物。 [5] The (A) phenol resin has the following general formula (9):

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

{In Formula (10), R ₁₂ and R ₁₃ are each independently a monovalent group having 1 to 10 carbon atoms selected from a hydrocarbon group or an alkoxy group, and n ₄ is an integer of 2 or 3. Yes, n ₅ is an integer from 0 to 2, n ₆ is an integer from 0 to 3, m ₂ is an integer from 1 to 500, and 2 ≦ (n ₄ + n ₅ ) ≦ 4 , N ₅ is 2, the two R ₁₂ may be the same or different from each other, and when n ₆ is 2-3, each of the plurality of R ₁₃ is the same Or may be different. } The photosensitive resin composition as described in any one of [1]-[4] which is a phenol resin which has both the structures represented by} in the same resin frame | skeleton.

｛式（１１）中、Ｘ_３は、単結合又は炭素数１〜１０の２価の有機基を表し、そしてＹ_１は、アミノ基、ヒドロキシル基、カルボキシル基、アミド基及びアルコキシ基から成る群から選ばれる少なくとも１つの置換基を有する１価の基を表す。｝

｛式（１２）中、Ｘ_３は、単結合又は炭素数１〜１０の２価の有機基を表し、そしてＹ_２は、炭素数１〜２０の芳香族基、メルカプト基、グリシジル基、ビニル基、アクリロイル基及びメタクリロイル基から成る群から選ばれる少なくとも一つの置換基を有する１価の有機基を表す。｝
で表される基である、［１］〜［５］のいずれか一項に記載の感光性樹脂組成物。 [6] In the general formula (3), Y ₀ represents the following general formula (11) or (12):

{In Formula (11), X ₃ represents a single bond or a divalent organic group having 1 to 10 carbon atoms, and Y ₁ is a group consisting of an amino group, a hydroxyl group, a carboxyl group, an amide group and an alkoxy group. Represents a monovalent group having at least one substituent selected from: }

{In Formula (12), X ₃ represents a single bond or a divalent organic group having 1 to 10 carbon atoms, and Y ₂ represents an aromatic group, mercapto group, glycidyl group, vinyl having 1 to 20 carbon atoms. Represents a monovalent organic group having at least one substituent selected from the group consisting of a group, an acryloyl group and a methacryloyl group. }
The photosensitive resin composition as described in any one of [1]-[5] which is group represented by these.

｛式（１３）中、Ｘ_４及びＸ_５は、それぞれ独立に、炭素数１〜２０の１価の有機基を表し、Ｘ_６及びＸ_１０は、それぞれ独立に、炭素数１〜１０の２価の有機基を表し、Ｘ_７及びＸ_８は、それぞれ独立に、炭素数１〜１０の１価の有機基を表し、Ｘ_９は、４価の有機基を表し、そしてｓは、０〜２の整数である。｝で表される基から選ばれる少なくとも１つの基である、［６］に記載の感光性樹脂組成物。 [7] In the general formula (11), Y ₁ represents the following general formula (13):

{In Formula (13), X ₄ and X ₅ each independently represent a monovalent organic group having 1 to 20 carbon atoms, and X ₆ and X ₁₀ are each independently 2 of 1 to 10 carbon atoms. X ₇ and X ₈ each independently represent a monovalent organic group having 1 to 10 carbon atoms, X ₉ represents a tetravalent organic group, and s represents 0 to 0 It is an integer of 2. } The photosensitive resin composition as described in [6], which is at least one group selected from the group represented by:

｛式（１４）中、Ｘ_１１は、炭素数１〜２０の１価の有機基を表し、ｔは、０〜５の整数であり、ｔが２〜５である場合には、複数のＸ_１１は、それぞれ同一であるか、又は異なっていてよく、Ｘ_１２は、水素原子又はメチル基を表し、ｕは、０〜５の整数であり、ｕが２〜５である場合には、複数のＸ_１２は、それぞれ同一であるか、又は異なっていてよく、そしてＸ_１３及びＸ_１４は、それぞれ独立に、炭素数１〜１０の２価の基を表す。｝で表される基から選ばれる少なくとも１つの基である、［６］に記載の感光性樹脂組成物。 [8] In the general formula (12), Y ₂ represents the following general formula (14):

{In Formula (14), X ₁₁ represents a monovalent organic group having 1 to 20 carbon atoms, t is an integer of 0 to 5, and when t is 2 to 5, ₁₁ may be the same or different from each other, X ₁₂ represents a hydrogen atom or a methyl group, u is an integer of 0 to 5, and when u is 2 to 5, X ₁₂ in each may be the same or different, and X ₁₃ and X ₁₄ each independently represent a divalent group having 1 to 10 carbon atoms. } The photosensitive resin composition as described in [6], which is at least one group selected from the group represented by:

[9] The following steps:
(1) The process of forming the photosensitive resin layer containing the photosensitive resin composition as described in any one of [1]-[8] on a board | substrate,
(2) a step of exposing the photosensitive resin layer;
(3) removing exposed or unexposed areas with a developer to obtain a relief pattern; and (4) heat treating the relief pattern;
A method for producing a cured relief pattern comprising:

  [10] A cured relief pattern produced by the method according to [9].

  [11] 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 [10].

  [12] A display body device including 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 [10]. .

  To provide an excellent cured film that can be cured at a low temperature, has an excellent relief pattern shape after curing, and does not generate wrinkles when sputtered on the cured relief pattern, according to the present invention. Photosensitive resin, a method of forming a cured relief pattern that forms a pattern using the photosensitive resin, 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.

  In the embodiment, the photosensitive resin composition comprises the following components (A) to (D): (A) a phenol resin, (B) a photoacid generator, (C) a solvent, and (D) a silane compound. including. Hereinafter, each component will be described in order.

  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 or different from each other.

｛式（１）中、ａは、２又は３の整数であり、ｂは、０〜２の整数であり、２≦（ａ＋ｂ）≦４であり、Ｒ_１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である場合には、２つのＲ_１は、互いに同一であるか、又は異なっていてよく、そして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、及び芳香族基を有する２価の有機基から成る群から選ばれる少なくとも１つの２価の有機基を表す。｝ (A) Phenolic Resin In the embodiment, the (A) phenolic resin has a structure represented by the following general formula (1).

{In Formula (1), a is an integer of 2 or 3, b is an integer of 0-2, 2 <= (a + b) <= 4, and R < ₁ > is C1-C20 1 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, two R _{1 s} are the same or different from each other And 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, the following general formula (2):

(In formula (2), p is an integer of 1 to 10.) At least one selected from the group consisting of a divalent alkylene oxide group represented by formula (2) and a divalent organic group having an aromatic group. Represents a divalent organic group. }

｛式（１５）中、Ｒ_１５、Ｒ_１６及びＲ_１７は、それぞれ独立に、水素原子、不飽和結合を有していてもよい炭素数１〜１０の脂肪族基、炭素数３〜２０の脂環式基、又は炭素数６〜２０の芳香族基を表し、そしてＲ_１８は、不飽和結合を有していてもよい炭素数１〜１０の２価の脂肪族基、炭素数３〜２０の２価の脂環式基、又は炭素数６〜２０の２価の芳香族基を表す。｝ In the general formula (1), R ₁ is limited as long as it is at least one 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. However, 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 It is preferably at least one monovalent substituent selected from the group consisting of four groups represented by the following general formula (15).

{In Formula (15), R ₁₅ , R ₁₆ and R ₁₇ are each independently a hydrogen atom, an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, or 3 to 20 carbon atoms. Represents an alicyclic group or an aromatic group having 6 to 20 carbon atoms, and R ₁₈ is a divalent aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond; 20 bivalent alicyclic group or a C6-C20 bivalent aromatic group is represented. }

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

In the embodiment, in the general formula (1), b is not limited as long as it is an integer of 0 to 2, but is preferably 0 or 1 from the viewpoint of alkali solubility and elongation. When b is 2, the two R _{1 s} may be the same as or different from each other.

  Furthermore, in the embodiment, in the general formula (1), a and b satisfy the relationship of 2 ≦ (a + b) ≦ 4.

｛式（４）中、Ｒ_２、Ｒ_３、Ｒ_４及びＲ_５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いる炭素数１〜１０の１価の脂肪族基であり、ｎ_１は、０〜４の整数であり、Ｒ_６は、ハロゲン原子、水酸基又は１価の有機基から選択され、ｎ_１が１の整数である場合には、Ｒ_６は、水酸基、又は水酸基を有する１価の有機基であり、そしてｎ_１が２〜４の整数である場合には、Ｒ_６の少なくとも１つは、水酸基、又は水酸基を有する１価の有機基であり、かつ複数のＲ_６は、それぞれ同一であるか、又は異なっていてよい。｝

｛式（５）中、Ｒ_７、Ｒ_８、Ｒ_９及びＲ_１０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いる炭素数１〜１０の１価の脂肪族基を表し、そして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。）で表されるアルキレンオキシド基、及び下記式（６）：

で表される２価の基から成る群から選ばれる少なくとも１つの２価の有機基である。｝ In the 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. It is at least one divalent organic group selected from the group consisting of an alicyclic group, a divalent alkylene oxide group represented by the general formula (2), and a divalent organic group having an aromatic group. Among these divalent organic groups, X is preferably at least one of organic groups represented by the following general formulas (4) and (5) from the viewpoint of the toughness of the film after curing.

{In Formula (4), 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. A monovalent aliphatic group having 1 to 10 carbon atoms substituted with an atom, n ₁ is an integer of 0 to 4, and R ₆ is selected from a halogen atom, a hydroxyl group or a monovalent organic group; , N ₁ is an integer of 1, R ₆ is a hydroxyl group or a monovalent organic group having a hydroxyl group, and when n ₁ is an integer of 2 to 4, at least R ₆ One is a hydroxyl group or a monovalent organic group having a hydroxyl group, and the plurality of R ₆ may be the same or different from each other. }

{In Formula (5), 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 substituted with an atom, and W represents a single bond, a chain aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, fluorine C3-C20 alicyclic group which may be substituted by atom, the following general formula (2):

(In formula (2), p is an integer of 1 to 10.) and the following formula (6):

And at least one divalent organic group selected from the group consisting of divalent groups represented by: }

  In the general formula (5), W is represented by a single bond, an alkylene oxide group represented by the general formula (2), and the above formula (6) from the viewpoint of the elongation of the cured film. Of the divalent organic groups, a divalent organic group selected from an ester group, an amide group or a sulfonyl group is preferred.

In the embodiment, in the general formula (1), X is preferably a divalent organic group represented by the general formula (4) or (5), and represented by the general formula (5). The divalent organic group is more preferably a divalent organic group represented by the following general formula (7) from the viewpoint of the elongation of the cured film, and further represented by the following general formula (8). Particularly preferred is a divalent organic group.

  In the general formula (1), the proportion of the portion containing the phenolic hydroxyl group and the portion represented by X can form a pattern when the photosensitive resin composition is formed, and the elongation after curing is high. Even if the metal layer is formed by sputtering, it is not limited as long as the ratio is adjusted so that wrinkles are not generated in the metal film and the cured film, but in particular, from the viewpoint of elongation, the ratio of the portion represented by X is: Based on the total mass of the monomer units, it is preferably 20% by mass or more, and more preferably 30% by mass or more.

｛式（９）中、Ｒ_１１は、炭化水素基又はアルコキシ基から選ばれる炭素数１〜１０の１価の基であり、ｎ_２は、２又は３の整数であり、ｎ_３は、０〜２の整数であり、ｍ_１は、１〜５００の整数であり、２≦（ｎ_２＋ｎ_３）≦４であり、そしてｎ_３が２である場合には、２つのＲ_１１は、互いに同一であるか、又は異なっていてよい。｝

｛式（１０）中、Ｒ_１２及びＲ_１３は、それぞれ独立に、炭化水素基又はアルコキシ基から選ばれる炭素数１〜１０の１価の基であり、ｎ_４は、２又は３の整数であり、ｎ_５は、０〜２の整数であり、ｎ_６は、０〜３の整数であり、ｍ_２は、１〜５００の整数であり、２≦（ｎ_４＋ｎ_５）≦４であり、ｎ_５が２である場合には、２つのＲ_１２は、互いに同一であるか、又は異なっていてよく、そしてｎ_６が２〜３である場合には、複数のＲ_１３は、それぞれ同一であるか、又は異なっていてよい。｝ The phenol resin (A) represented by the general formula (1) has both the structure represented by the following general formula (9) and the structure represented by the following general formula (10) in the same resin skeleton. It is particularly preferable to have it.

{In Formula (9), R ₁₁ is a monovalent group having 1 to 10 carbon atoms selected from a hydrocarbon group or an alkoxy group, n ₂ is an integer of 2 or 3, and n ₃ is 0 When m ₁ is an integer from ₁ to 500, 2 ≦ (n ₂ + n ₃ ) ≦ 4, and n ₃ is 2, the two R ₁₁ are They may be the same or different. }

{In Formula (10), R ₁₂ and R ₁₃ are each independently a monovalent group having 1 to 10 carbon atoms selected from a hydrocarbon group or an alkoxy group, and n ₄ is an integer of 2 or 3. Yes, n ₅ is an integer from 0 to 2, n ₆ is an integer from 0 to 3, m ₂ is an integer from 1 to 500, and 2 ≦ (n ₄ + n ₅ ) ≦ 4 , N ₅ is 2, the two R ₁₂ may be the same or different from each other, and when n ₆ is 2-3, each of the plurality of R ₁₃ is the same Or may be different. }

M ₂ of the above general formula (9) m ₁ and the general formula in (10) in represents the total number of the respective repeating units in the polymer backbone, each independently, in toughness and alkaline aqueous solution of the cured film From the viewpoint of solubility, the lower limit is preferably 2, more preferably 3, and the upper limit is preferably 450, more preferably 400. Yes, more preferably 350. m ₁ and m ₂ are preferably 3 or more from the viewpoint of toughness of the cured film, and are preferably 350 or less from the viewpoint of solubility in an alkaline aqueous solution. The position of the structural unit represented by the general formula (9) and the structural unit represented by the general formula (10) in the polymer may be a block or random.

The higher the structural ratio represented by the general formula (9), the higher the (A) phenol resin having both the structures represented by the general formula (9) and the general formula (10) in the same resin skeleton, The cured film has good physical properties and excellent heat resistance. On the other hand, the higher the structural ratio represented by the general formula (10), the better the alkali solubility and the pattern shape after curing. Excellent. Therefore, as a range of the ratio of the structure represented by the general formula (9) and the structure represented by the general formula (10), m ₁ : m ₂ = 90: 10 to 20:80 is a physical property of the cured film. From the viewpoint of the above, m ₁ : m ₂ = 80: 20 to 40:60 is more preferable from the viewpoint of the physical properties and alkali solubility of the cured film, and m ₁ : m ₂ = 70: 30 to 50:50 is the cured film. It is particularly preferable from the viewpoints of physical properties, pattern shape, and alkali solubility.

  Typically, the (A) phenol resin can be synthesized by polymerizing a phenol compound and a copolymer component. Specifically, the copolymer component includes a compound having an aldehyde group (including a compound that decomposes to produce an aldehyde compound, such as trioxane), a compound having a ketone group, and two methylol groups in the molecule. A compound having at least one compound selected from the group consisting of a compound having two alkoxymethyl groups in the molecule, and a compound having two haloalkyl groups in the molecule. The copolymer component is preferably a component comprising at least one of these. For example, for phenol and / or phenol derivatives (hereinafter also referred to as “phenol compounds”) as shown below, for example, aldehyde compounds, ketone compounds, methylol compounds, alkoxymethyl compounds, diene compounds, haloalkyl compounds, etc. By polymerizing the copolymer component, the (A) phenol resin can be obtained. From the viewpoint of reaction control and the stability of the obtained phenolic resin and phenolic resin composition, the charged molar ratio of the phenolic compound and the copolymer component is preferably 5: 1 to 1.01: 1. More preferably, it is 5: 1 to 1.1: 1.

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

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

  (A) Examples of the phenol compound that can be used to obtain the phenol resin include resorcinol, xylenol, catechol, methyl catechol, ethyl catechol, hexyl catechol, benzyl catechol, nitrobenzyl catechol, methyl resorcinol, ethyl resorcinol, hexyl resorcinol, benzyl Resorcinol, nitrobenzyl resorcinol, hydroquinone, caffeic acid, dihydroxybenzoic acid, methyl dihydroxybenzoate, ethyl dihydroxybenzoate, butyl dihydroxybenzoate, propyl dihydroxybenzoate, benzyl dihydroxybenzoate, dihydroxybenzamide, dihydroxybenzaldehyde, dihydroxyacetophenone, Dihydroxybenzophenone, dihydroxyben Nitrile, 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, tri Methyl hydroxybenzoate, ethyl trihydroxybenzoate, butyl trihydroxybenzoate, propyl trihydroxybenzoate, benzyl trihydroxybenzoate, trihydroxy Nzuamido, trihydroxy benzaldehyde, trihydroxy acetophenone, trihydroxybenzophenone, trihydroxy benzonitrile and the like.

  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, 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, triallyl isocyanurate, isocyanuric Diallyl propyl and the like.

  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) A phenol resin can be obtained by condensing the above-mentioned phenol compound and the above-mentioned copolymerization component by dehydration, dehydrohalogenation or dealcoholization, or by polymerizing while cleaving the unsaturated bond. Moreover, you may use a catalyst at the time of superposition | polymerization of the above-mentioned phenolic compound and the above-mentioned copolymerization component. Examples of the catalyst include an acidic catalyst and an alkaline catalyst. 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 an embodiment, (A) the amount of the catalyst used to obtain the phenol resin is 0.01 to the number of moles of the aldehyde compound, ketone compound, methylol compound, alkoxymethyl compound, diene compound or haloalkyl compound. The range is preferably from mol% to 100 mol%.

  (A) When performing the synthesis reaction of a phenol resin, an organic solvent can be used as needed. Specific examples of the organic solvent that can be used include, but are not limited to, bis (2-methoxyethyl) ether, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol. Examples include dimethyl ether, cyclohexanone, cyclopentanone, toluene, xylene, γ-butyrolactone, N-methyl-2-pyrrolidone and the like. 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 (A) phenol resin, 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.

  The (A) phenol resin may be a polymer obtained by polymerizing a phenol compound that is not a raw material having the structure of the general formula (1), for example, a monohydric phenol within a range not impairing the effects of the present invention. The range that does not impair 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 for the (A) phenol resin.

(B) Photoacid generator In embodiment, if the photosensitive resin composition is a composition which can form a resin pattern in response to actinic rays (radiation) represented by an ultraviolet-ray, an electron beam, X-ray | X_line, etc. The photosensitive resin composition may be any of negative type (unirradiated part is eluted by development) or positive type (irradiated part is eluted by development).

  In the first embodiment, since the photosensitive resin composition is used as a negative type, (B) the photoacid generator is a compound that generates an acid upon irradiation with radiation, and the generated acid is the above-mentioned (A) By causing a crosslinking reaction between the phenol resin and the crosslinking agent, the crosslinked product becomes insoluble in the developer. Examples of such compounds 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-tert-butylphenyl) iodonium tetrafluoroborate, bis (4-tert-butylphenyl) iodonium hexafluoroarsenate, bis (4-tert-butylphenyl) Iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium trifluoroacetate, bis (4-tert-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 the compounds (i) to (iii), 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 are preferable, and diaryl iodonium salts include diphenyl Iodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodine Nitrifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate and the like are preferable, and triarylsulfonium salts include triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium methanesulfonate. 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate and the like are preferable.

  In addition to the above compounds (i) to (iii), the following compounds can also be used as the (B) photoacid generator:

(1) Diazoketone compound Examples of the diazoketone compound include a 1,3-diketo-2-diazo compound, a diazobenzoquinone compound, a diazonaphthoquinone compound, and the like. Specific examples thereof include 1,2-naphtho of phenols. Mention may be made of quinonediazide-4-sulfonic acid ester compounds.

(2) Sulfone Compound Examples of the sulfone compound include β-ketosulfone compounds, β-sulfonylsulfone compounds, and α-diazo compounds of these compounds. Specific examples thereof include 4-trisphenacylsulfone, mesi Examples thereof include tilphenacyl sulfone 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 specific examples of the sulfonic acid compound 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) Product name “Irgacure PAG103”), [2- (n-octanesulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (Ciba Specialty Chemicals) Product name "Irgaku" APAG108 "), 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 oxime ester compound (5) is particularly preferable.

  In 1st embodiment, it is preferable that the compounding quantity of (B) photo-acid generator with respect to 100 mass parts of (A) phenol resin is 0.1 mass part-50 mass parts, and 1 mass part-40 mass parts. More preferably, it is a part. If the blending amount is 0.1 parts by mass or more, an effect of improving the sensitivity can be obtained. On the other hand, if the blending amount is 50 parts by mass or less, the mechanical properties of the cured film are improved. preferable.

  In the second embodiment, since the photosensitive resin composition is used as a positive type, (B) the photoacid generator includes (i) to (iii) and (1) to (6) above. The photoacid generator and / or quinonediazide compound shown are preferably used. From the viewpoint of the physical properties of the cured film, the (B) photoacid generator used in the positive photosensitive resin composition is particularly preferably a quinonediazide compound. This is because the amount of the quinonediazide compound thermally decomposed during curing and remaining in the cured film is extremely low.

  Examples of the quinonediazide compound include compounds having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure (hereinafter, the compound having the latter structure is also referred to as “NQD compound”). These compounds are described in, for example, 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”), which is 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 predetermined amount of 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, tetrahydrofuran, NQD compounds can be obtained by conducting esterification in the presence of a basic catalyst such as triethylamine and washing the resulting product with water and drying.

｛式中、Ｑは、水素原子、又は下記式群：

のいずれかで表されるナフトキノンジアジドスルホン酸エステル基であるが、全てのＱが同時に水素原子であることはない。｝。 From the viewpoint of cured film properties such as sensitivity and elongation, examples of preferable NQD compounds 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.

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

  In 2nd embodiment, the compounding quantity of (B) photo-acid generator is 0.1 mass part-70 mass parts with respect to 100 mass parts of (A) phenol resin, Preferably 1 mass part- 40 parts by mass, more preferably 5 to 30 parts by mass. If the blending amount is 0.1 parts by mass or more, good sensitivity can be obtained. On the other hand, if it is 70 parts by mass or less, the mechanical properties of the cured film are preferable.

(C) Solvent Examples of the (C) solvent include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons and the like. More specifically, examples of the solvent (C) include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, and 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 dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 1,2- Chloroethane, 1,4-dichloro butane, chlorobenzene, o- dichlorobenzene, anisole, hexane, may be used heptane, benzene, toluene, xylene, mesitylene and the like. Among these, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ-butyrolactone from the viewpoints of resin solubility, resin composition stability, and adhesion to a substrate. , Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenyl glycol, and tetrahydrofurfuryl alcohol are preferred.

  In embodiment, the compounding quantity of the solvent in the photosensitive resin composition becomes like this. Preferably it is the range of 100 mass parts-1000 mass parts with respect to 100 mass parts of (A) phenol resin, More preferably, it is 120 mass parts. It is the range of -700 mass parts, More preferably, it is the range of 125 mass parts-500 mass parts.

｛式（３）中、Ｘ_１及びＸ_２は、それぞれ独立に、炭素数１〜１０の１価の有機基を表し、ｓは、０〜２の整数であり、そしてＹ_０は、炭素数１〜２０の１価の有機基を表す。｝ (D) Silane Compound (D) The silane compound is not particularly limited as long as it is an organic compound containing an alkoxysilyl group as represented by the following general formula (3).

{In Formula (3), X ₁ and X ₂ each independently represent a monovalent organic group having 1 to 10 carbon atoms, s is an integer of 0 to 2, and Y ₀ is the number of carbon atoms. 1 to 20 monovalent organic groups are represented. }

｛式（１１）中、Ｘ_３は、単結合又は炭素数１〜１０の２価の有機基を表し、そしてＹ_１は、アミノ基、ヒドロキシル基、カルボキシル基、アミド基及びアルコキシ基から成る群から選ばれる少なくとも１つの置換基を有する１価の基を表す。｝

｛式（１２）中、Ｘ_３は、単結合又は炭素数１〜１０の２価の有機基を表し、そしてＹ_２は、炭素数１〜２０の芳香族基、メルカプト基、グリシジル基、ビニル基、アクリロイル基及びメタクリロイル基から成る群から選ばれる少なくとも一つの置換基を有する１価の有機基を表す。｝ In the general formula (3), Y ₀ is preferably a group represented by the following general formula (11) or (12).

{In Formula (11), X ₃ represents a single bond or a divalent organic group having 1 to 10 carbon atoms, and Y ₁ is a group consisting of an amino group, a hydroxyl group, a carboxyl group, an amide group and an alkoxy group. Represents a monovalent group having at least one substituent selected from: }

{In Formula (12), X ₃ represents a single bond or a divalent organic group having 1 to 10 carbon atoms, and Y ₂ represents an aromatic group, mercapto group, glycidyl group, vinyl having 1 to 20 carbon atoms. Represents a monovalent organic group having at least one substituent selected from the group consisting of a group, an acryloyl group and a methacryloyl group. }

｛式（１３）中、Ｘ_４及びＸ_５は、それぞれ独立に、炭素数１〜２０の１価の有機基を表し、Ｘ_６及びＸ_１０は、それぞれ独立に、炭素数１〜１０の２価の有機基を表し、Ｘ_７及びＸ_８は、それぞれ独立に、炭素数１〜１０の１価の有機基を表し、Ｘ_９は、４価の有機基を表し、そしてｓは、０〜２の整数である。｝ In the general formula (11), from the viewpoint of suppressing appearance defects such as wrinkles and blisters that may occur on the cured relief pattern when it is sputtered, and from the viewpoint of elongation of the cured film. Y ₁ is preferably at least one selected from five groups represented by the following general formula (13).

{In Formula (13), X ₄ and X ₅ each independently represent a monovalent organic group having 1 to 20 carbon atoms, and X ₆ and X ₁₀ are each independently 2 of 1 to 10 carbon atoms. X ₇ and X ₈ each independently represent a monovalent organic group having 1 to 10 carbon atoms, X ₉ represents a tetravalent organic group, and s represents 0 to 0 It is an integer of 2. }

｛式（１４）中、Ｘ_１１は、炭素数１〜２０の１価の有機基を表し、ｔは、０〜５の整数であり、ｔが２〜５である場合には、複数のＸ_１１は、それぞれ同一であるか、又は異なっていてよく、Ｘ_１２は、水素原子又はメチル基を表し、ｕは、０〜５の整数であり、ｕが２〜５である場合には、複数のＸ_１２は、それぞれ同一であるか、又は異なっていてよく、そしてＸ_１３及びＸ_１４は、それぞれ独立に、炭素数１〜１０の２価の基を表す。｝ In the general formula (12), Y ₂ is represented by the following general formula (12) from the viewpoint of suppressing appearance defects such as wrinkles and blisters that may occur on the pattern when the cured relief pattern is sputtered. It is preferably at least one selected from the three groups represented by 14).

{In Formula (14), X ₁₁ represents a monovalent organic group having 1 to 20 carbon atoms, t is an integer of 0 to 5, and when t is 2 to 5, ₁₁ may be the same or different from each other, X ₁₂ represents a hydrogen atom or a methyl group, u is an integer of 0 to 5, and when u is 2 to 5, X ₁₂ in each may be the same or different, and X ₁₃ and X ₁₄ each independently represent a divalent group having 1 to 10 carbon atoms. }

｛式（１６）中、Ｘ_１４及びＸ_１５は、それぞれ独立に、炭素数１〜１０の２価の有機基を表し、Ｘ_１６及びＸ_１７は、それぞれ独立に、炭素数１〜１０の１価の有機基を表し、そしてｓは、０〜２の整数である。｝

｛式（１７）中、Ｘ_２１及びＸ_２３は、それぞれ独立に、炭素数１〜１０の２価の有機基を表し、Ｘ_２２は、４価の有機基を表し、Ｘ_１９、Ｘ_２０、Ｘ_２４及びＸ_２５は、それぞれ独立に、炭素数１〜１０の１価の有機基を表し、そしてｓは、０〜２の整数である。｝

｛式（１８）中、Ｘ_２６は、−ＮＨ−Ｒ_３０又は−Ｏ−Ｒ_３１（式中、Ｒ_３０及びＲ_３１は、それぞれ独立に、１価の有機基を表す。）で表される１価の基であり、Ｘ_２７は、炭素数１〜１０の２価の有機基を表し、Ｘ_２８及びＸ_２９は、それぞれ独立に、炭素数１〜１０の１価の有機基を表し、そしてｓは、０〜２の整数である。｝

｛式（１９）中、Ｘ_３２は、２価の有機基を表し、Ｘ_３３及びＸ_３４は、それぞれ独立に、１価の有機基を表し、そしてｓは、０〜２の整数である。｝ As the compound in which Y ₀ is represented by the general formula (11), compounds represented by the following general formulas (16) to (19) are more preferable from the viewpoint of adhesion of the cured film to the substrate.

{Wherein _{(16), X 14} and _{X 15} each independently represent a divalent organic group having 1 to 10 carbon _{atoms, X 16} and _{X 17} are each independently 1 to 10 carbon atoms Represents an organic group having a valence, and s is an integer of 0 to 2. }

{Wherein _{(17), X 21} and _{X 23} each independently represent a divalent organic group having 1 to 10 carbon _{atoms, X 22} represents a tetravalent organic _group, X _{19, X 20,} X ₂₄ and X ₂₅ each independently represent a monovalent organic group having 1 to 10 carbon atoms, and s is an integer of 0 to 2. }

{In Formula (18), X ₂₆ is represented by -NH-R ₃₀ or -O-R ₃₁ (wherein R ₃₀ and R ₃₁ each independently represents a monovalent organic group). A monovalent group, X ₂₇ represents a divalent organic group having 1 to 10 carbon atoms, X ₂₈ and X ₂₉ each independently represents a monovalent organic group having 1 to 10 carbon atoms, And s is an integer of 0-2. }

{Wherein _{(19), X 32} represents a divalent organic _{group, X 33} and _{X 34} each independently represents a monovalent organic group, and s is an integer from 0 to 2. }

  The alkoxysilyl group-containing silane compound represented by the general formula (16) or (17) is not limited. For example, an acid anhydride or acid dianhydride and an amino group-containing silane compound are organically mixed. It can manufacture by making it react at 20-100 degreeC for 30 minutes-10 hours in a solvent.

  Examples of the acid anhydride include maleic anhydride, succinic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhymic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic acid, and phthalic anhydride. It is done.

  Examples of acid dianhydrides include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, and 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride. 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic acid Dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic Acid dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5 6-tetracarboxylic dianhydride, 4, -Dimethyl-1,2,3,5,6,7-hexahydronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetra Carboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic Acid dianhydride, 1,4,5,8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenyltetracarboxylic dianhydride, 3,3 ″, 4,4 ″ -p-terphenyl Tetracarboxylic dianhydride, 2,2 ", 3,3" -p-ter Phenyltetracarboxylic dianhydride, 2,3,3 ″, 4 ″ -p-terphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -propane dianhydride, 2 , 2-bis (3,4-dicarboxyphenyl) -propane dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, bis (3,4- Dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, peri Len-2,3,8,9-tetracarboxylic dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, perylene-4,5,10,11-tetracarboxylic dianhydride Perylene-5,6,11,12-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride Phenanthrene-1,2,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride Anhydrides, thiophene-2,3,4,5-tetracarboxylic dianhydride, 4,4′-hexafluoroisopropylidenediphthalic dianhydride and the like can be mentioned.

  Examples of the silane compound having an amino group include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-aminopropylethyldimethoxysilane. Silane, γ-aminopropylethyldiethoxysilane, γ-aminopropyldimethylmethoxysilane, γ-aminopropyldimethylethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropyldiethylmethoxysilane, γ-aminopropyldiethylethoxy Silane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyl Examples include dimethoxysilane and 4-aminobutyldimethylmethoxysilane.

Among the alkoxysilyl group-containing silane compounds represented by the general formula (16), a compound represented by the following structure is particularly preferable from the viewpoint of adhesion of the cured film to the substrate.

Among the alkoxysilyl group-containing silane compounds represented by the general formula (17), a compound represented by the following structure is particularly preferable from the viewpoint of adhesion of the cured film to the substrate.

  The alkoxysilyl group-containing silane compound represented by the general formula (18) is classified into a urea type and a urethane type, and is generally obtained by reacting an silane compound having an amino group with an isocyanate compound or a carbonate ester derivative, respectively. be able to. In this case, examples of the silane compound having an amino group include the aforementioned compounds, and examples of the isocyanate compound include cyclohexyl isocyanate, n-hexyl isocyanate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, Examples include 1-naphthyl isocyanate, n-octadecyl isocyanate, phenyl isocyanate, m-tolyl isocyanate, p-tolyl isocyanate, n-propyl isocyanate, isopropyl isocyanate, ethyl isocyanate, and benzyl isocyanate.

  Examples of the carbonate derivative include chlorocarbonate compounds such as ethyl chlorocarbonate, methyl chlorocarbonate, n-butyl chlorocarbonate, isobutyl chlorocarbonate, Z-chloride, 2-methoxyethyl chlorocarbonate, or di-carbonate Examples thereof include carbonate dianhydrides such as t-butyl. Among these carbonic acid ester derivatives, di-t-butyl dicarbonate is preferable because it does not use chloride and therefore does not require an operation such as removal of chlorine ions after the reaction. In addition, when di-t-butyl dicarbonate is used, the resulting t-butoxycarbonyl group is completely eliminated by firing at about 200 ° C., and thus excellent adhesion even at lower temperatures. Is preferable.

  In addition, the alkoxysilyl group-containing silane compound represented by the general formula (18) can also be obtained by reacting an isocyanate group-containing silane compound with an amino compound or an alcohol. Examples of isocyanate group-containing silane compounds include 3-triethoxysilylpropyl isocyanate, 3-trimethoxysilylpropyl isocyanate, 3-dimethoxymethylsilylpropyl isocyanate, and amino compounds include, for example, aromatic or fatty acids. Group monoamines and the like. Moreover, as alcohol, monohydric alcohol etc. can be used, for example.

Among the alkoxysilyl group-containing silane compounds represented by the general formula (18), a compound represented by the following structure is particularly preferable from the viewpoint of adhesion of the cured film to the substrate.

  Specific examples of the alkoxysilyl group-containing silane compound represented by the general formula (19) include N- (3-triethoxysilylpropyl) urea (for example, trade name LS3610 manufactured by Shin-Etsu Chemical Co., Ltd., AMAX Co., Ltd.). Company product name SIU9055.0, etc.), N- (3-trimethoxysilylpropyl) urea (product 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-metho Sidipropoxysilylpropyl) urea, N- (3-trimethoxysilylethyl) urea, N- (3-ethoxydimethoxysilylethyl) urea, N- (3-tripropoxysilylethyl) urea, N- (3-tripropoxy) Silylethyl) urea, N- (3-ethoxydipropoxysilylethyl) urea, N- (3-dimethoxypropoxysilylethyl) urea, N- (3-methoxydipropoxysilylethyl) urea, N- (3-trimethoxy And silylbutyl) urea, N- (3-triethoxysilylbutyl) urea, and N- (3-tripropoxysilylbutyl) urea.

｛式（２０）中、Ｘ_３６は、炭素数１〜１０の２価の有機基を表し、Ｘ_３５、Ｘ_３７及びＸ_３８は、それぞれ独立に、炭素数１〜１０の１価の有機基を表し、ｓは、０〜２の整数であり、そしてｔは、０〜５の整数である。｝

｛式（２１）中、Ｘ_３９は、水素原子又はメチル基を表し、Ｘ_４０は、下記式：

で表される１２種類の基から選ばれる少なくとも１つの２価の基であり、Ｘ_４１は、２価の有機基を表し、Ｘ_４２及びＸ_４３は、それぞれ独立に、炭素数１〜１０の１価の有機基を表し、ｓは、０〜２の整数であり、そしてｕは、１〜３の整数である。｝

｛式（２２）中、Ｘ_４４は、下記式：

で表される１２種類の基から選ばれる少なくとも１つの２価の基であり、Ｘ_４５は、炭素数１〜１０の２価の有機基を表し、Ｘ_４６及びＸ_４７は、それぞれ独立に、炭素数１〜１０の１価の有機基を表し、そしてｓは、０〜２の整数である。｝ Examples of the compound in which Y ₂ in the general formula (12) is represented by the general formula (14) include compounds represented by the following general formulas (20) to (22).

{Wherein _{(20), X 36} represents a divalent organic group having 1 to 10 carbon _atoms, X _{35, X 37} and _{X 38} each independently represent a monovalent organic group having 1 to 10 carbon atoms S is an integer from 0 to 2, and t is an integer from 0 to 5. }

{Wherein _{(21), X 39} represents a hydrogen atom or a methyl _{group, X 40} is represented by the following formula:

And at least one divalent group selected from 12 types of groups represented by: X ₄₁ represents a divalent organic group, and X ₄₂ and X ₄₃ are each independently a group having 1 to 10 carbon atoms. A monovalent organic group is represented, s is an integer of 0-2, and u is an integer of 1-3. }

{In Formula (22), X ₄₄ represents the following formula:

X ₄₅ represents a divalent organic group having 1 to 10 carbon atoms, and X ₄₆ and X ₄₇ are each independently, A monovalent organic group having 1 to 10 carbon atoms is represented, and s is an integer of 0 to 2. }

  Specific examples of the alkoxysilyl group-containing silane compound represented by the general formula (20) include N-phenyl-γ-aminopropyltrimethoxysilane (trade name KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.), N-phenyl- γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyldimethoxymethylsilane, N-phenyl-γ-aminopropyldimethoxyethylsilane and the like can be mentioned. Among these, N-phenyl-γ-aminopropyltrimethoxysilane is particularly preferable from the viewpoint of adhesion of the cured film to the substrate.

Specific examples of the alkoxysilyl group-containing silane compound represented by the general formula (21) include 3- (m-aminophenoxy) propyltrimethoxysilane (trade name SLA0598.0 manufactured by Amax Co., Ltd.), m-amino. Phenyltrimethoxysilane (trade name SLA0599.0 manufactured by Amax Co., Ltd.), p-aminophenyltrimethoxysilane (trade name SLA0599.1 manufactured by Amax Co., Ltd.), aminophenyltrimethoxysilane (trade name SLA0599.2 manufactured by Amax Co., Ltd.) ) And the like. Among these, a compound represented by the following structure is particularly preferable from the viewpoint of adhesion of the cured film to the substrate.

Specific examples of the alkoxysilyl group-containing silane compound represented by the general formula (22) include 2- (trimethoxysilylethyl) pyridine (trade name SIT8396.0 manufactured by Amax Co., Ltd.), 2- (triethoxysilyl). And ethyl) pyridine, 2- (dimethoxysilylmethylethyl) pyridine, 2- (diethoxysilylmethylethyl) pyridine and the like. Among these, a compound represented by the following structure is particularly preferable from the viewpoint of adhesion of the cured film to the substrate.

As the compound in which Y ₂ in the general formula (12) has a mercapto group, specifically, 3-mercaptopropyltrimethoxysilane (for example, trade name KBM803 manufactured by Shin-Etsu Chemical Co., Ltd., trade name manufactured by Chisso Corporation, Siraace S810) Etc.), 3-mercaptopropyltriethoxysilane (trade name SIM6475.0, manufactured by Amax Co., Ltd.), 3-mercaptopropylmethyldimethoxysilane (for example, trade name LS1375, manufactured by Shin-Etsu Chemical Co., Ltd., trade name SIM6474. 0), mercaptomethyltrimethoxysilane (trade name: SIM6473.5C, manufactured by Amax Co., Ltd.), mercaptomethyltrimethoxysilane (trade name: SIM6473.0, manufactured by Amax Co., Ltd.), 3-mercaptopropyl Diethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercapto Propylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercapto Ethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropo Shishiran, 4-mercapto-butyl trimethoxysilane, 4-mercapto-butyl triethoxysilane, 4-mercapto-butyl tripropoxysilane the like.

Specific examples of the compound in which Y ₂ in the general formula (12) has a glycidyl group include 3-glycidoxypropyltriethoxysilane (manufactured by Shin-Etsu Silicone, trade name KBE403), 2- (3,4-epoxy (Cyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and the like.

Specific examples of the compound in which Y ₂ in the general formula (12) has a vinyl group include vinyltrimethoxysilane (trade name KBE1003 manufactured by Shin-Etsu Silicone), vinyltriethoxysilane, diethoxymethylvinylsilane, and the like.

Examples of the compound in which Y ₂ in the general formula (12) has an acryloyl group include 3-acryloxypropyltrimethoxysilane.

Examples of the compound in which Y ₂ in the general formula (12) has a methacryloyl group include, for example, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacrylate. Examples include loxypropyltriethoxysilane (trade name KBE503 manufactured by Shin-Etsu Silicone Co., Ltd.), 3- (methacryloxy) propyltri (2-methoxyethoxy) silane, and the like.

  Among the many silane compounds described above, from the viewpoint of suppressing occurrence of appearance defects such as wrinkles and blisters that may occur on the cured relief pattern when it is sputtered, the above general formula ( The silane compounds represented by 16) to (22) are preferable, and the silane compounds represented by the general formulas (16) to (19) are more preferable from the viewpoint of the elongation of the obtained cured film.

  The blending amount of the (D) silane compound used in the present invention is preferably in the range of 0.1 to 10 parts by mass, more preferably 0. It is the range of 5 to 8 parts by mass. The (D) silane compounds listed above may be appropriately selected depending on the type of substrate, and may be used alone or in combination of two or more.

[Other ingredients]
In the embodiment, the photosensitive resin composition may contain other components such as a cross-linking agent, a thermal acid generator, a dye, a surfactant, and a dissolution accelerator, as necessary.

  In this specification, when a relief pattern formed using a photosensitive resin composition is heat-cured, the crosslinking agent is (A) capable of crosslinking with a phenol resin, or the crosslinking agent itself forms a crosslinked network. A compound that can be formed. The crosslinking agent takes a structure having two or more crosslinking groups in the molecule, and can further improve the thermal properties, mechanical properties, or chemical resistance of a cured film formed from the photosensitive resin composition.

  The cross-linking agent is not particularly limited because (A) a compound capable of cross-linking with a phenol resin or a cross-linking agent itself can form a cross-linking network can be used. Examples include a methylol group and / or alkoxymethyl group-containing compound, an epoxy compound, an isocyanate group-containing compound, and a bismaleimide compound.

  Examples of the methylol group and / or alkoxymethyl group-containing compound include Cymel (registered trademark) 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300, My Coat 102, 105 (Mitsui Cytec Co., Ltd.), Nicarak (registered trademark) MX-270, -280, -290, Nicarak MS-11, Nicarak 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, DML-PFP, DML- BOC, BisCMP-F, DML-BisOC-Z, DML-BisOCHP-Z, DML-BisOC-P, DMOM-PTBT, TMOM-BP, TMOM-BPA, TML-BPAF-MF (manufactured by Honshu Chemical Industry Co., Ltd.) , Benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis (hydroxymethyl) biphenyl, dimethyl Bis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) diphenyl ester Ether, bis (methoxymethyl) benzophenone, methoxymethyl benzoate methoxymethyl, bis (methoxymethyl) biphenyl, dimethyl bis (methoxymethyl) biphenyl, and the like.

  Examples of the epoxy compound include 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, and naphthol-xylylene type epoxy. Resin, phenol-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 Glycidyl 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 (trade name, manufactured by Nippon Steel Chemical Co., Ltd.), NC-3000-H, EPPN-501H, EOCN-1020, NC-7000L, EPPN-201L, XD-1000, EOCN-4600 (trade name, Nippon Kayaku) Yaku Co., Ltd.), Epicoat (registered trademark) 1001, Epicoat 1007, Epicoat 1009, Epicoat 5050, Epicoat 5051, Epicoat 1031S, Epicoat 180S65, Epicoat 157H70, YX-315-7 (Trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EHPE3150, Plaxel G402, PUE101, PUE105 (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 (trade name, manufactured by Nagase ChemteX Corporation), Epolite (registered trademark) 70P, Epolite 100M F (trade name, manufactured by Kyoeisha Chemical) and the like.

  Examples of the isocyanate group-containing compound include 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, 1,3-phenylenebismethylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, Takenate (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 (trade name, manufactured by Asahi Kasei Chemicals Corporation) and the like.

  Examples of the bismaleimide compound include 4,4′-diphenylmethane bismaleimide, phenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4. , 4′-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, BM -4000, BMI-5100, BMI-7000, BMI-TMH, BMI-6000, BMI-8000 (trade name, Daiwa Kasei Kogyo Co., Ltd.), and the like.

  As a compounding quantity of the crosslinking agent in the photosensitive resin composition, 0.1 mass part-40 mass parts are preferable with respect to 100 mass parts of (A) phenol resin, and 1 mass part-30 mass parts are 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, while if it is 40 parts by mass or less, the stability of the photosensitive resin composition in the varnish state and It is preferable because the elongation of the thermosetting film is good.

  In the embodiment, the thermal acid generator is preferably blended into the photosensitive resin composition from the viewpoint of developing good thermal and mechanical properties of the cured product even when the curing temperature is lowered.

  The thermal acid generator may be a compound that generates an acid by heat. Examples of the thermal acid generator include, but are not limited to, allyl chloroacetate, n-butyl chloroacetate, t-butyl chloroacetate, ethyl chloroacetate, methyl chloroacetate, benzyl chloroacetate, isopropyl chloroacetate, chloro 2-methoxyethyl acetate, methyl dichloroacetate, methyl trichloroacetate, ethyl trichloroacetate, 2-ethoxyethyl trichloroacetate, t-butyl cyanoacetate, t-butyl methacrylate, ethyl trifluoroacetate, methyl trifluoroacetate, trifluoroacetic acid Phenyl, vinyl trifluoroacetate, isopropyl trifluoroacetate, allyl trifluoroacetate, ethyl benzoate, methyl benzoate, t-butyl benzoate, methyl 2-chlorobenzoate, ethyl 2-chlorobenzoate, 4-chlorobenzoic acid Ethyl, 2,5-dichloro Ethyl benzoate, methyl 2,4-dichlorobenzoate, ethyl p-fluorobenzoate, methyl p-fluorobenzoate, t-butyl pentachlorophenylcarboxylate, methyl pentafluoropropionate, ethyl pentafluoropropionate, t -Carboxylic acid esters such as butyl; 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 toluenesulfonate, n-hexyl p-toluenesulfonate, n-heptyl p-toluenesulfonate, n-octyl p-toluenesulfonate, 2-methoxyethyl p-toluenesulfonate, p-toluenesulfonic acid Propargyl, 3-butynyl p-toluenesulfonate, ethyl trifluoromethanesulfonate, n-butyl trifluoromethanesulfonate, ethyl perfluorobutanesulfonate, methyl perfluorobutanesulfonate, benzyl (4-hydroxyphenyl) methylsulfonium hexafluoro Antimonate, benzyl (4-hydroxyphenyl) methylsulfonium hexafluorophosphate, trimethylsulfonium methylsulfate, tri-p-sulfonium trifluoromethanesulfonate, trime Sulfonic acid esters such as tilsulfonium trifluoromethanesulfonate, pyridinium-p-toluenesulfonate, ethyl perfluorooctanesulfonate; 1,4-butane sultone, 2,4-butane sultone, 1,3-propane sultone, phenol red, Examples thereof include cyclic sulfonic acid esters such as bromocresol green and bromocresol purple; and 2-sulfobenzoic acid anhydride, p-toluenesulfonic acid anhydride, and phthalic acid anhydride.

  As a compounding quantity of the thermal acid generator in the photosensitive resin composition, 0.1 mass part-30 mass parts are preferable with respect to 100 mass parts of (A) phenol resin, and 0.5 mass part-10 mass parts are. More preferably, it is more preferably 1 part by mass to 5 parts by mass.

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

  Examples of the surfactant include not only nonionic surfactants such as polyglycols such as polypropylene glycol and polyoxyethylene lauryl ether or derivatives thereof, but also Florard (registered trademark, trade name, manufactured by Sumitomo 3M Co., Ltd.). ), Megafac (registered trademark, trade name, manufactured by Dainippon Ink & Chemicals, Inc.), Lumiflon (registered trademark, trade name, manufactured by Asahi Glass Co., Ltd.) and the like; And organosiloxane surfactants such as DBE (trade name, manufactured by Chisso Corporation) and Granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).

  As a compounding quantity of surfactant in the photosensitive resin composition, 0.01 mass part-10 mass parts are preferable with respect to 100 mass parts of (A) phenol resin.

  Examples of the dissolution accelerator include a compound having a hydroxyl group or a carboxyl group. 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. Examples include 2- (1-naphthyl) propionic acid, mandelic acid, atrolactic acid, α-methoxyphenylacetic acid, O-acetylmandelic acid, and itaconic acid.

  As a compounding quantity of the melt | dissolution promoter in the photosensitive resin composition, 0.1 mass part-30 mass parts are preferable with respect to 100 mass parts of (A) phenol resin.

<Method for forming cured relief pattern>
In another embodiment, a method for producing a cured relief pattern using the photosensitive resin composition described above is provided. The method for producing a cured relief pattern includes the following steps:
Forming a photosensitive resin layer containing a photosensitive resin composition on a substrate;
Exposing the photosensitive resin layer;
Developing the photosensitive resin layer after the exposure to obtain a relief pattern; and heating the relief pattern;
including.

An example of a method for producing a cured relief pattern will be described below.
First, the photosensitive resin composition described above is applied to a suitable support or substrate such as a silicon wafer, a ceramic substrate, an aluminum substrate, or the like. In the present specification, the term “substrate” includes a substrate on which a semiconductor element or a display element is formed in addition to an unprocessed substrate. When applying the photosensitive resin composition, an adhesion assistant such as a silane coupling agent may be applied in advance to the support or the substrate in order to ensure water-resistant adhesion between the pattern to be formed and the support. . Application of the photosensitive resin composition is performed by, for example, spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, or the like.

  Next, it prebakes at 80 to 140 degreeC, and dries the coating film of the photosensitive resin composition. The thickness of the coating after drying is preferably 1 μm to 500 μm.

  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 nm to 500 nm are preferable. From the viewpoint of pattern resolution and handleability, the light source wavelength is preferably the g-line, h-line or i-line of a mercury lamp, even if these are used alone or two or more actinic rays are mixed. Good. As the exposure apparatus, a contact aligner, a mirror projection, and a stepper are particularly preferable. You may heat a coating film again at 80 to 140 degreeC after exposure as needed.

  Next, development is performed by a method such as an immersion method, a paddle method, or a rotary spray method. By development, 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 composition to obtain a relief pattern.

  Examples of the developer include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, and aqueous ammonia; organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine; tetramethylammonium hydroxide, tetrabutylammonium An aqueous solution of a quaternary ammonium salt such as hydroxide, and an aqueous solution to which a water-soluble organic solvent such as methanol or ethanol or a surfactant is added in an appropriate amount can be used as necessary. Among these, an aqueous tetramethylammonium hydroxide solution is preferable, and the concentration of the tetramethylammonium hydroxide is preferably 0.5% by mass to 10% by mass, and more preferably 1% by mass to 5% by 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, for example.

  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 generally used for permanent film applications of semiconductor devices, the dehydration cyclization reaction proceeds by heating to 300 ° C or higher. However, in the method for producing a cured relief pattern according to the present invention, it can be cured even at a lower temperature, so that the semiconductor device or display body device which is vulnerable to heat can be used. Can also be suitably used. For example, a method for forming a cured relief pattern includes an insulating layer made of a high-dielectric material or a ferroelectric material having a process temperature restriction, such as an oxide of a refractory metal such as titanium, tantalum, or hafnium. It is suitably used for a semiconductor device. In addition, as long as the semiconductor device does not have such heat resistance limitation, of course, heat treatment at 300 ° C. to 400 ° C. may be performed in the embodiment. Such heat treatment can be performed by using a hot plate, an oven, or a temperature rising oven capable of setting a temperature program. As the atmospheric gas when performing the heat treatment, air may be used, or 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.

<Semiconductor device>
In another embodiment, a semiconductor device having a cured relief pattern manufactured by the method described above using the photosensitive resin composition described above is also provided. In this embodiment, the semiconductor device includes a semiconductor element and a cured film provided on the semiconductor element, and the cured film is the cured relief pattern described above. Further, 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. In the embodiment, the semiconductor device can be manufactured by combining a known semiconductor device manufacturing method and the above-described cured relief pattern manufacturing method.

<Display body device>
In another embodiment, a display device having a cured relief pattern manufactured by the method described above using the photosensitive resin composition described above is also provided. In this embodiment, the display device includes a display element and a cured film provided on the display element, and the cured film is the cured relief pattern described above. Further, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer interposed therebetween. For example, examples of the cured film include a surface protective film for TFT liquid crystal display elements or color filter elements, an insulating film, and a planarizing film, protrusions for MVA liquid crystal display devices, and barrier ribs for organic EL element cathodes. . In the embodiment, similarly to the semiconductor device described above, the display body device can be manufactured by combining a known display body device manufacturing method and the above-described cured relief pattern manufacturing method.

Hereinafter, although an embodiment is concretely explained by a synthesis example, an example, and a comparative example, the present 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.

<Tensile elongation measurement>
A sample for measuring elongation was prepared by the following method. The photosensitive resin compositions obtained in Examples and Comparative Examples were spin-coated on a 6-inch silicon wafer substrate provided with an aluminum vapor deposition layer on the outermost surface so that the film thickness after curing was about 10 μm, and 120 ° C. Then, pre-baking was performed on a hot plate 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 Mfg. This coating film was heated 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 film having a thickness of 10 μm. The obtained cured resin film was cut to a width of 3 mm with a dicing saw, and then peeled off from the wafer with a dilute hydrochloric acid aqueous solution, and the obtained 20 samples were left in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours or more. The elongation was measured with a tensile tester (Tensilon). The maximum value was used as the measurement value, and the measurement values of 20 samples were averaged. The measurement conditions of the tensile tester were as follows. The results are shown in Table 2.
Temperature: 23 ° C
Relative humidity: 50%
Initial sample length: 50 mm
Test speed: 40 mm / min
Load cell rating: 2kgf

<Evaluation of wrinkles on cured film after sputtering>
The photosensitive resin composition was spin-coated on a silicon wafer, and the silicon wafer and the spin-coated film were pre-baked on a hot plate at 120 ° C. for 180 seconds to form a coating film having a thickness of 10 μm. The film thickness was measured with a film thickness measuring device Lambda Ace (manufactured by Dainippon Screen). This coating film was exposed by irradiating it with i-line having an exposure amount of 500 mJ / cm ² using a stepper NSR2005i8A (Nikon Corporation) having an exposure wavelength of i-line (365 nm) through a reticle with a test pattern. After the exposure, only Example 25 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% tetramethylammonium hydroxide aqueous solution AZ-300MIF (manufactured by AZ Electronic Materials) for 100 seconds, and with pure water. After rinsing, curing was performed at 220 ° C. for 1 hour in a vertical curing furnace VF200B (manufactured by Koyo Thermo Systems Co., Ltd.) to obtain a cured relief pattern. On this wafer with a cured film pattern, sputtering was performed using a sputtering apparatus L-440S-FHL (apparatus name, manufactured by ULVAC) so that a metal layer of Ti2000 / Cu4000 was formed. In this evaluation, two types of sputtering (250 ° C. sputtering, 300 ° C. sputtering) were performed by changing the sputtering temperature. As a heating method, the wafer stage was heated and the temperature of the wafer surface was measured using a thermocouple. The processing conditions are as follows.
[250 ° C sputtering]
Step 1: Ar pre-sputter etching: 1 Pa, 400 W, 15 minutes Step 2: Ti 2000A: 0.5 Pa, 600 W, 15 minutes, 250 ° C.
Step 3: Cu 4000A: 0.5 Pa, 400 W, 14 minutes, 250 ° C.
[300 ° C sputtering]
Step 1: Ar pre-sputter etching: 1 Pa, 400 W, 15 minutes Step 2: Ti 2000A: 0.5 Pa, 600 W, 15 minutes, 300 ° C.
Step 3: Cu 4000A: 0.5 Pa, 400 W, 14 minutes, 300 ° C.

  After the treatment, the surface was observed with an optical microscope using a lens with a magnification of 10 times to the eye and a magnification of 20 times with an objective lens, and was observed for wrinkles, blisters or poor appearance. At this time, when the wrinkles, blisters or appearance defects are generated by 250 ° C. sputtering, “x” indicates that wrinkles, blisters or appearance defects do not occur with 250 ° C. sputtering, but wrinkles, blisters or appearance defects do not occur by 300 ° C. sputtering. “△” indicates the case where the occurrence of the wrinkle occurs, and “◯” indicates the case where the wrinkle, the swelling or the appearance defect does not occur even at 300 ° C. sputtering. The results are shown in Table 2.

[Synthesis Example 1]
<Synthesis of 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 for 2 hours while maintaining 140 ° C.

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

[Synthesis Example 2]
<Synthesis of 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 (A-2) comprising BMMB was obtained with a yield of 65%.

[Synthesis Example 3]
<Synthesis of 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 dissolved 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 for 3 hours while maintaining 120 ° C.

  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 performed to obtain a copolymer (A-3) composed of resorcinol / BMMB / 2,6-bis (hydroxymethyl) -p-cresol in a yield of 77%.

[Synthesis Example 4]
<Synthesis of Silane Compound D-1>
To a 500 ml three-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 148.13 g (0.1 mol) of phthalic anhydride and 147.8 g of GBL (gamma butyrolactone) as a solvent were added and stirred. To 30 ° C. After 22.14 g (0.1 mol) of γ-aminopropyltriethoxysilane was charged into the dropping funnel, this was dropped into the flask over 30 minutes and stirred at room temperature for 12 hours to give a silane compound (D-1). Got.

[Synthesis Example 5]
<Synthesis of Silane Compound D-2>
In a 500 ml three-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 16.11 g (0.05 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and GBL (gamma-butyrolactone) as a solvent 153 g was added and stirred, and the flask was adjusted to 30 ° C. in a thermostatic bath. After 22.14 g (0.1 mol) of γ-aminopropyltriethoxysilane was charged into the dropping funnel, this was dropped into the flask over 30 minutes, stirred at room temperature for 12 hours, and the silane compound (D-2). Got.

[Synthesis Example 6]
<Synthesis of Silane Compound D-3>
To a 500 ml three-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 22.14 g (0.1 mol) of γ-aminopropyltriethoxysilane and 116.6 g of GBL (gamma butyrolactone) as a solvent were added and stirred. Was adjusted to 30 ° C. in a thermostatic bath. After charging 21.8 g (0.1 mol) of di-t-butyl dicarbonate into the dropping funnel, it was dropped into the flask over 30 minutes, and it was confirmed that carbon dioxide gas was released. Confirmed that it rose to After stirring the product at room temperature for 12 hours, a silane compound (D-3) was obtained.

[Synthesis Example 7]
<Synthesis of Silane Compound D-4>
To a 500 ml three-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 22.14 g (0.1 mol) of γ-aminopropyltriethoxysilane and 116.6 g of GBL (gamma butyrolactone) as a solvent were added and stirred. Was adjusted to 30 ° C. in a thermostatic bath. After 11.9 g (0.1 mol) of phenyl isocyanate was charged into the dropping funnel, this was dropped into the flask over 30 minutes, and it was confirmed that the liquid temperature had risen to 50 ° C. After stirring the product at room temperature for 12 hours, a silane compound (D-4) was obtained.

[Example 1]
As shown in Table 1, phenol resin (A-1) 100 parts by mass, photoacid generator (B-1) 12 parts by mass, silane compound (D-1) 6 parts by mass, crosslinking agent (E-1) 5 parts by mass. Part was dissolved in 228 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 the composition and its cured film were measured according to the evaluation method. The obtained results are shown in Table 2.

[Examples 2 to 24]
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 2.

[Example 25]
As shown in Table 1, 100 parts by mass of the phenol resin (A-1), 5 parts by mass of the photoacid generator (B-2), 6 parts by mass of the silane compound (D-1), and 10 parts by mass of the crosslinking agent (E-1). Part was dissolved in 225 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 the composition and its cured film were measured according to the evaluation method. The obtained results are shown in Table 2.

[Comparative Examples 1-3]
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 2.

[Comparative Example 4]
Among the compositions described in Example 1 of Patent Document 3, the phenol resin (A-4, A-5), the photoacid generator (B-3), the silane compound (D-10), and the crosslinking agent ( For E-1, E-2), the same components were used at the same composition ratio. These were dissolved in 462 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 the composition and its cured film were measured according to the evaluation method. The obtained results are shown in Table 2.

[Comparative Example 5]
Among the compositions described in Example 1 of Patent Document 4, the same composition ratio is used for the phenol resin (A-6), the photoacid generator (B-4), and the silane compound (D-1). Used in. To these, 5 parts by mass of a crosslinking agent (E-1) was added, dissolved in 234 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 the composition and its cured film were measured according to the evaluation method. The obtained results are shown in Table 2.

｛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ジャパン社製、商品名；イルガキュア ＰＡＧ１２１）
Ｂ−３：トリアリルスルホニウムヘキサフルオロフォスフェート（旭電化工業社製、商品名；ＳＰ−１５０）
Ｂ−４：下記式で表される光酸発生剤：

｛式中、Ｑの内６７％が以下の：

で表される構造であり、残余が水素原子である。｝
＜（Ｃ）溶剤＞
Ｃ−１：γ―ブチロラクトン（ＧＢＬ）
＜（Ｄ）シラン化合物＞
Ｄ−１：合成例４に記載したシラン化合物
Ｄ−２：合成例５に記載したシラン化合物
Ｄ−３：合成例６に記載したシラン化合物
Ｄ−４：合成例７に記載したシラン化合物
Ｄ−５：Ｎ−（３−トリエトキシシリルプロピル）ウレア（アヅマックス株式会社製、商品名ＳＩＵ９０５５．０）
Ｄ−６：Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン（信越化学工業株式会社製、商品名 ＫＢＭ５７３）
Ｄ−７：３−（ｍ−アミノフェノキシ）プロピルトリメトキシシラン（アヅマックス株式会社製、商品名ＳＬＡ０５９８．０）
Ｄ−８：２−（トリメトキシシリルエチル）ピリジン（アヅマックス株式会社製、商品名ＳＩＴ８３９６．０）
Ｄ−９：３−メルカプトプロピルトリメトキシシラン（チッソ株式会社製、商品名サイラエースＳ８１０）
Ｄ−１０：３−グリシドキシプロピルトリエトキシシラン（信越シリコーン社製、商品名ＫＢＥ４０３）
Ｄ−１１：３−メタクリロキシプロピルトリエトキシシラン（信越シリコーン社製 商品名ＫＢＥ５０３）
Ｄ−１２：ビニルトリメトキシシラン（信越シリコーン社製 商品名ＫＢＥ１００３）
＜（Ｅ）架橋剤＞
Ｅ−１：１，３，４，６−テトラキス（メトキシメチル）グリコールウリル（三和ケミカル製、商品名；ニカラックＭＸ−２７０）
Ｅ−２：ビスフェノールＡ型エポキシ化合物（ジャパンエポキシレジン社製、商品名；エピコート８２８） The composition described in Table 1 is as follows.
<(A) Alkali-soluble resin>
A-1: Copolymer composed of phloroglucinol / BMMB, polystyrene equivalent weight average molecular weight (Mw) = 15,000
A-2: Copolymer consisting of methyl 3,5-dihydroxybenzoate / BMMB, polystyrene equivalent weight average molecular weight (Mw) = 21,000
A-3: copolymer consisting of resorcinol / BMMB / 2,6-bis (hydroxymethyl) -p-cresol, polystyrene-reduced weight average molecular weight (Mw) = 9,900
A-4: Polyparavinylphenol, polystyrene equivalent weight average molecular weight (Mw) = 10,000 (manufactured by Maruzen Petrochemical Co., Ltd., product names: Marcalinker M, S-4)
A-5: Phenol / biphenylene resin, polystyrene-equivalent weight average molecular weight (Mw) = 2,400 (Maywa Kasei Co., Ltd., product name MEH-7851M)
A-6: Novolac resin, polystyrene-equivalent weight average molecular weight (Mw) = 10,600 (manufactured by Asahi Organic Materials Co., Ltd., product name EP4080G)
<(B) Photoacid generator>
B-1: Photoacid generator represented by the following formula:

{In the formula, 83% of Q is the following:

The remainder is a hydrogen atom. }
B-2: Oxime ester compound (BASF Japan, trade name; Irgacure PAG121)
B-3: Triallylsulfonium hexafluorophosphate (Asahi Denka Kogyo Co., Ltd., trade name: SP-150)
B-4: Photoacid generator represented by the following formula:

{In the formula, 67% of Q is the following:

The remainder is a hydrogen atom. }
<(C) Solvent>
C-1: γ-butyrolactone (GBL)
<(D) Silane compound>
D-1: Silane compound described in Synthesis Example 4 D-2: Silane compound described in Synthesis Example 5 D-3: Silane compound described in Synthesis Example 6 D-4: Silane compound described in Synthesis Example 7 D- 5: N- (3-triethoxysilylpropyl) urea (manufactured by Amax Co., Ltd., trade name: SIU9055.0)
D-6: N-phenyl-γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM573)
D-7: 3- (m-aminophenoxy) propyltrimethoxysilane (manufactured by Amax Co., Ltd., trade name SLA0598.0)
D-8: 2- (trimethoxysilylethyl) pyridine (manufactured by Amax Co., Ltd., trade name SIT83396)
D-9: 3-Mercaptopropyltrimethoxysilane (manufactured by Chisso Corporation, trade name: Sila Ace S810)
D-10: 3-glycidoxypropyltriethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., trade name KBE403)
D-11: 3-Methacryloxypropyltriethoxysilane (trade name KBE503 manufactured by Shin-Etsu Silicone)
D-12: Vinyltrimethoxysilane (trade name KBE1003 manufactured by Shin-Etsu Silicone)
<(E) Crosslinking agent>
E-1: 1,3,4,6-tetrakis (methoxymethyl) glycoluril (manufactured by Sanwa Chemical Co., Ltd., trade name: Nicalak MX-270)
E-2: Bisphenol A type epoxy compound (Japan Epoxy Resin, trade name: Epicoat 828)

  From the results shown in Table 2, it is possible to form an excellent cured film that is excellent in tensile elongation of the cured film and that does not generate wrinkles or the like after the sputtering process. Therefore, it is possible to provide an interlayer insulating film, a surface protective film, and the like for a semiconductor element that are excellent in these various characteristics.

  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 (8)

(A) The following general formula (1):

[In the formula (1), a is an integer of 2 or 3, b is an integer of 0 to 2, 2 ≦ (a + b) ≦ 4, and R ₁ is 1 having 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, two R _{1 s} are the same or different from each other And X is the following general formula (5):

{In Formula (5), 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 substituted with an atom, and W represents a single bond, a chain aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, fluorine C3-C20 alicyclic group which may be substituted by atom, the following general formula (2):

(In formula (2), p is an integer of 1 to 10.) and the following formula (6):

And at least one divalent organic group selected from the group consisting of divalent groups represented by: } Is a divalent group represented by: A phenolic resin having a structure represented by :
(B) a photoacid generator,
(C) solvent, and (D) the following general formula (3):

{In Formula (3), X ₁ and X ₂ each independently represent a monovalent organic group having 1 to 10 carbon atoms, s is an integer of 0 to 2, and Y ₀ is the number of carbon atoms. 1 to 20 monovalent organic groups are represented. } A silane compound represented by
A photosensitive resin composition comprising: In the general formula (1), X represents the following general formula (7):

In a divalent organic group represented by the photosensitive resin composition of claim 1. In the general formula (1), X represents the following general formula (8):

The photosensitive resin composition of Claim 1 or 2 which is a bivalent organic group represented by these. The (A) phenol resin has the following general formula (9):

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

{In Formula (10), R ₁₂ and R ₁₃ are each independently a monovalent group having 1 to 10 carbon atoms selected from a hydrocarbon group or an alkoxy group, and n ₄ is an integer of 2 or 3. Yes, n ₅ is an integer from 0 to 2, n ₆ is an integer from 0 to 3, m ₂ is an integer from 1 to 500, and 2 ≦ (n ₄ + n ₅ ) ≦ 4 , N ₅ is 2, the two R ₁₂ may be the same or different from each other, and when n ₆ is 2-3, each of the plurality of R ₁₃ is the same Or may be different. } The photosensitive resin composition as described in any one of Claims 1-3 which is a phenol resin which has both the structures represented by} in the same resin frame | skeleton. In the general formula (3), Y ₀ represents the following general formula (11) or (12):

{In Formula (11), X ₃ represents a single bond or a divalent organic group having 1 to 10 carbon atoms, and Y ₁ is a group consisting of an amino group, a hydroxyl group, a carboxyl group, an amide group and an alkoxy group. Represents a monovalent group having at least one substituent selected from: }

{In Formula (12), X ₃ represents a single bond or a divalent organic group having 1 to 10 carbon atoms, and Y ₂ represents an aromatic group, mercapto group, glycidyl group, vinyl having 1 to 20 carbon atoms. Represents a monovalent organic group having at least one substituent selected from the group consisting of a group, an acryloyl group and a methacryloyl group. }
The photosensitive resin composition as described in any one of Claims 1-4 which is group represented by these. In the general formula (11), Y ₁ represents the following general formula (13):

{In Formula (13), X ₄ and X ₅ each independently represent a monovalent organic group having 1 to 20 carbon atoms, and X ₆ and X ₁₀ are each independently 2 of 1 to 10 carbon atoms. X ₇ and X ₈ each independently represent a monovalent organic group having 1 to 10 carbon atoms, X ₉ represents a tetravalent organic group, and s represents 0 to 0 It is an integer of 2. } The photosensitive resin composition of Claim 5 which is at least 1 group chosen from group represented by these. In the general formula (12), Y ₂ represents the following general formula (14):

{In Formula (14), X ₁₁ represents a monovalent organic group having 1 to 20 carbon atoms, t is an integer of 0 to 5, and when t is 2 to 5, ₁₁ may be the same or different from each other, X ₁₂ represents a hydrogen atom or a methyl group, u is an integer of 0 to 5, and when u is 2 to 5, X ₁₂ in each may be the same or different, and X ₁₃ and X ₁₄ each independently represent a divalent group having 1 to 10 carbon atoms. } The photosensitive resin composition of Claim 5 which is at least 1 group chosen from group represented by these. The following steps:
(1) step of the photosensitive resin layer formed on a substrate comprising a photosensitive resin composition according to any one of claim 1 to 7
(2) a step of exposing the photosensitive resin layer;
(3) removing exposed or unexposed areas with a developer to obtain a relief pattern; and (4) heat treating the relief pattern;
A method for producing a cured relief pattern comprising: