JP2014178471A - Photosensitive resin composition, production method of cured relief pattern, semiconductor device and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition containing a specific phenolic resin, which can be cured at a low temperature, which has excellent tensile elongation of a cured film, which gives a superior relief pattern shape after cured, and which gives a cured film suppressing pattern abnormality even when a wafer with a cured relief pattern of the cured film is subjected to a reflow process, and to provide a production method of a cured relief pattern for forming a pattern by using the photosensitive resin composition, and a semiconductor device and a display device having the cured relief pattern.SOLUTION: A positive photosensitive resin composition is provided, comprising: (A) 100 parts by mass of a phenolic resin having a specific structure; (B) 0.1 to 20 parts by mass of at least one triazole compound selected from the group consisting of compounds expressed by general formula group (1) described below; and (C) 0.1 to 70 parts by mass of a compound having a quinonediazide group.

Description

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

  Conventionally, polyimide resins and polybenzoxazole resins having excellent heat resistance, electrical characteristics, and mechanical characteristics have been widely used for permanent films used in semiconductor devices, such as surface protective films and interlayer insulating films. These resins have a problem that they are corrosive to metals such as copper and copper alloys that are widely used as semiconductor materials. As a solution to this problem, a photosensitive composition containing a nitrogen-containing heterocyclic compound has been proposed. Specifically, a photosensitive resin composition containing triazole or a derivative thereof in a polyimide resin (see Patent Document 1). ), A polyimide precursor, a polybenzoxazole precursor, 1H-tetrazole, and a photosensitive resin composition containing the derivative thereof (see Patent Document 2), a polyimide precursor, a polyoxazole precursor, and a purine derivative. A photosensitive resin composition (see Patent Document 3) is proposed.

  Here, since the polyimide resin and the polybenzoxazole resin described above have a cyclic structure and the solubility in various solvents is low as it is, generally the precursor that has opened the cyclic structure is dissolved in the solvent. A composition is used. Therefore, in order to manufacture a semiconductor device, a step of closing the precursor is necessary after the step of applying the composition on the semiconductor element. This ring closing step is usually performed by thermosetting in which the coating film is heated to 300 ° C. or higher.

  However, in recent years, semiconductor devices that are vulnerable to high-temperature processes compared to conventional products have been developed, and a material for forming a surface protective film and an interlayer insulating film has been required to have a reduced thermosetting temperature. Increasingly, curability is required.

  As a solution to this problem, there has been proposed a surface protective film and a photosensitive resin composition for an interlayer insulating film using a phenol resin that does not require a ring-closing step (and therefore can be cured at a low temperature) (see Patent Document 4). And as a photosensitive composition containing a phenol resin and a heterocyclic compound, a positive resist composition containing an alkali-soluble novolak resin, a benzotriazole-based compound (see Patent Document 5), and the like have been proposed. .

JP 2005-10360 A JP 2006-227387 A JP 2012-194520 A International Publication No. 2012/036130 Pamphlet JP 2010-176012 A

As described above, in recent years, a material for forming a permanent film such as a surface protective film and an interlayer insulating film has been required to have a reduced thermosetting temperature. There is an increasing demand for applicable film properties.
However, the above-mentioned Patent Documents 1 to 4 do not describe the cured film characteristics when thermally cured at 250 ° C. or less, and Patent Document 5 uses a photoresist as the application, so that the cured film (permanently cured) There was no description of evaluation as (film).

  As a result of investigation by the present inventor, the photosensitive composition according to Patent Document 5 is improved when compared with the protective film and the insulating film that are put into practical use when the thermosetting at 200 ° C. causes sagging of the relief pattern. There was room to be done (see Comparative Example 7 below). In addition, when the resin film is applied to a semiconductor device as a permanent film, the tensile elongation of the cured resin film is one of important film properties. However, the above-mentioned Patent Document 5 does not describe the tensile elongation of the cured relief pattern. When this inventor examined, compared with the cured relief pattern formed from the polyimide resin or polybenzoxazole resin currently utilized, there existed room which should be improved about tensile elongation (Comparative Example 7 mentioned later) reference).

  In the case of a semiconductor having a bump electrode, as a method of forming the bump electrode in the semiconductor process, after applying flux to the electrode pad, mounting a solder ball and performing a reflow process, the bump is fused, and the bump electrode is formed. There is a method of forming. At this time, the protective film and the insulating film are exposed to the high temperature of reflow in the state where the flowed flux is in contact, so after reflow, pattern abnormalities such as pattern cracks and surface irregularities, film thickness changes such as swelling and film loss, etc. The problem may occur. Therefore, when the resin film is used for a semiconductor having bump electrodes, it is one of important characteristics that it can be applied to reflow processing.

  Therefore, the present invention can be cured at a low temperature (for example, 250 ° C. or lower, more typically 200 ° C. or lower), has excellent tensile elongation of the cured film, and has an excellent relief pattern shape after curing A photosensitive resin composition containing a specific phenol resin that gives a cured film with suppressed pattern abnormality even when a wafer with a cured relief pattern is subjected to reflow treatment, and a cured relief that forms a pattern using the photosensitive resin composition It is an object of the present invention to provide a pattern manufacturing method and a semiconductor device and a display device having the cured relief pattern.

｛式中、Ｐ₁，Ｐ₂，Ｐ₃，Ｐ₄及びＰ₅は、それぞれ独立に、水素原子、水酸基、メルカプト基、アミノ基、カルボキシル基、炭素数１〜３０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数３〜３０の置換又は非置換の脂環式基、置換又は非置換のフェニル基、及び、置換又は非置換のベンジル基からなる群から選択される基であり、ここで、Ｐ₁及びＰ₂は、縮合して置換若しくは非置換のベンゼン環又はヘテロ原子１個を有する６員の複素環を形成してもよい。｝で表される化合物からなる群から選択される少なくとも１種のトリアゾール化合物：０．１〜２０質量部、並びに
（Ｃ）キノンジアジド基を有する化合物：０．１〜７０質量部、
を含むポジ型感光性樹脂組成物であって、
前記（Ａ）フェノール樹脂が、
（ａ１）下記一般式（２）：

｛式中、ａは、１〜３の整数であり、ｂは、０〜３の整数であり、１≦（ａ＋ｂ）≦４であり、Ｒ₁は、炭素数１〜２０の１価の有機基、ハロゲン原子、ニトロ基及びシアノ基からなる群から選択される１価の置換基を表し、ｂが２又は３である場合には、複数のＲ₁は、互いに同一でも又は異なっていてもよく、Ｘは、不飽和結合を有していてもよい炭素数２〜１０の２価の脂肪族基、炭素数３〜２０の２価の脂環式基、下記一般式（３）：

（式中、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、及び炭素数６〜２０の芳香族環を有する２価の有機基からなる群から選択される２価の有機基を表す。｝で表される繰り返し単位を有するフェノール樹脂、並びに、
（ａ２）エーテル結合、水酸基、エステル結合、カルボキシル基、チオエーテル結合、チオール基、チオエステル結合、スルホ基、スルホニル基、ウレタン結合、ウレア結合、チオウレタン結合、及びチオ尿素結合からなる群から選択される少なくとも１つの官能基を有する炭素数４〜１００の化合物で変性されている、フェノール樹脂、
からなる群から選択される少なくとも１種のフェノール樹脂を含む、ポジ型感光性樹脂組成物。
［２］ 前記トリアゾール化合物が、下記一般式群（４）：

｛式中、Ｐ₆，Ｐ₇及びＰ₈は、それぞれ独立に水酸基、メルカプト基、アミノ基、カルボキシル基、ニトロ基、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数３〜２０の置換又は非置換の脂環式基、置換又は非置換のフェニル基、及び、置換又は非置換のベンジル基からなる群から選択される基であり、ｋ１，ｋ２及びｋ３はそれぞれ独立に０〜３の整数であり、ｋ１，ｋ２及びｋ３がそれぞれ２又は３である場合には、複数のＰ₆，Ｐ₇及びＰ₈は互いに同一でも又は異なっていてもよく、Ｐ₃は前記一般式群（１）で定義したものと同じである。｝
で表される化合物からなる群から選択される少なくとも１種である、上記［１］に記載のポジ型感光性樹脂組成物。
［３］ 前記Ｐ₃が、下記一般式（５）：

｛式中、ｈは、１〜５の整数であり、そしてＰ₉は、水素原子、水酸基、カルボキシル基、メルカプト基、炭素数１〜１０の直鎖又は分岐鎖の脂肪族基、少なくとも１個の水酸基で置換された炭素数１〜１０の直鎖又は分岐鎖の脂肪族基、及び少なくとも１個のカルボキシル基で置換された炭素数１〜１０の直鎖又は分岐鎖の脂肪族基からなる群から選択される１価の基である。｝で表される１価の基、並びに下記一般式（６）：

｛式中、ｉは、１〜５の整数であり、そしてＰ₁₀及びＰ₁₁はそれぞれ独立に炭素数１〜１０の直鎖又は分岐鎖の脂肪族基、少なくとも１個の水酸基で置換された炭素数１〜１０の直鎖又は分岐鎖の脂肪族基、少なくとも１個のカルボキシル基で置換された炭素数１〜１０の直鎖又は分岐鎖の脂肪族基からなる群から選択される１価の基である。｝で表される１価の基からなる群から選択される１価の基である、上記［１］又は［２］に記載のポジ型感光性樹脂組成物。
［４］ 前記一般式（２）中のＸが、下記一般式（７）：

｛式中、Ｒ₂、Ｒ₃、Ｒ₄、及びＲ₅は、それぞれ独立に、水素原子、炭素数１〜１０の１価の脂肪族基、又は水素原子の一部若しくは全部がフッ素原子で置換されてなる炭素数１〜１０の１価の脂肪族基であり、ｎ₁は０〜４の整数であって、ｎ₁が１〜４の整数である場合のＲ₆は、ハロゲン原子、又は炭素数１〜１２の１価の有機基であり、ｎ₁が２〜４の整数である場合の複数のＲ₆は互いに同一でも又は異なっていてもよい。｝で表される２価の基、及び下記一般式（８）：

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

（式中、ｐは、１〜１０の整数である。）で表される２価のアルキレンオキシド基、及び下記式群（９）：

で表される２価の基からなる群から選択される２価の有機基である。｝で表される２価の基からなる群から選択される２価の有機基である、上記［１］〜［３］のいずれかに記載のポジ型感光性樹脂組成物。
［５］ 前記一般式（２）中のＸが、下記式（１０）：

で表される２価の有機基である、上記［１］〜［４］のいずれかに記載のポジ型感光性樹脂組成物。
［６］ 前記一般式（２）中のＸが、下記式（１１）：

で表される２価の有機基である、上記［１］〜［５］のいずれかに記載のポジ型感光性樹脂組成物。
［７］ 前記（Ａ）フェノール樹脂が、下記一般式（１２）：

｛式中、Ｒ₁₁は炭化水素基及びアルコキシ基からなる群から選択される炭素数１〜１０の１価の基であり、ｎ₂は１〜３であり、ｎ₃は０〜２の整数であり、ｍ₁は１〜５００の整数であり、２≦（ｎ₂＋ｎ₃）≦４であり、ｎ₃が２の場合には、複数のＲ₁₁は互いに同一でも又は異なっていてもよい。｝で表される繰り返し単位、及び下記一般式（１３）：

｛式中、Ｒ₁₂及びＲ₁₃はそれぞれ独立に炭化水素基及びアルコキシ基からなる群から選択される炭素数１〜１０の１価の基であり、ｎ₄は１〜３の整数であり、ｎ₅は０〜２の整数であり、ｎ₆は０〜３の整数であり、ｍ₂は１〜５００の整数であり、２≦（ｎ₄＋ｎ₅）≦４であり、ｎ₅が２の場合には、複数のＲ₁₂は互いに同一でも又は異なっていてもよく、ｎ₆が２又は３の場合には、複数のＲ₁₃は互いに同一でも又は異なっていてもよい。｝で表される繰り返し単位の両方を同一樹脂骨格内に有するフェノール樹脂である、上記［１］〜［６］のいずれかに記載のポジ型感光性樹脂組成物。
［８］ 前記（Ａ）フェノール樹脂が前記（ａ２）フェノール樹脂を含み、かつ前記（ａ２）フェノール樹脂が、エステル結合及びカルボキシル基からなる群から選択される少なくとも１つの官能基を有する炭素数４〜１００の化合物で変性されているフェノール樹脂である、上記［１］〜［７］のいずれかに記載の感光性樹脂組成物。
［９］ 前記（Ａ）フェノール樹脂が前記（ａ２）フェノール樹脂を含み、かつ前記（ａ２）フェノール樹脂が、炭素数４〜１００の不飽和脂肪酸及び炭素数４〜１００の不飽和脂肪酸エステルからなる群から選択される少なくとも１つの化合物で変性されているフェノール樹脂である、上記［１］〜［８］のいずれかに記載の感光性樹脂組成物。
［１０］ 更に（Ｅ）架橋剤：０．１〜４０質量部を含む、上記［１］〜［９］のいずれかに記載の感光性樹脂組成物。
［１１］ 以下の工程：
（１）上記［１］〜［１０］のいずれかに記載のポジ型感光性樹脂組成物を含むポジ型感光性樹脂層を基板上に形成する工程、
（２）該ポジ型感光性樹脂層を露光する工程、
（３）現像液により露光部を除去して、レリーフパターンを得る工程、及び
（４）該レリーフパターンを加熱処理する工程、
を含む、硬化レリーフパターンの製造方法。
［１２］ 上記［１１］に記載の方法により製造された、硬化レリーフパターン。
［１３］ 半導体素子と、該半導体素子の上部に設けられた硬化膜とを備える半導体装置であって、該硬化膜は、上記［１２］に記載の硬化レリーフパターンである、半導体装置。
［１４］ 表示体素子と、該表示体素子の上部に設けられた硬化膜とを備える表示体装置であって、該硬化膜は、上記［１２］に記載の硬化レリーフパターンである、表示体装置。 The present invention has the following configuration.
[1] (A) Phenolic resin: 100 parts by mass,
(B) The following general formula group (1):

{Wherein P ₁ , P ₂ , P ₃ , P ₄ and P ₅ are each independently a hydrogen atom, a hydroxyl group, a mercapto group, an amino group, a carboxyl group, an alkyl group having 1 to 30 carbon atoms, or 1 carbon atom. A group selected from the group consisting of 10 to 10 alkoxy groups, substituted or unsubstituted alicyclic groups having 3 to 30 carbon atoms, substituted or unsubstituted phenyl groups, and substituted or unsubstituted benzyl groups, Here, P ₁ and P ₂ may be condensed to form a substituted or unsubstituted benzene ring or a 6-membered heterocyclic ring having one heteroatom. } At least one triazole compound selected from the group consisting of compounds represented by: 0.1 to 20 parts by mass, and (C) a compound having a quinonediazide group: 0.1 to 70 parts by mass,
A positive photosensitive resin composition comprising:
The (A) phenol resin is
(A1) The following general formula (2):

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

(Wherein p is an integer of 1 to 10) and selected from the group consisting of a divalent alkylene oxide group and a divalent organic group having an aromatic ring having 6 to 20 carbon atoms. Represents a divalent organic group. }, A phenolic resin having a repeating unit represented by:
(A2) Selected from the group consisting of ether bond, hydroxyl group, ester bond, carboxyl group, thioether bond, thiol group, thioester bond, sulfo group, sulfonyl group, urethane bond, urea bond, thiourethane bond, and thiourea bond A phenol resin modified with a compound of 4 to 100 carbon atoms having at least one functional group,
A positive photosensitive resin composition comprising at least one phenol resin selected from the group consisting of:
[2] The triazole compound is represented by the following general formula group (4):

{Wherein P ₆ , P ₇ and P ₈ are each independently a hydroxyl group, mercapto group, amino group, carboxyl group, nitro group, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, carbon A group selected from the group consisting of a substituted or unsubstituted alicyclic group, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted benzyl group having 3 to 20, k1, k2 and k3 are each When each independently represents an integer of 0 to 3, and k1, k2 and k3 are each 2 or 3, the plurality of P ₆ , P ₇ and P ₈ may be the same or different from each other, and P ₃ is The same as defined in the general formula group (1). }
The positive photosensitive resin composition according to the above [1], which is at least one selected from the group consisting of compounds represented by:
[3] The P ₃ is represented by the following general formula (5):

{Wherein h is an integer of 1 to 5 and P ₉ is a hydrogen atom, a hydroxyl group, a carboxyl group, a mercapto group, a linear or branched aliphatic group having 1 to 10 carbon atoms, at least one A linear or branched aliphatic group having 1 to 10 carbon atoms substituted with a hydroxyl group and a linear or branched aliphatic group having 1 to 10 carbon atoms substituted with at least one carboxyl group A monovalent group selected from the group. } And the following general formula (6):

{Wherein i is an integer of 1 to 5 and P ₁₀ and P ₁₁ are each independently substituted with a linear or branched aliphatic group having 1 to 10 carbon atoms, at least one hydroxyl group A monovalent group selected from the group consisting of a linear or branched aliphatic group having 1 to 10 carbon atoms and a linear or branched aliphatic group having 1 to 10 carbon atoms substituted with at least one carboxyl group It is the basis of. } The positive photosensitive resin composition as described in [1] or [2] above, which is a monovalent group selected from the group consisting of monovalent groups represented by:
[4] X in the general formula (2) is the following general formula (7):

{Wherein 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 atoms. A substituted monovalent aliphatic group having 1 to 10 carbon atoms, n ₁ is an integer of 0 to 4, and when n ₁ is an integer of ₁ to 4, R ₆ is a halogen atom, or a monovalent organic group having 1 to 12 carbon atoms, more R ₆ may be the same or different from each other when n ₁ is an integer of 2 to 4. } And the following general formula (8):

{Wherein 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 part or all of the hydrogen atoms are substituted with fluorine atoms. Represents a monovalent aliphatic group having 1 to 10 carbon atoms, and W is a single bond, an aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, or a fluorine atom. A C3-C20 alicyclic group, the following general formula (3):

(Wherein p is an integer of 1 to 10), and the following formula group (9):

A divalent organic group selected from the group consisting of divalent groups represented by the formula: } The positive photosensitive resin composition according to any one of the above [1] to [3], which is a divalent organic group selected from the group consisting of divalent groups represented by:
[5] X in the general formula (2) is the following formula (10):

The positive photosensitive resin composition according to any one of the above [1] to [4], which is a divalent organic group represented by:
[6] X in the general formula (2) is the following formula (11):

The positive photosensitive resin composition according to any one of the above [1] to [5], which is a divalent organic group represented by:
[7] The (A) phenol resin is represented by the following general formula (12):

{Wherein R ₁₁ is a monovalent group having 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, n ₂ is 1 to 3, and n ₃ is an integer of 0 to 2. M ₁ is an integer of ₁ to 500, 2 ≦ (n ₂ + n ₃ ) ≦ 4, and when n ₃ is 2, a plurality of R ₁₁ may be the same as or different from each other. . } And the following general formula (13):

{Wherein R ₁₂ and R ₁₃ are each independently a monovalent group having 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, and n ₄ is an integer of 1 to 3; n ₅ is an integer of 0 to 2, n ₆ is an integer of 0 to 3, m ₂ is an integer of ₁ to 500, 2 ≦ (n ₄ + n ₅ ) ≦ 4, and n ₅ is 2 In this case, the plurality of R ₁₂ may be the same or different from each other, and when n ₆ is 2 or 3, the plurality of R ₁₃ may be the same or different from each other. } The positive photosensitive resin composition in any one of said [1]-[6] which is a phenol resin which has both the repeating units represented by} in the same resin frame | skeleton.
[8] Carbon number 4 wherein the (A) phenol resin includes the (a2) phenol resin, and the (a2) phenol resin has at least one functional group selected from the group consisting of an ester bond and a carboxyl group. The photosensitive resin composition in any one of said [1]-[7] which is a phenol resin modified | denatured with -100 compounds.
[9] The (A) phenol resin contains the (a2) phenol resin, and the (a2) phenol resin is composed of an unsaturated fatty acid having 4 to 100 carbon atoms and an unsaturated fatty acid ester having 4 to 100 carbon atoms. The photosensitive resin composition according to any one of [1] to [8] above, which is a phenol resin modified with at least one compound selected from the group.
[10] The photosensitive resin composition according to any one of [1] to [9], further including (E) a crosslinking agent: 0.1 to 40 parts by mass.
[11] The following steps:
(1) forming a positive photosensitive resin layer containing the positive photosensitive resin composition according to any one of [1] to [10] on a substrate;
(2) a step of exposing the positive photosensitive resin layer;
(3) removing the exposed portion with a developer to obtain a relief pattern; and (4) heat-treating the relief pattern;
A method for producing a cured relief pattern.
[12] A cured relief pattern produced by the method according to [11] above.
[13] A semiconductor device comprising a semiconductor element and a cured film provided on the semiconductor element, wherein the cured film is the cured relief pattern according to the above [12].
[14] A display device comprising a display element and a cured film provided on the display element, wherein the cured film is the cured relief pattern according to [12]. apparatus.

  According to the present invention, curing at a low temperature is possible, the cured film has excellent tensile elongation, an excellent relief pattern shape is obtained after curing, and pattern abnormalities can be suppressed even when a wafer with a cured relief pattern is reflow-treated. A photosensitive resin composition containing a specific phenol resin, a cured film obtained by using the photosensitive resin composition, a cured relief pattern for forming a pattern, and a method for producing the same, and A semiconductor device and a display device having a cured relief pattern can be provided.

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

<Positive photosensitive resin composition>
The positive photosensitive resin composition provided by one embodiment of the present invention is:
(A) phenol resin having a specific structure: 100 parts by mass,
(B) Triazole compound having a specific structure: 0.1 to 20 parts by mass, and (C) Compound having a quinonediazide group: 0.1 to 70 parts by mass,
Containing. Hereinafter, each component will be described in order.

｛式中、ａは、１〜３の整数であり、ｂは、０〜３の整数であり、１≦（ａ＋ｂ）≦４であり、Ｒ₁は、炭素数１〜２０の１価の有機基、ハロゲン原子、ニトロ基及びシアノ基からなる群から選択される１価の置換基を表し、ｂが２又は３である場合には、複数のＲ₁は、互いに同一でも又は異なっていてもよく、Ｘは、不飽和結合を有していてもよい炭素数２〜１０の２価の脂肪族基、炭素数３〜２０の２価の脂環式基、下記一般式（３）：

（式中、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、及び炭素数６〜２０の芳香族環を有する２価の有機基からなる群から選択される２価の有機基を表す。｝
で表される繰り返し単位を有するフェノール樹脂（以下、（ａ１）フェノール樹脂ともいう）、並びに、（ａ２）エーテル結合、水酸基、エステル結合、カルボキシル基、チオエーテル結合、チオール基、チオエステル結合、スルホ基、スルホニル基、ウレタン結合、ウレア結合、チオウレタン結合、及びチオ尿素結合からなる群から選択される少なくとも１つの官能基を有する炭素数４〜１００の化合物で変性されているフェノール樹脂（以下、（ａ２）フェノール樹脂、又は単に変性フェノール樹脂ともいう）からなる群から選択される少なくとも１種のフェノール樹脂を含む。（Ａ）フェノール樹脂は、熱硬化時に、例えばポリイミド前駆体を用いる場合の環化（イミド化）のような構造変化が起こらないため、低温（例えば２５０℃以下、より典型的には２００℃以下）での硬化が可能であるという利点を有する。 [(A) Phenolic resin]
The (A) phenol resin in the present embodiment is (a1) the following general formula (2):

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

(Wherein p is an integer of 1 to 10) and selected from the group consisting of a divalent alkylene oxide group and a divalent organic group having an aromatic ring having 6 to 20 carbon atoms. Represents a divalent organic group. }
A phenol resin having a repeating unit represented by (hereinafter also referred to as (a1) phenol resin), and (a2) an ether bond, a hydroxyl group, an ester bond, a carboxyl group, a thioether bond, a thiol group, a thioester bond, a sulfo group, A phenol resin modified with a compound having 4 to 100 carbon atoms and having at least one functional group selected from the group consisting of a sulfonyl group, a urethane bond, a urea bond, a thiourethane bond, and a thiourea bond (hereinafter referred to as (a2 And at least one phenol resin selected from the group consisting of phenolic resins or simply modified phenolic resins). (A) The phenol resin does not undergo structural changes such as cyclization (imidization) in the case of using a polyimide precursor at the time of thermosetting, so that the low temperature (for example, 250 ° C. or less, more typically 200 ° C. or less). ) Has the advantage that it can be cured.

  In this 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. The weight average molecular weight is preferably 700 or more from the viewpoint of applicability of the reflow treatment to the cured film, and is preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition.

  The measurement of the weight average molecular weight in this indication is performed by gel permeation chromatography (GPC), and can be calculated by a calibration curve created using standard polystyrene.

  In the present embodiment, when novolac, which is most widely used as a phenolic resin, is used, it is one of important characteristics required for a semiconductor protective film and an insulating film, when cured at a low temperature (for example, 200 ° C.). The tensile elongation was smaller than that of polyimide and polybenzoxazole which have been put to practical use as a protective film and an insulating film (see Comparative Example 7 described later). In the case of novolak, the reason why the tensile elongation was small is presumed to be that the intermolecular interaction acting between and between the polymers was small.

  On the other hand, when at least one resin selected from the group consisting of the phenol resin represented by the general formula (2) and the modified phenol resin is used as the phenol resin, the tensile elongation when cured at 200 ° C. is used. The degree can show a sufficiently large value (see Examples described later). Although the mechanism of high elongation is not clear, it is presumed that the intermolecular interaction acting between and between the polymers was large. That is, for the phenol resin represented by the general formula (2), the molecular structure has biphenyl or the like, and ππ stacking occurs in the molecule and between the molecules of the polymer. On the other hand, for the modified phenol resin, It is presumed that the phenolic hydroxyl group and the modifying group (for example, ester bond) form a hydrogen bond, which results in a pseudo-crosslinked state in the polymer molecule and between molecules, and can exhibit high elongation of the cured film. .

｛式中、ａは、１〜３の整数であり、ｂは、０〜３の整数であり、１≦（ａ＋ｂ）≦４であり、Ｒ₁は、炭素数１〜２０の１価の有機基、ハロゲン原子、ニトロ基及びシアノ基からなる群から選択される１価の置換基を表し、ｂが２又は３である場合には、複数のＲ₁は、互いに同一でも又は異なっていてもよく、Ｘは、不飽和結合を有していてもよい炭素数２〜１０の２価の脂肪族基、炭素数３〜２０の２価の脂環式基、下記一般式（３）：

（式中、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、及び炭素数６〜２０の芳香族環を有する２価の有機基からなる群から選択される２価の有機基を表す。｝
で表される繰り返し単位を有するフェノール樹脂を含むことが好ましい。上記の繰り返し単位を有するフェノール樹脂は、例えば従来使用されてきたポリイミド樹脂及びポリベンゾオキサゾール樹脂と比べて低温での硬化が可能であり、かつ良好な伸度を有する硬化膜の形成を可能にする。 [(A1) phenol resin]
In this embodiment, (A) phenol resin is represented by the following general formula (2):

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

(Wherein p is an integer of 1 to 10) and selected from the group consisting of a divalent alkylene oxide group and a divalent organic group having an aromatic ring having 6 to 20 carbon atoms. Represents a divalent organic group. }
It is preferable that the phenol resin which has a repeating unit represented by these is included. The phenol resin having the above repeating unit can be cured at a low temperature as compared with, for example, conventionally used polyimide resin and polybenzoxazole resin, and enables formation of a cured film having good elongation. .

｛式中、Ｒ₁₄、Ｒ₁₅及びＲ₁₆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３〜１０の脂環式基、又は炭素数６〜１８の芳香族基を表し、そしてＲ₁₇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３〜１０の２価の脂環式基、又は炭素数６〜１８の２価の芳香族基を表す。｝で表される４つの基からなる群から選択される１価の置換基であることが好ましい。 In the general formula (2), R ₁ represents a monovalent organic group having 1 to 20 carbon atoms, halogen from the viewpoint of reactivity when synthesizing a resin having a repeating unit represented by the general formula (2). It is a monovalent substituent selected from the group consisting of an atom, a nitro group and a cyano group. From the viewpoint of alkali solubility, R ₁ is a halogen atom, a nitro group, a cyano group, an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, an aromatic group having 6 to 20 carbon atoms, And the following general formula group (14):

{In the formula, R ₁₄ , R ₁₅ and R ₁₆ are each independently a hydrogen atom, an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, or an alicyclic group having 3 to 10 carbon atoms. Represents a group, or an aromatic group having 6 to 18 carbon atoms, and R ₁₇ is a divalent aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, 2 having 3 to 10 carbon atoms. Represents a valent alicyclic group or a divalent aromatic group having 6 to 18 carbon atoms. } Is preferably a monovalent substituent selected from the group consisting of four groups represented by:

  In the present embodiment, in the general formula (2), a is an integer of 1 to 3, but 2 is preferable from the viewpoint of alkali solubility and tensile elongation. Moreover, when a is 2, the substitution position of hydroxyl groups may be any of ortho, meta, and para positions. When a is 3, the substitution position between the hydroxyl groups may be any of 1,2,3-position, 1,2,4-position, 1,3,5-position, and the like. When a is 1, in order to improve alkali solubility, (A) phenol resin can further contain (a3) phenol resin mentioned later.

In the present embodiment, in the above general formula (2), b is an integer of 0 to 3, and is preferably 0 or 1 from the viewpoint of alkali solubility and tensile elongation. Moreover, when b is 2 or 3, several R < ₁ > may mutually be same or different.

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

｛式中、Ｒ₂、Ｒ₃、Ｒ₄及びＲ₅は、それぞれ独立に、水素原子、炭素数１〜１０の１価の脂肪族基、又は水素原子の一部若しくは全部がフッ素原子で置換されてなる炭素数１〜１０の１価の脂肪族基であり、ｎ₁は０〜４の整数であって、ｎ₁が１〜４の整数である場合のＲ₆は、ハロゲン原子、又は炭素数１〜１２の１価の有機基であり、ｎ₁が２〜４の整数である場合の複数のＲ₆は互いに同一でも又は異なっていてもよい。｝で表される２価の基、及び下記一般式（８）：

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

（式中、ｐは、１〜１０の整数である。）
で表される２価のアルキレンオキシド基、及び下記式群（９）：

で表される２価の基からなる群から選択される２価の有機基である。｝で表される２価の基からなる群から選択される２価の有機基であることが好ましい。上記炭素数６〜１２の芳香族環を有する２価の有機基の炭素数は、好ましくは８〜７５、より好ましくは８〜４０である。なお上記炭素数６〜１２の芳香族環を有する２価の有機基の構造は、一般的には、上記一般式（２）中、ＯＨ基及び任意のＲ₁基が芳香環に結合している構造とは異なる。 In this embodiment, in the said General formula (2), X is a C2-C10 bivalent which may have an unsaturated bond from a cured relief pattern shape and a viewpoint of the elongation of a cured film. From an aliphatic group, a divalent alicyclic group having 3 to 20 carbon atoms, an alkylene oxide group represented by the general formula (7), and a divalent organic group having an aromatic ring having 6 to 12 carbon atoms A divalent organic group selected from the group consisting of Among these divalent organic groups, X represents the following general formula (7) from the viewpoint of the toughness of the cured film.

{Wherein 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 substituted with fluorine atoms. Is a monovalent aliphatic group having 1 to 10 carbon atoms, n ₁ is an integer of 0 to 4, and when n ₁ is an integer of ₁ to 4, R ₆ is a halogen atom, or When it is a monovalent organic group having 1 to 12 carbon atoms and n ₁ is an integer of 2 to 4, a plurality of R ₆ may be the same as or different from each other. } And the following general formula (8):

{Wherein 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 part or all of the hydrogen atoms are substituted with fluorine atoms. Represents a monovalent aliphatic group having 1 to 10 carbon atoms, and W is a single bond, an aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, or a fluorine atom. A C3-C20 alicyclic group, the following general formula (3):

(In the formula, p is an integer of 1 to 10.)
And a divalent alkylene oxide group represented by the following formula group (9):

A divalent organic group selected from the group consisting of divalent groups represented by the formula: } Is preferably a divalent organic group selected from the group consisting of divalent groups represented by: The carbon number of the divalent organic group having an aromatic ring having 6 to 12 carbon atoms is preferably 8 to 75, more preferably 8 to 40. The structure of the divalent organic group having an aromatic ring having 6 to 12 carbon atoms is generally such that in the general formula (2), the OH group and an arbitrary R ₁ group are bonded to the aromatic ring. The structure is different.

で表される２価の有機基であることがより好ましく、さらに下記式（１１）：

で表される２価の有機基であることが特に好ましい。 Furthermore, the divalent organic group represented by the general formula (8) is represented by the following formula (10) from the viewpoint of pattern forming property of the resin composition and tensile elongation of the cured film after curing:

Is more preferably a divalent organic group represented by the following formula (11):

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

  The ratio of the structure represented by the above formula (11) in the whole X is preferably 20% by mass or more, and more preferably 30% by mass or more, particularly from the viewpoint of tensile elongation. The proportion is preferably 80% by mass or less, and more preferably 70% by mass or less, from the viewpoint of alkali solubility of the composition.

｛式中、Ｒ₁₁は炭化水素基及びアルコキシ基からなる群から選択される炭素数１〜１０の１価の基であり、ｎ₂は１〜３であり、ｎ₃は０〜２の整数であり、ｍ₁は１〜５００の整数であり、２≦（ｎ₂＋ｎ₃）≦４であり、ｎ₃が２の場合には、複数のＲ₁₁は互いに同一でも又は異なっていてもよい。｝

｛式中、Ｒ₁₂及びＲ₁₃はそれぞれ独立に炭化水素基及びアルコキシ基からなる群から選択される炭素数１〜１０の１価の基であり、ｎ₄は１〜３の整数であり、ｎ₅は０〜２の整数であり、ｎ₆は０〜３の整数であり、ｍ₂は１〜５００の整数であり、２≦（ｎ₄＋ｎ₅）≦４であり、ｎ₅が２の場合には、複数のＲ₁₂は互いに同一でも又は異なっていてもよく、ｎ₆が２又は３の場合には、複数のＲ₁₃は互いに同一でも又は異なっていてもよい。｝ Moreover, among the phenol resins having the repeating unit represented by the general formula (2), both the structure represented by the following general formula (12) and the structure represented by the following general formula (13) have the same resin skeleton. The phenol resin contained therein is particularly preferable from the viewpoints of alkali solubility of the composition and elongation of the cured film.

{Wherein R ₁₁ is a monovalent group having 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, n ₂ is 1 to 3, and n ₃ is an integer of 0 to 2. M ₁ is an integer of ₁ to 500, 2 ≦ (n ₂ + n ₃ ) ≦ 4, and when n ₃ is 2, a plurality of R ₁₁ may be the same as or different from each other. . }

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

M ₂ of m ₁ and the general formula of the general formula (12) (13) represents the total number of the respective repeating units in the backbone of the phenolic resin. That is, in (A) phenol resin, the repeating unit in parentheses in the structure represented by the general formula (12) and the repeating unit in parentheses in the structure represented by the general formula (13) are random, block Or they can be arranged in combination. m ₁ and m ₂ are each independently an integer of ₁ to 500, the lower limit is preferably 2, more preferably 3, and the upper limit is preferably 450, more preferably 400, and even more preferably 350. is there. m ₁ and m ₂ are each independently preferably 2 or more from the viewpoint of the toughness of the film after curing, and preferably 450 or less from the viewpoint of solubility in an alkaline aqueous solution. The total of m ₁ and m ₂ is preferably 2 or more, more preferably 4 or more, still more preferably 6 or more from the viewpoint of the toughness of the film after curing, and from the viewpoint of solubility in an alkaline aqueous solution, Preferably it is 200 or less, More preferably, it is 175 or less, More preferably, it is 150 or less.

In the phenol resin (A) having both the structure represented by the general formula (12) and the structure represented by the general formula (13) in the same resin skeleton, the structure represented by the general formula (12) The higher the molar ratio, the better the film physical properties after curing, the better the heat resistance, and the higher the molar ratio of the structure represented by the general formula (13), the better the alkali solubility and the curing. Excellent pattern shape later. Accordingly, the ratio m ₁ / m ₂ of the structure represented by the general formula (12) to the structure represented by the general formula (13) is preferably 20/80 or more from the viewpoint of film physical properties after curing. More preferably, it is 40/60 or more, more preferably 50/50 or more. From the viewpoint of alkali solubility and the shape of the cured relief pattern, it is preferably 90/10 or less, more preferably 80/20 or less, still more preferably 70. / 30 or less.

The phenol resin having the repeating unit represented by the general formula (2), that is, the (a1) phenol resin is typically a phenol compound and a copolymer component (specifically, a compound having an aldehyde group (trioxane)). Including a compound having a ketone group, a compound having two methylol groups in the molecule, a compound having two alkoxymethyl groups in the molecule, and a haloalkyl group in the molecule. One or more compounds selected from the group consisting of two compounds in the above), and more typically, monomer components comprising these can be synthesized by a polymerization reaction. For example, an aldehyde compound, a ketone compound, a methylol compound, an alkoxymethyl compound, a diene compound, a haloalkyl compound, etc. with respect to phenol and / or a phenol derivative (hereinafter also collectively referred to as “phenol compound”) as shown below (A2) to obtain a phenol resin. In this case, in the above general formula (2), the portion represented by the structure in which the OH group and an arbitrary R ₁ group are bonded to the aromatic ring is derived from the phenol compound, and the portion represented by X is the above-mentioned It comes from the polymerization component. From the viewpoint of reaction control and the stability of the obtained (a2) phenol resin and photosensitive resin composition, the charged molar ratio of the phenol compound and the copolymer component (phenol compound): (copolymer component) is 5 : 1 to 1.01: 1 is preferable, and 2.5: 1 to 1.1: 1 is more preferable.

  In this embodiment, the weight average molecular weight of the phenol resin represented by (A) the general formula (2) is preferably 700 to 100,000, more preferably 1,500 to 80,000, still more preferably. Is 2,000 to 50,000. The weight average molecular weight is preferably 700 or more from the viewpoint of applicability of the reflow treatment to the cured film, and is preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition.

  In this embodiment, examples of the phenol compound that can be used to obtain the phenol resin represented by the general formula (2) include cresol, ethylphenol, propylphenol, butylphenol, amylphenol, cyclohexylphenol, hydroxybiphenyl, and benzylphenol. , Nitrobenzylphenol, cyanobenzylphenol, adamantanephenol, nitrophenol, fluorophenol, chlorophenol, bromophenol, trifluoromethylphenol, N- (hydroxyphenyl) -5-norbornene-2,3-dicarboximide, N- (Hydroxyphenyl) -5-methyl-5-norbornene-2,3-dicarboximide, trifluoromethylphenol, hydroxybenzoic acid, hydroxybenzoate Methyl acid, ethyl hydroxybenzoate, benzyl hydroxybenzoate, hydroxybenzamide, hydroxybenzaldehyde, hydroxyacetophenone, hydroxybenzophenone, hydroxybenzonitrile, resorcinol, xylenol, catechol, methylcatechol, ethylcatechol, hexylcatechol, benzylcatechol, nitrobenzylcatechol , Methyl resorcinol, ethyl resorcinol, hexyl resorcinol, benzyl resorcinol, nitrobenzyl resorcinol, hydroquinone, caffeic acid, dihydroxybenzoic acid, methyl dihydroxybenzoate, ethyl dihydroxybenzoate, butyl dihydroxybenzoate, propyl dihydroxybenzoate, dihydroxybenzoic acid Benzyl, dihydro Sibenzamide, dihydroxybenzaldehyde, dihydroxyacetophenone, dihydroxybenzophenone, dihydroxybenzonitrile, N- (dihydroxyphenyl) -5-norbornene-2,3-dicarboximide, N- (dihydroxyphenyl) -5-methyl-5-norbornene- 2,3-dicarboximide, nitrocatechol, fluorocatechol, chlorocatechol, bromocatechol, trifluoromethylcatechol, nitroresorcinol, fluororesorcinol, chlororesorcinol, bromoresorcinol, trifluoromethylresorcinol, pyrogallol, phloroglucinol, 1, 2,4-trihydroxybenzene, trihydroxybenzoic acid, methyl trihydroxybenzoate, trihydroxybenzoate Examples include ethyl acid, butyl trihydroxybenzoate, propyl trihydroxybenzoate, benzyl trihydroxybenzoate, trihydroxybenzamide, trihydroxybenzaldehyde, trihydroxyacetophenone, trihydroxybenzophenone, and trihydroxybenzonitrile.

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

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

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

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

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

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

  The above-mentioned phenol compound and copolymer component are condensed by dehydration, dehydrohalogenation, or dealcoholization, or polymerized while cleaving the unsaturated bond, thereby being represented by (A) the general formula (2). A phenol resin can be obtained, but a catalyst may be used during the polymerization. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, methanesulfonic acid, p-toluenesulfonic acid, dimethyl sulfuric acid, diethyl sulfuric acid, acetic acid, oxalic acid, 1-hydroxyethylidene-1,1. Examples include '-diphosphonic acid, zinc acetate, boron trifluoride, boron trifluoride / phenol complex, boron trifluoride / ether complex, and the like. On the other hand, examples of the alkaline catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, triethylamine, pyridine, 4-N, N-dimethylaminopyridine, piperidine, Piperazine, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, Examples include ammonia and hexamethylenetetramine.

  In this embodiment, the amount of the catalyst used for obtaining the phenol resin represented by the general formula (2) is the total number of moles of the copolymer component, preferably an aldehyde compound, a ketone compound, a methylol compound, an alkoxymethyl. It is preferably in the range of 0.01 mol% to 100 mol% with respect to 100 mol% of the total number of moles of the compound, diene compound and haloalkyl compound.

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

  In addition, the phenol resin represented by general formula (2) may be obtained by polymerizing a phenol compound that does not become a raw material having the structure of general formula (2) within a range that does not impair 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 of the phenol resin represented by the general formula (2).

[(A2) Phenolic resin]
In the present embodiment, (a2) phenolic resin (that is, modified phenolic resin) is a phenolic resin modified with a compound having a functional group capable of hydrogen bonding with a phenolic hydroxyl group (OH). More specifically, modified phenolic resins are ether bonds, hydroxyl groups, ester bonds, carboxyl groups, thioether bonds, thiol groups, thioester bonds, sulfo groups, sulfonyl groups, urethane bonds, urea bonds, thiourethane bonds, and thioureas. The phenol resin is modified with a compound having 4 to 100 carbon atoms and having at least one functional group selected from the group consisting of a bond. From the viewpoints of cost and tensile elongation of the cured film, the functional group is preferably an ester bond or a carboxyl group. Moreover, it is preferable from a viewpoint of the heat resistance of a cured film, and a reflow process applicability that carbon number of the compound which has this ester bond or a carboxyl group is 4-100.

  The compound having 4 to 100 carbon atoms having an ester bond or a carboxyl group (hereinafter, simply referred to as “ester bond or carboxyl group-containing compound”) is limited as long as it is a compound capable of reacting with phenol and a derivative thereof or a phenol resin. However, from the viewpoint of reactivity, it preferably has an unsaturated hydrocarbon group. This unsaturated hydrocarbon group preferably contains two or more unsaturated groups from the viewpoint of residual stress of the cured film and applicability of reflow treatment. Moreover, from the viewpoint of the compatibility of the resin composition and the flexibility of the cured film, the unsaturated hydrocarbon group preferably has 8 to 80 carbon atoms, more preferably 10 to 60 carbon atoms.

  A phenol resin modified with a compound having an ester bond or a carboxyl group is a reaction product of phenol or a derivative thereof (generically also referred to as a phenol compound in the present disclosure) and a compound having an ester bond or a carboxyl group (hereinafter referred to as “phenol compound”). This is a polycondensation product of an “ester bond or carboxyl group-containing compound-modified phenol compound”) and an aldehyde, or a reaction product of a phenol resin and an ester bond or a carboxyl group-containing compound.

  Examples of the phenol compound include phenol; o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2, 3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethyl Alkylphenols such as phenol; alkoxyphenols such as methoxyphenol and 2-methoxy-4-methylphenol; alkenylphenols such as vinylphenol and allylphenol; aralkylphenols such as benzylphenol; Coxycarbonylphenol; Arylcarbonylphenol such as benzoyloxyphenol; Halogenated phenol such as chlorophenol; Polyhydroxybenzene such as catechol, resorcinol, pyrogallol; Bisphenol such as bisphenol A and bisphenol F; α- or β-naphthol Naphthol derivatives; hydroxyalkylphenols such as p-hydroxyphenyl-2-ethanol, p-hydroxyphenyl-3-propanol and p-hydroxyphenyl-4-butanol; hydroxyalkylcresols such as hydroxyethylcresol; monoethylene oxide adduct of bisphenol Alcoholic hydroxyl group-containing phenol derivatives such as monopropylene oxide adducts of bisphenol; p-hydroxypheny Acid, p- hydroxy phenylpropionic acid, p- hydroxyphenyl butanoic acid, p- hydroxycinnamic acid, hydroxybenzoic acid, hydroxyphenyl benzoate, hydroxyphenoxy benzoate, carboxyl group-containing phenol derivatives such as di-phenolic acids. Further, methylolated products of the above phenol derivatives such as bishydroxymethyl-p-cresol may be used as the phenol derivative. A phenol compound is used individually by 1 type or in combination of 2 or more types.

Preferred examples of the ester bond or carboxyl group-containing compound include unsaturated fatty acids and unsaturated fatty acid esters from the viewpoint of heat resistance of the cured film.
Suitable unsaturated fatty acids and unsaturated fatty acid esters include vegetable oils, crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, erucic acid, nervonic acid, linoleic acid, α-linolenic acid Eleostearic acid, stearidonic acid, arachidonic acid, eicosapentaenoic acid, sardine acid and docosahexaenoic acid. Among these, vegetable oils that are unsaturated fatty acid esters are particularly preferred.

  The vegetable oil is an ester of glycerin and an unsaturated fatty acid, and is an non-drying oil having an iodine value of 100 or less, a semi-drying oil of more than 100 and less than 130, or a drying oil of 130 or more. Non-drying oils include, for example, olive oil, Asa seed oil, cashew oil, potato oil, camellia oil, castor oil, and peanut oil. Examples of semi-drying oils include corn oil, cottonseed oil, and sesame oil. Examples of the drying oil include paulownia oil, linseed oil, soybean oil, walnut oil, safflower oil, sunflower oil, camellia oil and coconut oil. Moreover, you may use the processed vegetable oil obtained by processing these vegetable oils.

  Among the above vegetable oils, it is preferable to use a non-drying oil from the viewpoint of preventing gelation accompanying the progress of excessive reaction and improving the yield in the reaction of phenol or a derivative thereof or a phenol resin with a vegetable oil. On the other hand, it is preferable to use a drying oil from the viewpoint of improving the adhesion, mechanical properties and thermal shock resistance of the resist pattern. Among the drying oils, tung oil, linseed oil, soybean oil, walnut oil and safflower oil are preferable, and tung oil and linseed oil are more preferable because the effects of the present invention can be more effectively and reliably exhibited. These vegetable oils are used alone or in combination of two or more.

  The reaction of phenol or a derivative thereof with an ester bond or a carboxyl group-containing compound is preferably performed at 50 to 130 ° C. From the viewpoint of reducing the residual stress of the cured film, the reaction ratio between phenol or a derivative thereof and the ester bond-containing compound is preferably 1 to 100 parts by mass of the ester bond-containing compound with respect to 100 parts by mass of phenol or a derivative thereof. 5 to 50 parts by mass is more preferable. If the ester bond-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease, and if it exceeds 100 parts by mass, the heat resistance of the cured film tends to decrease. In the above reaction, if necessary, p-toluenesulfonic acid, trifluoromethanesulfonic acid, or the like may be used as a catalyst.

  A phenol resin modified with an ester bond-containing compound is produced by polycondensation of an ester bond or a carboxyl group-containing compound-modified phenol compound generated by the above reaction with an aldehyde. Aldehydes are, for example, formaldehyde, acetaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde, hydroxyphenylacetaldehyde, methoxyphenylacetaldehyde, crotonaldehyde, chloroacetaldehyde, chlorophenylacetaldehyde, acetone, glyceraldehyde, glyoxylic acid, methyl glyoxylate, Phenyl glyoxylate, hydroxyphenyl glyoxylate, formylacetic acid, methyl formylacetate, 2-formylpropionic acid, methyl 2-formylpropionate, pyruvic acid, repric acid, 4-acetylbutyric acid, acetone dicarboxylic acid and 3,3′- Selected from 4,4'-benzophenone tetracarboxylic acid. Further, a formaldehyde precursor such as paraformaldehyde or trioxane may be used. These aldehydes are used alone or in combination of two or more.

  The reaction between the aldehydes and the ester bond or carboxyl group-containing compound-modified phenol compound is a polycondensation reaction, and conventionally known synthesis conditions for phenol resins can be used. The reaction is preferably performed in the presence of a catalyst such as an acid or a base, and an acid catalyst is more preferably used from the viewpoint of the degree of polymerization (molecular weight) of the resin. Examples of the acid catalyst include hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, and oxalic acid. These acid catalysts can be used alone or in combination of two or more.

  The above reaction is preferably carried out usually at a reaction temperature of 100 to 120 ° C. Moreover, although reaction time changes with kinds and quantity of a catalyst to be used, it is 1 to 50 hours normally. After completion of the reaction, the reaction product is dehydrated under reduced pressure at a temperature of 200 ° C. or lower to obtain a phenol resin modified with an ester bond-containing compound. In the reaction, a solvent such as toluene, xylene, or methanol can be used.

  A phenol resin modified with an ester bond or a carboxyl group-containing compound is obtained by polycondensing the above ester bond or carboxyl group-containing compound-modified phenol compound with an aldehyde together with a compound other than phenol such as m-xylene. You can also. In this case, the molar ratio of the compound other than phenol to the compound obtained by reacting the phenol compound with the ester bond or carboxyl group-containing compound is preferably less than 0.5.

  The phenol resin modified with an ester bond or a carboxyl group-containing compound can also be obtained by reacting a phenol resin with an ester bond or a carboxyl group-containing compound. A phenol resin is a polycondensation product of a phenol compound and aldehydes. In this case, as a phenol compound and aldehydes, the thing similar to the phenol compound and aldehyde mentioned above can be used, and a phenol resin is compoundable on the conventionally well-known conditions as mentioned above.

  Specific examples of phenolic resins obtained from phenolic compounds and aldehydes include phenol / formaldehyde novolak resins, cresol / formaldehyde novolak resins, xylylenol / formaldehyde novolak resins, resorcinol / formaldehyde novolak resins and phenol-naphthol / formaldehyde novolak resins. .

  As the ester bond or carboxyl group-containing compound to be reacted with the phenol resin, the same ester bond or carboxyl group-containing compound as described above can be used.

  The reaction between the phenol resin and the ester bond or carboxyl group-containing compound is usually preferably carried out at 50 to 130 ° C. In addition, the reaction ratio between the phenol resin and the ester bond or carboxyl group-containing compound is 1 to 100 mass of the ester bond-containing compound with respect to 100 parts by mass of the phenol resin from the viewpoint of improving the flexibility of the cured film (resist pattern). Part, preferably 2 to 70 parts by weight, and more preferably 5 to 50 parts by weight. If the ester bond-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease, and if it exceeds 100 parts by mass, the possibility of gelation during the reaction tends to increase, and the heat resistance of the cured film Tend to decrease. At this time, if necessary, p-toluenesulfonic acid, trifluoromethanesulfonic acid or the like may be used as a catalyst. In addition, solvents, such as toluene, xylene, methanol, tetrahydrofuran, can be used for reaction.

  It is also possible to use an acid-modified phenol resin by reacting a polybasic acid anhydride with the phenolic hydroxyl group of the phenol resin modified with an ester bond or a carboxyl group-containing compound produced by the above method. By acid-modifying with a polybasic acid anhydride, a carboxy group is introduced and the solubility in an alkaline aqueous solution (developer) is further improved.

  The polybasic acid anhydride is not particularly limited as long as it has an acid anhydride group formed by dehydration condensation of a carboxy group of a polybasic acid having a plurality of carboxy groups. Examples of the polybasic acid anhydride include phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride Dibasic acid anhydrides such as methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride and trimellitic anhydride, biphenyltetra Carboxylic dianhydride, naphthalene tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic anhydride and benzophenone tetra Carboxylic acid aromatic tetracarboxylic acid dianhydride such as dianhydride. You may use these individually by 1 type or in combination of 2 or more types. Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride, and more preferably at least one selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride, and hexahydrophthalic anhydride. In this case, there is an advantage that a resist pattern having a better shape can be formed.

  The reaction between the phenolic hydroxyl group and the polybasic acid anhydride can be carried out at 50 to 130 ° C. In this reaction, the polybasic acid anhydride is preferably reacted with 0.10 to 0.80 mol, more preferably 0.15 to 0.60 mol with respect to 1 mol of the phenolic hydroxyl group, More preferably, the reaction is performed at 20 to 0.40 mol. If the polybasic acid anhydride is less than 0.10 mol, the developability tends to decrease, and if it exceeds 0.80 mol, the alkali resistance of the unexposed area tends to decrease.

  In addition, you may contain a catalyst in the said reaction as needed from a viewpoint of performing reaction rapidly. Examples of the catalyst include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, and phosphorus compounds such as triphenylphosphine.

  The acid value of the phenol resin further modified with polybasic acid anhydride is preferably 30 to 200 mgKOH / g, more preferably 40 to 170 mgKOH / g, and further preferably 50 to 150 mgKOH / g. . When the acid value is less than 30 mgKOH / g, it tends to require a longer time for alkali development than when the acid value is in the above range, and when it exceeds 200 mgKOH / g, the acid value is in the above range. In comparison with the above, the developer resistance of the unexposed portion tends to be lowered.

  The compound having an ether bond is not limited as long as it has this bond, and examples thereof include vinyl ether, allyl ether, methyl vinyl ether, methyl allyl ether, ethyl vinyl ether, and ethyl allyl ether.

  The compound having a hydroxyl group is not limited as long as it has this functional group, but vinyl alcohol, allyl alcohol, 4-vinyl-2-methoxyphenol, 4-ethenylphenol, 2-vinylphenol, 4-vinylphenol, Examples include vinylphenol and 6-methyl-2-allylphenol.

  The compound having a thioether bond is not limited as long as it has this bond, and examples thereof include methylallyl thioether, allyl sulfide, and ethyl (vinylthiomethyl) ether.

  The compound having a thiol group is not limited as long as it has this functional group. However, allyl mercaptan, 2-vinylbenzenethiol, 4- (vinyldimethylsilyl) -1-butanethiol, allylthiol, 2- (Allyldimethylsilyl) ethanethiol, and the like.

  The compound having a sulfo group is not limited as long as it has this functional group, and examples thereof include vinyl sulfonic acid, 2-propene-1-sulfonic acid, and allyl methanesulfonate.

  The sulfonyl group is not limited as long as it has this functional group, and examples thereof include phenyl vinyl sulfone, vinyl methyl sulfone, and divinyl sulfone.

  The compound having a urethane bond is not limited as long as it has this bond, but 2- (carbamoyloxymethyl) -2-methylpentyl = allylcarbamate, tert-butyl N-allylcarbazate, etc. Is mentioned.

  The compound having a urea bond is not limited as long as it has this bond, but N-vinyl-N, N′-trimethylene urea, allyl urea, allyl isopropyl acetyl urea, 1-vinyl urea, N— (2,6-Dimethylphenyl) -N-vinyl-N′-ethylurea and the like.

  The compound having a thiourethane bond, a thiourea bond, or a thioester bond is not limited as long as it has this bond, but 1-allyl-2-thiourea, 1-allyl-3- (2-hydroxy Ethyl) -2-thiourea, 1-allyl-3- (3,4,5-trimethoxybenzoyl) thiourea, 1-allyl-3- (2-formylphenyl) thiourea, 1-phenyl-2-allyl -3-benzoylisothiourea, 1-allyl-3- (2-hydroxyethyl) -2-thiourea, and the like.

  (A2) The molecular weight of the phenol resin is preferably 1000 to 500000, more preferably 2000 to 200000, more preferably 2000 to 100000 in terms of weight average molecular weight in consideration of solubility in an alkaline aqueous solution and the balance between photosensitive properties and cured film properties. More preferably.

  (A) A phenol resin may consist of (a1) phenol resin and / or (a2) phenol resin, and may further contain an additional phenol resin. The total ratio of (A1) phenol resin and (a2) phenol resin in (A) phenol resin is preferably 5% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more. Although the said ratio may be 100 mass%, from a viewpoint of obtaining the effect by an additional component favorably, it can be 95 mass% or less, or 85 mass% or less, or 70 mass% or less, for example.

  For example, in this embodiment, (A) the phenol resin is a phenol selected from novolak and polyhydroxystyrene in order to improve alkali solubility in addition to (a1) phenol resin and / or (a2) phenol resin. It may further contain a resin (hereinafter also referred to as (a3) phenol resin). In particular, when a is 1 in the above general formula (2), in order to improve alkali solubility, (A) a phenol resin selected from novolak and polyhydroxystyrene ((a3) a phenol resin) Furthermore, it is preferable to include.

  The total amount of (a1) phenol resin and (a2) phenol resin and the mixing ratio of (a3) phenol resin is {(a1) + (a2)} / (a3) = 5/95 to 95 / in mass ratio. A range of 5 is preferable. This mixing ratio is 5 from the viewpoints of solubility in an alkaline aqueous solution, sensitivity and resolution when forming a resist pattern, residual stress of the cured film, applicability to reflow treatment, and tensile elongation of the cured film. / 95 to 95/5 is preferable, 10/90 to 90/10 is more preferable, 15/85 to 85/15 is more preferable, 20/80 to 80/20 is further preferable, and 30/70 to 70 is preferable. Particularly preferred is / 30.

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

  In the present disclosure, polyhydroxystyrene means all polymers containing hydroxystyrene as a polymerized unit. The polyhydroxystyrene is preferably polyparavinylphenol. Polyparavinylphenol means all polymers containing paravinylphenol as polymerized units. Unless it is contrary to the object of the present invention, polymer units other than hydroxystyrene (for example, paravinylphenol) can be used to constitute polyhydroxystyrene (for example, polyparavinylphenol). In the polyhydroxystyrene, the ratio of the number of moles of hydroxystyrene units based on the number of moles of all polymerized units is preferably 10 mol% to 99 mol%, more preferably 20 to 97 mol%, still more preferably 30 to 95 mol. %. When the ratio is 10 mol% or more, it is advantageous from the viewpoint of alkali solubility of the photosensitive resin composition, and when it is 99 mol% or less, a cured film obtained by curing a composition containing a copolymer component described later. This is advantageous from the viewpoint of reflow applicability. The polymerization unit other than hydroxystyrene (for example, paravinylphenol) may be any compound copolymerizable with paravinylphenol. Examples of polymer units other than paravinylphenol include, but are not limited to, methyl acrylate, methyl methacrylate, hydroxyethyl acrylate, butyl methacrylate, octyl acrylate, 2-ethoxyethyl methacrylate, t-butyl acrylate, 1, 5-pentanediol diacrylate, N, N-diethylaminoethyl acrylate, ethylene glycol diacrylate, 1,3-propanediol diacrylate, decamethylene glycol diacrylate, decamethylene glycol dimethacrylate, 1,4-cyclohexanediol diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripropylene glycol diacrylate, glycerol triacrylate 2,2-di (p-hydroxyphenyl) -propane dimethacrylate, triethylene glycol diacrylate, polyoxyethyl-2--2-di (p-hydroxyphenyl) -propane dimethacrylate, triethylene glycol dimethacrylate, Polyoxypropyltrimethylolpropane triacrylate, ethylene glycol dimethacrylate, butylene glycol dimethacrylate, 1,3-propanediol dimethacrylate, butylene glycol dimethacrylate, 1,3-propanediol dimethacrylate, 1,2,4-butanetriol Trimethacrylate, 2,2,4-trimethyl-1,3-pentanediol dimethacrylate, pentaerythritol trimethacrylate, 1-phenylethylene-1,2 Esters of acrylic acid such as dimethacrylate, pentaerythritol tetramethacrylate, trimethylolpropane trimethacrylate, 1,5-pentanediol dimethacrylate and 1,4-benzenediol dimethacrylate; styrene and, for example, 2-methylstyrene and vinyl Examples thereof include substituted styrene such as toluene; monomers such as vinyl esters such as vinyl acrylate and vinyl methacrylate; and o-vinylphenol and m-vinylphenol.

  Moreover, as a novolak and polyhydroxystyrene demonstrated above, each can be used individually by 1 type or in combination of 2 or more types.

  In the embodiment, the mass average molecular weights of novolak and polyhydroxystyrene are each preferably 700 to 100,000, more preferably 1,500 to 80,000, still more preferably 2,000 to 50,000. It is. The mass average molecular weight is preferably 700 or more from the viewpoint of applicability to reflow treatment, and is preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition.

｛式中、Ｐ₁，Ｐ₂，Ｐ₃，Ｐ₄及びＰ₅は、それぞれ独立に、水素原子、水酸基、メルカプト基、アミノ基、カルボキシル基、炭素数１〜３０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数３〜３０の置換又は非置換の脂環式基、置換又は非置換のフェニル基、及び、置換又は非置換のベンジル基からなる群から選択される基であり、ここで、Ｐ₁及びＰ₂は、縮合して置換若しくは非置換のベンゼン環又はヘテロ原子１個を有する６員の複素環を形成してもよい。｝
で表される化合物からなる群から選択される少なくとも１種のトリアゾール化合物（本開示で、（Ｂ）トリアゾール化合物ともいう）を含む。ポジ型感光性樹脂組成物が（Ｂ）トリアゾール化合物のような特定の含窒素化合物を含むことにより、硬化膜のリフロー処理適用性（硬化レリーフパターン付きウエハーをリフロー処理してもパターン異常が抑えられること）を向上することが出来る。リフロー処理適用性が向上する化学メカニズムは定かではないが、（Ｂ）トリアゾール化合物は有機アミンの性質を有し、ブレンステッド塩基であるため、熱硬化時に架橋剤とフェノール化合物（モノマー、オリゴマー等）との架橋を促進し、硬化物の架橋密度が向上しているためと考えられる。 [(B) Triazole compound]
In the present embodiment, the positive photosensitive resin composition includes (B) the following general formula group (1):

{Wherein P ₁ , P ₂ , P ₃ , P ₄ and P ₅ are each independently a hydrogen atom, a hydroxyl group, a mercapto group, an amino group, a carboxyl group, an alkyl group having 1 to 30 carbon atoms, or 1 carbon atom. A group selected from the group consisting of 10 to 10 alkoxy groups, substituted or unsubstituted alicyclic groups having 3 to 30 carbon atoms, substituted or unsubstituted phenyl groups, and substituted or unsubstituted benzyl groups, Here, P ₁ and P ₂ may be condensed to form a substituted or unsubstituted benzene ring or a 6-membered heterocyclic ring having one heteroatom. }
And at least one triazole compound selected from the group consisting of the compounds represented by (in this disclosure, also referred to as (B) triazole compound). When the positive photosensitive resin composition contains a specific nitrogen-containing compound such as (B) a triazole compound, the applicability of reflow treatment of a cured film (pattern anomalies can be suppressed even when a wafer with a cured relief pattern is reflowed) Can be improved. The chemical mechanism that improves the reflow treatment applicability is not clear, but (B) Triazole compounds have the properties of organic amines and are Bronsted bases, so crosslinking agents and phenolic compounds (monomers, oligomers, etc.) during thermosetting This is probably because the crosslinking density of the cured product is improved.

  In this disclosure, a hetero atom intends a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom.

P ₁ , P _2, P ₄ and P ₅ are preferably each independently a mercapto group, an amino group, or an alkyl group from the viewpoint of applicability of the cured product to reflow treatment.

｛式中、Ｐ₆，Ｐ₇及びＰ₈は、それぞれ独立に水酸基、メルカプト基、アミノ基、カルボキシル基、ニトロ基、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数３〜２０の置換又は非置換の脂環式基、置換又は非置換のフェニル基、及び、置換又は非置換のベンジル基からなる群から選択される基であり、ｋ１，ｋ２及びｋ３はそれぞれ独立に０〜３の整数であり、ｋ１，ｋ２及びｋ３がそれぞれ２又は３である場合には、複数のＰ₆，Ｐ₇及びＰ₈は互いに同一でも又は異なっていてもよく、Ｐ₃は前記一般式群（１）で定義したものと同じである。｝
で表される化合物からなる群から選択される少なくとも１種が好ましい。 In the general formula group (1), P ₁ and P ₂ can be condensed to form a substituted or unsubstituted benzene ring or a 6-membered heterocyclic ring. Among them, from the viewpoint of reflow treatment applicability and discoloration of the metal substrate after curing when the cured film is formed on the metal substrate, the following general formula group (4)

{Wherein P ₆ , P ₇ and P ₈ are each independently a hydroxyl group, mercapto group, amino group, carboxyl group, nitro group, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, carbon A group selected from the group consisting of a substituted or unsubstituted alicyclic group, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted benzyl group having 3 to 20, k1, k2 and k3 are each When each independently represents an integer of 0 to 3, and k1, k2 and k3 are each 2 or 3, the plurality of P ₆ , P ₇ and P ₈ may be the same or different from each other, and P ₃ is The same as defined in the general formula group (1). }
At least one selected from the group consisting of compounds represented by

P ₆ , P ₇ and P ₈ are preferably each independently a hydroxyl group, an alkyl group, an amino group, a carboxyl group, or a nitro group from the viewpoint of applicability of the cured product of the composition to a reflow treatment.

｛式中、ｈは、１〜５の整数であり、そしてＰ₉は、水素原子、水酸基、カルボキシル基、メルカプト基、炭素数１〜１０の直鎖又は分岐鎖の脂肪族基、少なくとも１個の水酸基で置換された炭素数１〜１０の直鎖又は分岐鎖の脂肪族基、及び少なくとも１個のカルボキシル基で置換された炭素数１〜１０の直鎖又は分岐鎖の脂肪族基からなる群から選択される１価の基である。｝

｛式中、ｉは、１〜５の整数であり、そしてＰ₁₀及びＰ₁₁はそれぞれ独立に炭素数１〜１０の直鎖又は分岐鎖の脂肪族基、少なくとも１個の水酸基で置換された炭素数１〜１０の直鎖又は分岐鎖の脂肪族基、少なくとも１個のカルボキシル基で置換された炭素数１〜１０の直鎖又は分岐鎖の脂肪族基からなる群から選択される１価の基である。｝

｛式中、ｐは、０〜６の整数であり、そしてｑは、１〜６の整数である。｝ In the above general formula group (1), P ₃ is a perspective of the reflow treatment application of the cured product of the composition, from a monovalent group represented by the following formula (5), (6) and (18) Is preferably a group selected from the group consisting of monovalent groups represented by the following formulas (5) and (6).

{Wherein h is an integer of 1 to 5 and P ₉ is a hydrogen atom, a hydroxyl group, a carboxyl group, a mercapto group, a linear or branched aliphatic group having 1 to 10 carbon atoms, at least one A linear or branched aliphatic group having 1 to 10 carbon atoms substituted with a hydroxyl group and a linear or branched aliphatic group having 1 to 10 carbon atoms substituted with at least one carboxyl group A monovalent group selected from the group. }

{Wherein i is an integer of 1 to 5 and P ₁₀ and P ₁₁ are each independently substituted with a linear or branched aliphatic group having 1 to 10 carbon atoms, at least one hydroxyl group A monovalent group selected from the group consisting of a linear or branched aliphatic group having 1 to 10 carbon atoms and a linear or branched aliphatic group having 1 to 10 carbon atoms substituted with at least one carboxyl group It is the basis of. }

{Wherein p is an integer from 0 to 6 and q is an integer from 1 to 6. }

｛式中、ｈは、一般式（５）で定義したものと同じである。｝
で表される基が好ましい。 Among the groups represented by the above general formula (5), the following general formula (15):

{Wherein h is the same as defined in general formula (5). }
The group represented by these is preferable.

｛式中、ｊは、１〜９の整数であり、Ｐ₉及びＰ₁₀は、それぞれ独立に水素原子、水酸基又はカルボキシル基であり、そしてｉは一般式（６）で定義したものと同じである。｝

｛式中、ｋは、１〜２の整数であり、そしてｉは一般式（６）で定義したものと同じである。｝ Among the groups represented by the general formula (6), groups represented by the following general formulas (16) and (17) are preferable from the viewpoint of applicability of the reflow treatment of the cured product.

{Wherein j is an integer of 1 to 9, P ₉ and P ₁₀ are each independently a hydrogen atom, a hydroxyl group or a carboxyl group, and i is the same as defined in the general formula (6) is there. }

{Wherein k is an integer of 1 to 2 and i is the same as defined in general formula (6). }

  Specific examples of the triazole compound represented by the general formula group (1) include 1,2,3-triazole, 1,2,4-triazole, 3-mercapto-4-methyl-4H-1,2,4. -Triazole, 3-mercapto-1,2,4-triazole, 4-amino-3,5-dimethyl-4H-1,2,4-triazole, 4-amino-3,5-dipropyl-4H-1,2 , 4-triazole, 3-amino-5-isopropyl-1,2,4-triazole, 4-amino-3-mercapto-5-methyl-4H-1,2,4-triazole, 3-amino-5-mercapto -1,2,4-triazole, 3-amino-5-methyl-4H-1,2,4-triazole, 4-amino-1,2,4-triazole, 4-amino-3,5-dimethyl-1 , 2,4-tri Sol, 4-amino-5-methyl-4H-1,2,4-triazole-3-thiol, 3,5-diamino-1H-1,2,4-triazole, 1,2,3-benzotriazole, 1 -Aminobenzotriazole, 1-hydroxybenzotriazole, 4-hydroxy-1H-benzotriazole, 1- (hydroxymethyl) benzotriazole, 2-aminobenzotriazole, 5-amino-1H-benzotriazole, 4-methyl-1H- Benzotriazole, 5-methyl-1H-benzotriazole, 1H-benzotriazole 4-carboxylic acid, 1H-benzotriazole 5-carboxylic acid, 4-nitro-1H-benzotriazole, 5-nitro-1H-benzotriazole, 5, 6-dimethyl-1,2,3-benzotriazole, 1- [ 2-ethylhexylamino) methyl] -benzotriazole, 1- (1 ′, 2′-dicarboxyethyl) benzotriazole, 1- (2,3-dicarboxypropyl) benzotriazole, 1- [N, N-bis ( 2-ethylhexyl) aminomethyl] tolyltriazole, 1- [N, N-bis (hydroxyethyl) aminomethyl] tolyltriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole, 1- [ N, N-bis (2-hydroxyethyl) aminomethyl] benzotriazole, 1- [N-2-hydroxyethylaminomethyl] benzotriazole, 1- [N, N-bis (2-hydroxyethyl) aminomethyl]- 4-carboxybenzotriazole, 1- [N, N-bis (2-hydroxyethyl) aminomethyl] -5 Ruboxybenzotriazole, 1- [N, N-bis (2-hydroxyethyl) aminomethyl] -4-methylbenzotriazole, 1- [N, N-bis (2-hydroxyethyl) aminomethyl] -5-methyl Benzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] -4-methylbenzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] -5-methylbenzotriazole, 1H -1,2,3-triazole [4,5-6] pyridine, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5 t-butylphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-t-octylphenyl) -2H-benzotriazole, 2- (2H-ben Triazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4,6-di-t-pentylphenol, 2- (3,5-di-t-butyl-2- Hydroxyphenyl) -1-benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) -1-benzotriazole, 2- (2-hydroxy-5-t-octylphenyl) -1-benzotriazole, 2 -(Benzotriazol-1-yl) -p-cresol, 2- (benzotriazol-1-yl) -4,6-di-t-pentylphenol, 4-azabenzotriazole, 1-hydroxy-7-azabenzo Examples include, but are not limited to, triazole, 1-acetyl-1H-1,2,3-triazolo [4,5-6] pyridine, and the like. These may be used alone or in combination of two or more.

  Among the triazole compounds represented by the general formula group (1), 1,2,3-triazole, 1,2,4-triazole and derivatives thereof, 1, from the viewpoint of applicability of the reflow treatment of the cured product, At least one selected from the group consisting of 2,3-benzotriazole and derivatives thereof is preferable, and substituted benzotriazole (that is, benzotriazole in which a hydrogen atom of a benzene ring and / or a triazole ring is substituted) is particularly preferable. Particularly preferred examples of substituted benzotriazoles include 4-methyl-1H-benzotriazole, 5-methyl-1H-benzotriazole, 1H-benzotriazole 4-carboxylic acid, 1H-benzotriazole 5-carboxylic acid, 1- [N, N-bis (2-hydroxyethyl) aminomethyl] -4-methylbenzotriazole, 1- [N, N-bis (2-hydroxyethyl) aminomethyl] -5-methylbenzotriazole, 1-hydroxy-7-aza Benzotriazole.

  (B) The compounding quantity of a triazole compound is 0.1-20 mass parts with respect to 100 mass parts of (A) phenol resin, Preferably it is 0.5-10 mass parts, More preferably, it is 0.5-5 mass. Part. It is. If the blending amount is less than 0.1 parts by mass, the applicability of the reflow treatment of the cured film tends to be impaired. On the other hand, if it exceeds 20 parts by mass, the storage stability of the composition tends to deteriorate.

[(C) Compound having quinonediazide group]
Examples of the compound (C) having a quinonediazide group (hereinafter also referred to as “(C) quinonediazide compound”) include a compound having a 1,2-benzoquinonediazide structure and a compound having a 1,2-naphthoquinonediazide structure, US Pat. No. 2,772,972, US Pat. No. 2,797,213 and US Pat. No. 3,669,658 are known substances. The (C) quinonediazide compound includes 1,2-naphthoquinonediazide-4-sulfonic acid ester of a polyhydroxy compound having a specific structure described in detail below, and 1,2-naphthoquinonediazide-5-sulfone of the polyhydroxy compound. It is preferably at least one compound selected from the group consisting of acid esters (hereinafter also referred to as “NQD compound”).

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

｛式中、Ｘ₁及びＸ₂は、それぞれ独立に、水素原子又は炭素数１〜６０（好ましくは、炭素数１〜３０）の１価の有機基を表し、Ｘ₃及びＸ₄は、それぞれ独立に、水素原子又は炭素数１〜６０（好ましくは、炭素数１〜３０）の１価の有機基を表し、ｒ１、ｒ２、ｒ３及びｒ４は、それぞれ独立に、０〜５の整数であり、ｒ３及びｒ４の少なくとも１つは、１〜５の整数であり、（ｒ１＋ｒ３）≦５であり、そして（ｒ２＋ｒ４）≦５である。｝

｛式中、Ｚは、炭素数１〜２０の４価の有機基を表し、Ｘ₅、Ｘ₆、Ｘ₇及びＸ₈は、それぞれ独立に、炭素数１〜３０の１価の有機基を表し、ｒ６は、０又は１の整数であり、ｒ５、ｒ７、ｒ８及びｒ９は、それぞれ独立に、０〜３の整数であり、ｒ１０、ｒ１１、ｒ１２及びｒ１３は、それぞれ独立に、０〜２の整数であり、そしてｒ１０、ｒ１１、ｒ１２及びｒ１３の全てが０になることはない。｝

｛式中、ｒ１４は、１〜５の整数を表し、ｒ１５は、３〜８の整数を表し、（ｒ１４×ｒ１５）個のＬは、それぞれ独立に、炭素数１〜２０の１価の有機基を表し、（ｒ１５）個のＴ¹及び（ｒ１５）個のＴ²はそれぞれ独立に水素原子又は炭素数１〜２０の１価の有機基を表す。｝

｛式中、Ａは、脂肪族の３級又は４級炭素を含む２価の有機基を表し、そしてＭは、２価の有機基を表し、好ましくは下記化学式：

で表される３つの基から選択される２価の基を表す。｝

｛式中、ｒ１７、ｒ１８、ｒ１９及びｒ２０は、それぞれ独立に、０〜２の整数であり、ｒ１７、ｒ１８、ｒ１９及びｒ２０の少なくとも１つは、１又は２であり、Ｘ₁₀〜Ｘ₁₉は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルケニル基、アルコキシ基、アリル基及びアシル基からなる群から選択される１価の基を表し、そしてＹ₁、Ｙ₂及びＹ₃は、は、それぞれ独立に、単結合、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ₂−、−ＣＯ−、−ＣＯ₂−、シクロペンチリデン、シクロヘキシリデン、フェニレン、及び炭素数１〜２０の２価の有機基からなる群から選択される２価の基を表す。｝ In the present embodiment, (C) the compound having a quinonediazide group is a 1,2-naphthoquinonediazide-4-sulfonic acid ester of a hydroxy compound represented by the following general formulas (19) to (26) and / or 1, A 2-naphthoquinonediazide-5-sulfonic acid ester compound is preferable from the viewpoints of sensitivity and resolution when forming a resist pattern.

{Wherein, X ₁ and X ₂ each independently represent a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms (preferably 1 to 30 carbon atoms), and X ₃ and X ₄ are each Independently, it represents a hydrogen atom or a monovalent organic group having 1 to 60 carbon atoms (preferably 1 to 30 carbon atoms), and r1, r2, r3 and r4 are each independently an integer of 0 to 5. , R3 and r4 are integers of 1 to 5, (r1 + r3) ≦ 5 and (r2 + r4) ≦ 5. }

{In the formula, Z represents a tetravalent organic group having 1 to 20 carbon atoms, and X ₅ , X ₆ , X ₇ and X ₈ are each independently a monovalent organic group having 1 to 30 carbon atoms. R6 is an integer of 0 or 1, r5, r7, r8 and r9 are each independently an integer of 0 to 3, and r10, r11, r12 and r13 are each independently 0 to 2 And all of r10, r11, r12, and r13 cannot be zero. }

{Wherein r14 represents an integer of 1 to 5, r15 represents an integer of 3 to 8, and (r14 × r15) L's are each independently a monovalent organic having 1 to 20 carbon atoms. And (r15) T ¹ and (r15) T ² each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. }

{Wherein A represents a divalent organic group containing an aliphatic tertiary or quaternary carbon, and M represents a divalent organic group, preferably the following chemical formula:

Represents a divalent group selected from the three groups represented by: }

{Wherein, r17, r18, r19 and r20 are each independently an integer of 0 to 2, r17, r18, at least one of r19 and r20 is 1 or 2, X ₁₀ to X ₁₉ is Each independently represents a monovalent group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group and an acyl group, and Y ₁ , Y ₂ and Y ₃ are Each independently represents a single bond, —O—, —S—, —SO—, —SO ₂ —, —CO—, —CO ₂ —, cyclopentylidene, cyclohexylidene, phenylene, and 20 represents a divalent group selected from the group consisting of 20 divalent organic groups. }

｛式中、Ｘ₂₀及びＸ₂₁は、それぞれ独立に、水素原子、アルキル基、アルケニル基、アリール基、及び置換アリール基から成る群から選択される少なくとも１つの１価の基を表し、Ｘ₂₂、Ｘ₂₃、Ｘ₂₄及びＸ₂₅は、それぞれ独立に、水素原子又はアルキル基を表し、ｒ２１は、１〜５の整数であり、そしてＸ₂₆、Ｘ₂₇、Ｘ₂₈及びＸ₂₉は、それぞれ独立に、水素原子又はアルキル基を表す。｝
で表される３つの２価の有機基から選択されることが好ましい。 In a further embodiment, in the general formula (23), Y _{1 to} Y ₃ are each independently the following general formula:

{Wherein, X ₂₀ and X ₂₁ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, and at least one monovalent group selected from the group consisting of substituted aryl group, X ₂₂ , X ₂₃ , X ₂₄ and X ₂₅ each independently represent a hydrogen atom or an alkyl group, r 21 is an integer of 1 to 5, and X ₂₆ , X ₂₇ , X ₂₈ and X ₂₉ are each independently Represents a hydrogen atom or an alkyl group. }
It is preferable to be selected from three divalent organic groups represented by:

｛式中、ｒ１６は、それぞれ独立に、０〜２の整数であり、そしてＸ₉は、それぞれ独立に、水素原子又は炭素数１〜２０の１価の有機基を表し、Ｘ₉が複数で存在する場合には複数のＸ₉は、互いに同一でも又は異なっていてもよく、そしてＸ₉は、下記一般式：

（式中、ｒ１８は、０〜２の整数であり、Ｘ₃₁は、水素原子、アルキル基、及びシクロアルキル基からなる群から選択される１価の有機基を表し、そしてｒ１８が２である場合には、２つのＸ₃₁は、互いに同一でも又は異なっていてもよい。）
で表される１価の有機基であることが好ましい。｝

｛式中、Ｘ₃₂は、水素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基及び炭素数１〜２０のシクロアルキル基からなる群から選択される１価の有機基を表す。｝

｛式中、ｒ１９は、それぞれ独立に、０〜２の整数であり、Ｘ₃₃は、それぞれ独立に、水素原子又は下記一般式：

（式中、ｒ２０は、０〜２の整数であり、Ｘ₃₅は、水素原子、アルキル基及びシクロアルキル基からなる群から選択され、そしてｒ２０が２である場合には、２つのＸ₃₅は、互いに同一でも又は異なっていてもよい。）で表される１価の有機基を表し、そしてＸ₃₄は、水素原子、炭素数１〜２０のアルキル基、及び炭素数１〜２０のシクロアルキル基からなる群から選択される。｝

Examples of the compound represented by the general formula (19) include hydroxy compounds represented by the following formulas (24) to (28).

{Wherein, r16 are each independently an integer of 0 to 2, and X ₉ each independently represents a monovalent organic group hydrogen atom or a C 1 to 20, X ₉ is a plurality When present, the plurality of X ₉ may be the same or different from each other, and X ₉ is represented by the following general formula:

(Wherein, the r18, is an integer of 0 to 2, X ₃₁ is a hydrogen atom, an alkyl group, and a monovalent organic radical selected from the group consisting of cycloalkyl, and r18 is 2 In some cases, the two X ₃₁ may be the same or different from each other.)
It is preferable that it is a monovalent organic group represented by these. }

{Wherein X ₃₂ is a monovalent organic group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and a cycloalkyl group having 1 to 20 carbon atoms. Represents. }

{Wherein, r19 are each independently an integer of 0 to 2, X ₃₃ each independently represent a hydrogen atom or the following general formula:

(Wherein, r20 is an integer of 0 to 2, X ₃₅ is a hydrogen atom, alkyl group, and the group consisting of cycloalkyl group and, if r20 is 2, two X ₃₅ is And may be the same or different from each other.), And X ₃₄ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl having 1 to 20 carbon atoms. Selected from the group consisting of groups. }

As a compound represented by the said General formula (24), the sensitivity when the hydroxy compound represented by following formula (29)-(31) is made into NQD thing is high, and in the photosensitive resin composition. This is preferable because of low precipitation.

As the compound represented by the general formula (25), the hydroxy compound represented by the following formula (32) has high sensitivity when made into an NQD compound and has low precipitation in the photosensitive resin composition. This is preferable.

As the compound represented by the general formula (26), the hydroxy compounds represented by the following formulas (33) to (35) have high sensitivity when converted into NQD compounds, and in the photosensitive resin composition. This is preferable because of low precipitation.

で表される構造を有する４価の基であることが好ましい。 In the general formula (20), Z is not particularly limited as long as it is a tetravalent organic group having 1 to 20 carbon atoms, but from the viewpoint of sensitivity, the following formula:

It is preferable that it is a tetravalent group which has a structure represented by these.

Among the compounds represented by the general formula (20), the hydroxy compounds represented by the following formulas (36) to (39) have high sensitivity when converted into NQD compounds, and in the photosensitive resin composition. This is preferable because of its low precipitation.

｛式中、ｒ４０は、それぞれ独立に、０〜９の整数である。｝ As the compound represented by the general formula (21), the hydroxy compound represented by the following formula (40) has high sensitivity when it is an NQD compound and has low precipitation in the photosensitive resin composition. This is preferable.

{In formula, r40 is an integer of 0-9 each independently. }

As the compound represented by the general formula (22), the hydroxy compounds represented by the following formulas (41) and (42) have high sensitivity when converted into NQD compounds, and in the photosensitive resin composition. This is preferable because of low precipitation.

As the compound represented by the general formula (23), specifically, an NQD product of a polyhydroxy compound represented by the following formula (43) is highly sensitive and precipitates in the photosensitive resin composition. It is preferable because of its low nature.

  (C) When the compound having a quinonediazide group has a 1,2-naphthoquinonediazidosulfonyl group, this group is a 1,2-naphthoquinonediazide-5-sulfonyl group or a 1,2-naphthoquinonediazide-4-sulfonyl group. Either may be sufficient. Since the 1,2-naphthoquinonediazide-4-sulfonyl group can absorb the i-line region of a mercury lamp, it is suitable for i-line exposure. On the other hand, the 1,2-naphthoquinonediazide-5-sulfonyl group can absorb even the g-line region of a mercury lamp and is suitable for exposure with g-line.

  In this embodiment, it is preferable to select one or both of 1,2-naphthoquinonediazide-4-sulfonic acid ester compound and 1,2-naphthoquinonediazide-5-sulfonic acid ester compound depending on the wavelength to be exposed. . Further, a 1,2-naphthoquinonediazide sulfonic acid ester compound having a 1,2-naphthoquinonediazide-4-sulfonyl group and a 1,2-naphthoquinonediazide-5-sulfonyl group in the same molecule can be used, A 2-naphthoquinonediazide-4-sulfonic acid ester compound and a 1,2-naphthoquinonediazide-5-sulfonic acid ester compound may be mixed and used.

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

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

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

  In this case, 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. It can also be used by mixing with a sulfonyl ester compound.

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

  (C) In the compound having a quinonediazide group, the average esterification rate of the naphthoquinonediazidesulfonyl ester of the hydroxy compound is preferably 10% to 100%, more preferably 20% to 100%, from the viewpoint of development contrast. Further preferred.

  In embodiment, the compounding quantity of the compound which has (C) quinonediazide group in positive photosensitive resin composition is 0.1 mass part-70 mass parts with respect to 100 mass parts of (A) phenol resin. Preferably, they are 1 mass part-40 mass parts, More preferably, they are 3 mass parts-30 mass parts, More preferably, they are 5 mass parts-30 mass parts. If this compounding amount is 0.1 parts by mass or more, good sensitivity is obtained, while if it is 70 parts by mass or less, the mechanical properties of the cured film are good.

[(D) Solvent]
The positive photosensitive resin composition in the present embodiment can contain a solvent (D) as necessary.

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

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

[Other ingredients]
The photosensitive resin composition of the present invention can contain various additives such as (E) a crosslinking agent, a thermal acid generator, a silane coupling agent, a dye, and a dissolution accelerator, if necessary. .

  (E) The crosslinking agent can be crosslinked with (A) the phenol resin when the relief pattern formed using the photosensitive resin composition of the present invention is heat-cured, or the crosslinking agent itself forms a crosslinked network. A compound that can be used. (E) The crosslinking agent has a structure having two or more crosslinking groups in the molecule, and can further improve the thermal properties, mechanical properties, and reflow treatment applicability of a cured film formed from the photosensitive resin composition. I can do it.

  (E) As a crosslinking agent, for example, Cymel (registered trademark) 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, which is a compound containing a methylol group and / or an alkoxymethyl group, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174; UFR65, 300; Mycoat 102, 105 (Mitsui Cytec Co., Ltd.); Nicalac (registered trademark) MX-270, -280, -290; Nicalac MS-11; Nicalak MW-30, -100, -300, -390, -750 (manufactured by Sanwa Chemical Co., Ltd.), DML-OCHP, DML-MBPC, DML-BPC, DML-PEP, DML-34X, DML-PSBP, DML-PTBP, DML-PCHP, DML-POP, D L-PFP, DML-MBOC, BisCMP-F, DML-BisOC-Z, DML-BisOCHP-Z, DML-BisOC-P, DMOM-PTBT, TMOM-BP, TMOM-BPA, TML-BPAF-MF (above, Honshu Chemical Industry Co., Ltd.), benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis ( Hydroxymethyl) biphenyl, dimethylbis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxy) Methyl) diphenyl ether, bis (methoxymethyl) benzophenone, methoxymethyl benzoate methoxymethyl, bis (methoxymethyl) biphenyl, dimethyl bis (methoxymethyl) biphenyl, and the like.

  Also, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol type epoxy resin, trisphenol type epoxy resin, tetraphenol type epoxy resin, phenol-xylylene type epoxy resin, naphthol-xylylene type epoxy resin, phenol, which are oxirane compounds -Naphthol type epoxy resin, phenol-dicyclopentadiene type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, diethylene glycol diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, 1 , 1,2,2-tetra (p-hydroxyphenyl) ethanetetraglycidyl ether, glycerol triglycidyl Ether, ortho-secondary butylphenyl glycidyl ether, 1,6-bis (2,3-epoxypropoxy) naphthalene, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, YDB-340, YDB-412, YDF-2001, YDF-2004 (Above product name, manufactured by Nippon Steel Chemical Co., Ltd.), NC-3000-H, EPPN-501H, EOCN-1020, NC-7000L, EPPN-201L, XD-1000, EOCN-4600 (above product name, Japan) Manufactured by Kayaku Co., Ltd.), Epicoat (registered trademark) 1001, Epicoat 1007, Epicoat 1009, Epicoat 5050, Epicoat 5051, Epicoat 1031S, Epicoat 180S65, Epicoat 157H70, YX-315-7 (Product name, Japan Epoxy Resin Co., Ltd.), EHPE3150, Plaxel G402, PUE101, PUE105 (Product name, 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 (above 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, Polite 100MF (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), and the like.

  Further, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, 1,3-phenylenebismethylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, takenate (is an isocyanate group-containing compound) (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.

  Further, 4,4′-diphenylmethane bismaleimide, phenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4, which are bismaleimide compounds. '-Diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, 4,4'-diphenyl ether bismaleimide, 4,4' -Diphenylsulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene, BMI-1000, BMI-1100, BMI-2000, BMI-2300, BMI- 3000, BMI-400 , BMI-5100, BMI-7000, BMI-TMH, BMI-6000, BMI-8000 (trade name, manufactured by Daiwa Kasei Kogyo Co., Ltd.), etc. However, it is not limited to these.

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

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

  Examples of the thermal acid generator include a salt formed from a strong acid such as an onium salt having a function of generating an acid by heat and a base, and imide sulfonate.

  Examples of the onium salt include diaryliodonium salts such as aryldiazonium salts and diphenyliodonium salts; di (alkylaryl) iodonium salts such as di (t-butylphenyl) iodonium salts; trialkylsulfonium salts such as trimethylsulfonium salts; Examples thereof include dialkyl monoaryl sulfonium salts such as dimethylphenylsulfonium salt; diarylmonoalkyl iodonium salts such as diphenylmethylsulfonium salt; triarylsulfonium salts and the like.

  Among these, di (t-butylphenyl) iodonium salt of paratoluenesulfonic acid, di (t-butylphenyl) iodonium salt of trifluoromethanesulfonic acid, trimethylsulfonium salt of trifluoromethanesulfonic acid, dimethyl of trifluoromethanesulfonic acid Phenylsulfonium salt, diphenylmethylsulfonium salt of trifluoromethanesulfonic acid, di (t-butylphenyl) iodonium salt of nonafluorobutanesulfonic acid, diphenyliodonium salt of camphorsulfonic acid, diphenyliodonium salt of ethanesulfonic acid, benzenesulfonic acid A dimethylphenylsulfonium salt, a diphenylmethylsulfonium salt of toluenesulfonic acid, and the like are preferable.

  Moreover, as a salt formed from a strong acid and a base, the salt formed from the following strong acids and a base other than the above-mentioned onium salt, for example, a pyridinium salt can also be used. Strong acids include p-toluenesulfonic acid, arylsulfonic acid such as benzenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, perfluoroalkylsulfonic acid such as nonafluorobutanesulfonic acid, methanesulfonic acid, ethanesulfonic acid And alkylsulfonic acid such as butanesulfonic acid. Examples of the base include pyridine, alkylpyridines such as 2,4,6-trimethylpyridine, N-alkylpyridines such as 2-chloro-N-methylpyridine, and halogenated-N-alkylpyridines.

  As the imide sulfonate, for example, naphthoyl imide sulfonate, phthalimide sulfonate, or the like can be used, but it is not limited as long as it is a compound that generates an acid by heat.

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

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

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

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

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

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

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

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

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

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

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

  Next, development can be carried out using a developer by selecting from methods such as dipping, paddle, and rotary spraying. By developing, the exposed portion can be eluted and removed from the applied photosensitive resin layer to obtain a relief pattern.

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

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

  Finally, a cured relief pattern can be obtained by heating the relief pattern thus obtained. The heating temperature is preferably 150 ° C. or higher and 300 ° C. or lower, more preferably 250 ° C. or lower, and further preferably 170 ° C. or higher and 220 ° C. or lower. The positive photosensitive resin composition provided by the present invention has an advantage that sufficient film physical properties (for example, reflow treatment applicability) can be realized even when cured at a low temperature such as the above temperature.

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

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

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

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

Hereinafter, although this embodiment is concretely demonstrated by a synthesis example, an Example, and a comparative example, this invention is not limited to this.
The measurement conditions for each evaluation item are as shown below.

<Tensile elongation measurement>
A sample for measuring elongation according to this embodiment was produced 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 200 ° 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 number 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 shape of cured relief pattern>
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. This coating film was exposed by irradiating an i-line with an exposure dose of 500 mJ / cm ² through a reticle with a test pattern using a stepper NSR2005i8A (Nikon Corp.) having an exposure wavelength of i-line (365 nm). Next, after developing with a developing machine (D-SPIN) at 23 ° C. using a 2.38% tetramethylammonium hydroxide aqueous solution AZ-300MIF (manufactured by AZ Electronic Materials), rinsing with pure water, In a vertical curing furnace VF200B (manufactured by Koyo Thermo System Co., Ltd.), curing was performed at 200 ° C. for 1 hour in a nitrogen atmosphere to obtain a cured relief pattern. The cured pattern was observed with an optical microscope and evaluated according to the following criteria. The results are shown in Table 2.
◯: The 50 μm square relief pattern is maintained without being filled.
X: 50 μm square relief pattern is buried.

<Reflow test>
The photosensitive resin compositions obtained in Examples and Comparative Examples were spin-coated so that the film thickness after curing was about 10 μm, and pre-baked on a hot plate at 120 ° C. for 180 seconds to form a coating film. . The film thickness was measured with a film thickness measuring device, Lambda Ace (manufactured by Dainippon Screen). This coating film was exposed by irradiating an i-line with an exposure amount of 500 mJ / cm ² through a reticle with a test pattern using a stepper NSR2005i8A (manufactured by Nikon Corporation) having an exposure wavelength of i-line (365 nm). Next, it is developed with a developing machine D-SPIN (manufactured by SOKUDO) at 23 ° C. using a 2.38 mass% tetramethylammonium hydroxide aqueous solution AZ-300MIF (manufactured by AZ Electronic Materials) for 100 seconds, and pure water After rinsing, curing was performed at 200 ° C. for 1 hour in a vertical curing furnace VF200B (manufactured by Koyo Thermo System Co., Ltd.) under a nitrogen atmosphere to obtain a cured relief pattern. In Comparative Example 7 which will be described later, the pattern evaluation after the curing relief pattern described above caused pattern breakage after curing, so this reflow test was not performed.

After applying flux WS600 (Cookson Electronics Co., Ltd.) to the resulting cured relief pattern, the wafer with the pattern was reflowed in a reflow furnace 810-II-5Z (Koyo Thermo System Co., Ltd.). The reflow processing conditions were such that the heater temperature and conveyor speed were adjusted and the wafer was heated at 260 ° C. for 30 seconds or longer. After the treatment, washed with water, air-dried, dried in an atmosphere of 23 ° C. and 50% RH for 5 hours or more, and then the appearance of the cured pattern (observed with an optical microscope) and change in film thickness (stylus type step gauge KLA-Tencor P-15) Was measured). The evaluation criteria are as follows. The results are listed in Table 2.
◯: No pattern abnormality occurs and the film thickness change is less than 10%.
(Triangle | delta): Either generation | occurrence | production of pattern abnormality or film reduction or swelling of 10% or more of film thickness changes is seen.
X: Pattern abnormality occurred and film thickness change or swelling of 10% or more was observed.
−: Pattern breakage occurs after curing, and no reflow test is performed {pattern abnormality: pattern crack or pattern surface roughness}

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

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

  Next, the reaction vessel was cooled in the atmosphere, and 100 g of tetrahydrofuran was separately added thereto and stirred. The reaction diluted solution is dropped into 4 L of water under high-speed stirring to disperse and precipitate the resin, which is recovered, appropriately washed with water, dehydrated and then vacuum dried to obtain a copolymer of phloroglucinol / BMMB (phenolic resin). (A-1)) was obtained with a yield of 70%. The weight average molecular weight calculated | required by standard polystyrene conversion of this GPC method of A-1 was 15,000.

  In addition, the weight average molecular weight of resin obtained by each synthesis example was measured on condition of the following using gel permeation chromatography (GPC), and calculated | required the weight average molecular weight in standard polystyrene conversion.

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 LiBr / NMP
Flow rate: 1 ml / min.

[Synthesis Example 2]
<Synthesis of phenol resin (A-2)>
Synthesis was performed in the same manner as in Synthesis Example 1 using 128.3 g (0.76 mol) of methyl 3,5-dihydroxybenzoate instead of phloroglucinol of Synthesis Example 1, and methyl 3,5-dihydroxybenzoate / A copolymer composed of BMMB (phenol resin (A-2)) was obtained with a yield of 65%. The weight average molecular weight calculated | required by standard polystyrene conversion of this GPC method of A-2 was 21,000.

[Synthesis Example 3]
<Synthesis of phenol resin (A-3)>
A separable flask with a Dean-Stark apparatus having a capacity of 1.0 L was purged with nitrogen, and then in the separable flask, 81.3 g (0.738 mol) of resorcinol, 84.8 g (0.35 mol) of BMMB, p-toluenesulfone 3.81 g (0.02 mol) of acid and 116 g of propylene glycol monomethyl ether (hereinafter also referred to as PGME) were mixed and stirred at 50 ° C. to dissolve the solid matter.

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

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

  After completion of the reaction, the same treatment as in Synthesis Example 1 was carried out to obtain a copolymer (phenol resin (A-3)) consisting of resorcinol / BMMB / 2,6-bis (hydroxymethyl) -p-cresol in a yield of 77%. I got it. The weight average molecular weight calculated | required by standard polystyrene conversion of GPC method of this A-3 was 9,900.

[Synthesis Example 4]
<Synthesis of phenol resin (A-5)>
100 parts by mass of phenol, 43 parts by mass of linseed oil and 0.1 part by mass of trifluoromethanesulfonic acid were mixed and stirred at 120 ° C. for 2 hours to obtain a dry oil-modified phenol derivative. Next, 130 g of the above dry oil-modified phenol derivative, 16.3 g of paraformaldehyde and 1.0 g of oxalic acid were mixed and stirred at 90 ° C. for 3 hours to carry out a reaction. Next, after heating up to 120 degreeC and stirring under reduced pressure for 3 hours, the reaction liquid was cooled to room temperature under atmospheric pressure, and the dry oil modified phenol resin (A-5) which is a reaction product was obtained. The weight average molecular weight calculated | required by standard polystyrene conversion of this GPC method of A-5 was 25,000.

[Synthesis Example 5]
<Synthesis of phenol resin (A-6)>
The dry oil-modified phenol derivative (130 g), paraformaldehyde (16.3 g) and oxalic acid (1.0 g) were mixed and stirred at 90 ° C. for 3 hours for reaction. Subsequently, after heating up to 120 degreeC and stirring under reduced pressure for 3 hours, 29 g of succinic anhydride and 0.3 g of triethylamine were added to the reaction liquid, and it stirred at 100 degreeC under atmospheric pressure for 1 hour. The reaction solution was cooled to room temperature to obtain a dry oil-modified phenol resin (A-6) as a reaction product. The weight average molecular weight calculated | required by standard polystyrene conversion of GPC method of this A-6 was 28,000.

[Example 1]
As shown in Table 1, phenol resin (A-1) 100 parts by mass, triazole compound (B-1) 1 part by mass, quinonediazide group-containing compound (C-1) 12 parts by mass, and crosslinking agent (E-1) 5 parts by mass was dissolved in 219 parts by mass of the solvent (D-1) and filtered through a 0.1 μm filter to prepare a positive photosensitive resin composition. The properties of this composition and its cured film were measured according to the evaluation method described above. The obtained results are shown in Table 2.

[Examples 2 to 20]
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 Examples 1 to 7]
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.

  The composition described in Table 1 is as follows.

<(A) Phenolic resin>
A-1: Copolymer composed of phloroglucinol / BMMB, polystyrene equivalent weight average molecular weight (Mw) = 15,000
A-2: Copolymer composed of methyl 3,5-dihydroxybenzoate / BMMB, polystyrene equivalent weight average molecular weight (Mw) = 21,000
A-3: A copolymer comprising resorcinol / BMMB / 2,6-bis (hydroxymethyl) -p-cresol, polystyrene-reduced weight average molecular weight (Mw) = 9,900
A-4: Phenol / biphenylene resin, polystyrene-reduced weight average molecular weight (Mw) = 2,400 (Maywa Kasei Co., Ltd., product name MEH-7851M)
A-5: Compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms (drying oil) modified phenolic resin, polystyrene equivalent weight average molecular weight (Mw) = 25,000
A-6: Compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms (drying oil) modified phenolic resin, polystyrene equivalent weight average molecular weight (Mw) = 28,000
A-7: Novolac resin, polystyrene-equivalent weight average molecular weight (Mw) = 10,600 (product name EP-4080G, manufactured by Asahi Organic Materials Co., Ltd.)

Ｂ−２：

Ｂ−３：

Ｂ−４：

<(B) Triazole compound>
B-1:

B-2:

B-3:

B-4:

（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。） <(C) Compound having quinonediazide group>
C-1: Photoacid generator represented by the following formula:

(Wherein 83% of Q is the following:

The remainder is a hydrogen atom. )

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

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

  As can be seen from the results shown in Table 2, in each example, low temperature curing (200 ° C.) is possible, and the cured film has excellent tensile elongation, and after curing, an excellent relief pattern shape is obtained and cured. Even if a wafer with a relief pattern is subjected to a reflow process, an excellent cured film having no pattern abnormality can be formed. Therefore, according to the present invention, it is possible to provide an interlayer insulating film, a surface protective film, and the like for a semiconductor element 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 (14)

(A) phenol resin: 100 parts by mass,
(B) The following general formula group (1):

{Wherein P ₁ , P ₂ , P ₃ , P ₄ and P ₅ are each independently a hydrogen atom, a hydroxyl group, a mercapto group, an amino group, a carboxyl group, an alkyl group having 1 to 30 carbon atoms, or 1 carbon atom. A group selected from the group consisting of 10 to 10 alkoxy groups, substituted or unsubstituted alicyclic groups having 3 to 30 carbon atoms, substituted or unsubstituted phenyl groups, and substituted or unsubstituted benzyl groups, Here, P ₁ and P ₂ may be condensed to form a substituted or unsubstituted benzene ring or a 6-membered heterocyclic ring having one heteroatom. } At least one triazole compound selected from the group consisting of compounds represented by: 0.1 to 20 parts by mass, and (C) a compound having a quinonediazide group: 0.1 to 70 parts by mass,
A positive photosensitive resin composition comprising:
The (A) phenol resin is
(A1) The following general formula (2):

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

(Wherein p is an integer of 1 to 10) and selected from the group consisting of a divalent alkylene oxide group and a divalent organic group having an aromatic ring having 6 to 20 carbon atoms. Represents a divalent organic group. }, A phenolic resin having a repeating unit represented by:
(A2) Selected from the group consisting of ether bond, hydroxyl group, ester bond, carboxyl group, thioether bond, thiol group, thioester bond, sulfo group, sulfonyl group, urethane bond, urea bond, thiourethane bond, and thiourea bond A phenol resin modified with a compound of 4 to 100 carbon atoms having at least one functional group,
A positive photosensitive resin composition comprising at least one phenol resin selected from the group consisting of: The triazole compound is represented by the following general formula group (4):

{Wherein P ₆ , P ₇ and P ₈ are each independently a hydroxyl group, mercapto group, amino group, carboxyl group, nitro group, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, carbon A group selected from the group consisting of a substituted or unsubstituted alicyclic group, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted benzyl group having 3 to 20, k1, k2 and k3 are each When each independently represents an integer of 0 to 3, and k1, k2 and k3 are each 2 or 3, the plurality of P ₆ , P ₇ and P ₈ may be the same or different from each other, and P ₃ is The same as defined in the general formula group (1). }
The positive photosensitive resin composition of Claim 1 which is at least 1 sort (s) selected from the group which consists of a compound represented by these. The P ₃ is represented by the following general formula (5):

{Wherein h is an integer of 1 to 5 and P ₉ is a hydrogen atom, a hydroxyl group, a carboxyl group, a mercapto group, a linear or branched aliphatic group having 1 to 10 carbon atoms, at least one A linear or branched aliphatic group having 1 to 10 carbon atoms substituted with a hydroxyl group and a linear or branched aliphatic group having 1 to 10 carbon atoms substituted with at least one carboxyl group A monovalent group selected from the group. } And the following general formula (6):

{Wherein i is an integer of 1 to 5 and P ₁₀ and P ₁₁ are each independently substituted with a linear or branched aliphatic group having 1 to 10 carbon atoms, at least one hydroxyl group A monovalent group selected from the group consisting of a linear or branched aliphatic group having 1 to 10 carbon atoms and a linear or branched aliphatic group having 1 to 10 carbon atoms substituted with at least one carboxyl group It is the basis of. } The positive photosensitive resin composition of Claim 1 or 2 which is a monovalent group selected from the group which consists of a monovalent group represented by these. X in the general formula (2) is the following general formula (7):

{Wherein 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 atoms. A substituted monovalent aliphatic group having 1 to 10 carbon atoms, n ₁ is an integer of 0 to 4, and when n ₁ is an integer of ₁ to 4, R ₆ is a halogen atom, or a monovalent organic group having 1 to 12 carbon atoms, more R ₆ may be the same or different from each other when n ₁ is an integer of 2 to 4. } And the following general formula (8):

{Wherein 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 part or all of the hydrogen atoms are substituted with fluorine atoms. Represents a monovalent aliphatic group having 1 to 10 carbon atoms, and W is a single bond, an aliphatic group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, or a fluorine atom. A C3-C20 alicyclic group, the following general formula (3):

(Wherein p is an integer of 1 to 10), and the following formula group (9):

A divalent organic group selected from the group consisting of divalent groups represented by the formula: } The positive photosensitive resin composition as described in any one of Claims 1-3 which is a bivalent organic group selected from the group which consists of a bivalent group represented by these. X in the general formula (2) is the following formula (10):

The positive photosensitive resin composition as described in any one of Claims 1-4 which is a bivalent organic group represented by these. X in the general formula (2) is the following formula (11):

The positive photosensitive resin composition as described in any one of Claims 1-5 which is a bivalent organic group represented by these. The (A) phenol resin is represented by the following general formula (12):

{Wherein R ₁₁ is a monovalent group having 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, n ₂ is 1 to 3, and n ₃ is an integer of 0 to 2. M ₁ is an integer of ₁ to 500, 2 ≦ (n ₂ + n ₃ ) ≦ 4, and when n ₃ is 2, a plurality of R ₁₁ may be the same as or different from each other. . } And the following general formula (13):

{Wherein R ₁₂ and R ₁₃ are each independently a monovalent group having 1 to 10 carbon atoms selected from the group consisting of a hydrocarbon group and an alkoxy group, and n ₄ is an integer of 1 to 3; n ₅ is an integer of 0 to 2, n ₆ is an integer of 0 to 3, m ₂ is an integer of ₁ to 500, 2 ≦ (n ₄ + n ₅ ) ≦ 4, and n ₅ is 2 In this case, the plurality of R ₁₂ may be the same or different from each other, and when n ₆ is 2 or 3, the plurality of R ₁₃ may be the same or different from each other. } The positive photosensitive resin composition as described in any one of Claims 1-6 which is a phenol resin which has both the repeating units represented by} in the same resin frame | skeleton.   The (A) phenol resin contains the (a2) phenol resin, and the (a2) phenol resin has at least one functional group selected from the group consisting of an ester bond and a carboxyl group. The photosensitive resin composition as described in any one of Claims 1-7 which is the phenol resin modified | denatured with the compound.   The (A) phenol resin includes the (a2) phenol resin, and the (a2) phenol resin is selected from the group consisting of unsaturated fatty acids having 4 to 100 carbon atoms and unsaturated fatty acid esters having 4 to 100 carbon atoms. The photosensitive resin composition as described in any one of Claims 1-8 which is the phenol resin modified | denatured with the at least 1 compound.   Furthermore, (E) Crosslinking agent: The photosensitive resin composition as described in any one of Claims 1-9 containing 0.1-40 mass parts. The following steps:
(1) A step of forming a positive photosensitive resin layer containing the positive photosensitive resin composition according to any one of claims 1 to 10 on a substrate,
(2) a step of exposing the positive photosensitive resin layer;
(3) removing the exposed portion with a developer to obtain a relief pattern; and (4) heat-treating the relief pattern;
A method for producing a cured relief pattern.   A cured relief pattern produced by the method according to claim 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 claim 12.   A display body device comprising a display body element and a cured film provided on the display body element, wherein the cured film is the cured relief pattern according to claim 12.