JP6454769B2 - Photosensitive resin composition, method for producing cured relief pattern, semiconductor device and display device - Google Patents

Description

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

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

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

In response to this requirement, Patent Document 1 discloses a composition using a phenol resin obtained by condensing phenols and aldehydes, and crosslinkable fine particles for improving the thermal shock resistance of the phenol resin. Has been proposed. Phenolic resin is a resin that is widely used as a base resin for resists that are temporarily used as a mask in the etching or film formation process when manufacturing semiconductor devices, and does not require the above-described ring closing process, and can be cured at low temperatures. It is excellent in cost and photosensitivity.
Patent Documents 2 and 3 also propose a photosensitive resin composition for a surface protective film and an interlayer insulating film using a phenol resin having a specific structure, and a cured product obtained from such a composition has a temperature of 175 ° C. or 250 ° C. Excellent mechanical properties even when cured at low temperature.

JP 2003-215789 A International Publication No. 2010/073948 Pamphlet International Publication No. 2012/036130 Pamphlet

  When applying a resin film as a permanent film to a semiconductor device, the shape of the cured relief pattern (particularly the cured relief pattern cross-sectional angle (that is, the internal angle formed by the side surface with respect to the formation surface) in the cured relief pattern) is an important film property. One. This is because when the wiring of a semiconductor device having a rectangular cross-sectional shape is covered with a cured relief pattern, the wiring can be covered without any problem if the cross-sectional angle of the relief pattern is large, but if the cross-sectional angle is small, the wiring does not follow the relief pattern, This is because it may be exposed and cause problems. As described above, there is a semiconductor device that is required to have a sufficiently large cross-sectional angle of the cured relief pattern.

  However, the above-mentioned Patent Documents 1 to 3 do not describe the cured relief pattern cross-sectional angle. As a result of studies by the present inventors, there is room for improvement in the sectional angle of the cured relief pattern compared to a cured relief pattern made of polyimide resin or polybenzoxazole resin that has been put to practical use as a semiconductor protective film or insulating film. (See Comparative Examples 1 to 10 described later).

  Therefore, the present invention contains a phenol resin that can be cured at low temperature (for example, curing at 200 ° C.) and can form a cured film that has an excellent cured relief pattern shape (that is, a cured relief pattern has a large cross-sectional angle). PROBLEM TO BE SOLVED: To provide a photosensitive resin composition, a cured relief pattern produced using the photosensitive resin composition, a method for producing the same, and a semiconductor device and a display device having the cured relief pattern as a cured film And

｛式中、Ｐ₁は、単結合であるか、又は、置換基を有していてもよく不飽和結合を有していてもよい炭素数１〜３０のｋ１価の鎖状脂肪族炭化水素基、置換基を有していてもよい炭素数３〜３０のｋ１価の脂環式炭化水素基、及び置換基を有していてもよい炭素数６〜３０の芳香族環を有するｋ１価の有機基、からなる群から選択されるｋ１価の有機基であり、
Ｐ₂は、水素原子であるか、又は、置換基を有していてもよく不飽和結合を有していてもよい炭素数１〜１０の１価の鎖状脂肪族炭化水素基、置換基を有していてもよい炭素数３〜１０の１価の脂環式炭化水素基、及び置換基を有していてもよい炭素数６〜２０の芳香族環を有する１価の有機基、からなる群から選択される１価の有機基であり、複数のＰ₂は、同一でも異なっていてもよく、そして
ｋ１は２〜４の整数である。｝
で表される化合物、及び／又は、
前記一般式（１）で表される化合物の酸無水物を含む、
上記［１］に記載の感光性樹脂組成物。
［３］
前記（Ｂ）化合物が、下記一般式（２）：

｛式中、Ｐ₁は、単結合であるか、又は、置換基を有していてもよく不飽和結合を有していてもよい炭素数１〜３０のｋ１価の鎖状脂肪族炭化水素基、置換基を有していてもよい炭素数３〜３０のｋ１価の脂環式炭化水素基、及び置換基を有していてもよい炭素数６〜３０の芳香族環を有するｋ１価の有機基、からなる群から選択されるｋ１価の有機基であり、そして
ｋ１は２〜４の整数である。｝
で表される化合物を含む、上記［１］又は［２］に記載の感光性樹脂組成物。
［４］
前記（Ｂ）化合物が、下記一般式（３）：

｛式中、Ｐ₃は、置換基を有していてもよく不飽和結合を有していてもよい炭素数１〜３０の（ｋ２×２）価の鎖状脂肪族炭化水素基、置換基を有していてもよい炭素数３〜３０の（ｋ２×２）価の脂環式炭化水素基、及び置換基を有していてもよい炭素数６〜３０の芳香族環を有する（ｋ２×２）価の有機基からなる群から選択される（ｋ２×２）価の有機基であり、
Ｐ₄は、酸素原子であるか、又は、下記一般式（４）：

（Ｐ₅は、水素原子であるか、又は、置換基を有していてもよく不飽和結合を有していてもよい炭素数１〜１０の１価の鎖状脂肪族炭化水素基、置換基を有していてもよい炭素数３〜１０の１価の脂環式炭化水素基、及び置換基を有していてもよい炭素数６〜２０の芳香族環を有する１価の有機基、からなる群から選択される１価の有機基である。）
で表される２価の有機基であり、複数存在する場合のＰ₄は、同一でも異なっていてもよく、そして
ｋ２は１〜２の整数である。｝
で表される化合物を含む、上記［１］に記載の感光性樹脂組成物。
［５］
前記（Ｂ）化合物が、下記一般式（５）：

｛式中、Ｐ₁は、単結合であるか、又は、置換基を有していてもよく不飽和結合を有していてもよい炭素数１〜３０のｋ３価の鎖状脂肪族炭化水素基、置換基を有していてもよい炭素数３〜３０のｋ３価の脂環式炭化水素基、及び置換基を有していてもよい炭素数６〜３０の芳香族環を有するｋ３価の有機基、からなる群から選択されるｋ３価の有機基であり、
Ｐ₆及びＰ₇はそれぞれ独立に、水素原子であるか、又は、置換基を有していてもよく不飽和結合を有していてもよい炭素数１〜１０の１価の鎖状脂肪族炭化水素基、置換基を有していてもよい炭素数３〜１０の１価の脂環式炭化水素基、及び置換基を有していてもよい炭素数６〜１０の芳香族環を有する１価の有機基、からなる群から選択される１価の有機基であり、複数のＰ₆及びＰ₇は、それぞれ同一でも異なっていてもよく、そして
ｋ３は２〜４の整数である。｝
で表される化合物を含む、上記［１］に記載の感光性樹脂組成物。
［６］
前記（Ａ）フェノール樹脂が、ノボラック及びポリヒドロキシスチレン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、上記［１］〜［５］のいずれか一項に記載の感光性樹脂組成物。
［７］
前記（Ａ）フェノール樹脂が、下記一般式（６）：

｛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価の置換基であり、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、そしてＸは、不飽和結合を有していてもよい炭素数２〜１０の２価の鎖状脂肪族炭化水素基、炭素数３〜２０の２価の脂環式炭化水素基、下記一般式（７）：

（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６〜１２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価の有機基である。｝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、上記［１］〜［５］のいずれか一項に記載の感光性樹脂組成物。
［８］
前記（Ａ）フェノール樹脂が前記一般式（６）で表される繰り返し単位を有するフェノール樹脂を含み、前記一般式（６）中のＸが下記一般式（８）：

｛式中、Ｒ₂、Ｒ₃、Ｒ₄及びＲ₅は、各々独立に、水素原子、炭素数１〜１０の１価の脂肪族炭化水素基、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価の脂肪族炭化水素基であり、ｎ₁は０〜４の整数であって、ｎ₁が１〜４の整数である場合のＲ₆は、ハロゲン原子、水酸基、又は炭素数１〜１２の１価の有機基であり、少なくとも１つのＲ₆は水酸基であり、ｎ₁が２〜４の整数である場合の複数のＲ₆は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（９）：

｛式中、Ｒ₇、Ｒ₈、Ｒ₉及びＲ₁₀は、各々独立に、水素原子、炭素数１〜１０の１価の脂肪族炭化水素基、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価の脂肪族炭化水素基であり、Ｗは、単結合、フッ素原子で置換されていてもよい炭素数１〜１０の鎖状脂肪族炭化水素基、フッ素原子で置換されていてもよい炭素数３〜２０の脂環式炭化水素基、下記一般式（７）：

（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（１０）：

で表される２価の基からなる群から選択される２価の基である。｝で表される２価の基からなる群から選択される２価の有機基を含む、上記［７］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一般式（６）で表される繰り返し単位を有するフェノール樹脂を含み、前記一般式（６）中のＸが下記式（１１）：

で表される２価の有機基を含む、上記［７］又は［８］に記載の感光性樹脂組成物。
［１０］
前記（Ａ）フェノール樹脂が、前記一般式（６）で表される繰り返し単位を有するフェノール樹脂を含み、前記一般式（６）中のＸが下記式（１２）：

で表される２価の有機基を含む、上記［７］〜［９］のいずれか一項に記載の感光性樹脂組成物。
［１１］
前記（Ａ）フェノール樹脂が、下記一般式（１３）：

｛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（１４）：

｛式中、Ｒ₁₂及びＲ₁₃は各々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を含む、上記［７］〜［１０］のいずれか一項に記載の感光性樹脂組成物。
［１２］
前記（Ａ）フェノール樹脂１００質量部に対して、前記（Ｂ）化合物０．０１〜２０質量部、及び前記（Ｃ）光酸発生剤０．１〜７０質量部を含有する、上記［１］〜［１１］のいずれか一項に記載の感光性樹脂組成物。
［１３］
前記（Ｃ）光酸発生剤がｏ−キノンジアジド化合物を含む、上記［１］〜［１２］のいずれか一項に記載の感光性樹脂組成物。
［１４］
以下の工程：
（１）上記［１］〜［１３］のいずれか一項に記載の感光性樹脂組成物を含む感光性樹脂層を基板上に形成する工程、
（２）該感光性樹脂層を露光する工程、
（３）現像液により露光部又は未露光部を除去して、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。
［１５］
上記［１４］に記載の方法により製造された、硬化レリーフパターン。
［１６］
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［１５］に記載の硬化レリーフパターンである、半導体装置。
［１７］
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［１５］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]
The following components (A) to (C):
(A) phenolic resin,
(B) a compound having 2 to 150 carbon atoms having at least one functional group selected from the group consisting of a carboxy group, an ester bond, an amide bond, a urethane bond and a urea bond, and a carboxyl group as a molecule. At least one compound selected from the group consisting of acid anhydrides of 2 to 150 carbon atoms having 2 to 4 therein, and (C) a photoacid generator,
A photosensitive resin composition comprising:
[2]
The compound (B) is represented by the following general formula (1):

{In the formula, P ₁ is a single bond or a C1-C30 chain aliphatic hydrocarbon which may have a substituent and may have an unsaturated bond. Group, a C3-C30 k1-valent alicyclic hydrocarbon group which may have a substituent, and a K1-valent having a C6-C30 aromatic ring which may have a substituent A k1-valent organic group selected from the group consisting of:
P ₂ is a hydrogen atom, or a monovalent chain aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent and may have an unsaturated bond, a substituent A monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms which may have a monovalent organic group having an aromatic ring having 6 to 20 carbon atoms which may have a substituent, A plurality of P ₂ may be the same or different, and k1 is an integer of 2 to 4. }
And / or
Including an acid anhydride of the compound represented by the general formula (1),
The photosensitive resin composition as described in [1] above.
[3]
The compound (B) is represented by the following general formula (2):

{In the formula, P ₁ is a single bond or a C1-C30 chain aliphatic hydrocarbon which may have a substituent and may have an unsaturated bond. Group, a C3-C30 k1-valent alicyclic hydrocarbon group which may have a substituent, and a K1-valent having a C6-C30 aromatic ring which may have a substituent A k1-valent organic group selected from the group consisting of: and k1 is an integer of 2-4. }
The photosensitive resin composition as described in said [1] or [2] containing the compound represented by these.
[4]
The compound (B) is represented by the following general formula (3):

{Wherein P ₃ represents a C 1-30 (k2 × 2) -valent chain aliphatic hydrocarbon group which may have a substituent and may have an unsaturated bond, a substituent A (k2 × 2) -valent alicyclic hydrocarbon group having 3 to 30 carbon atoms which may have an aromatic ring having 6 to 30 carbon atoms which may have a substituent (k2 × 2) a (k2 × 2) valent organic group selected from the group consisting of valent organic groups,
P ₄ is an oxygen atom, or the following general formula (4):

(P ₅ is a hydrogen atom or a monovalent linear aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a well-unsaturated bond may have a substituent, a substituted Monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms which may have a group, and monovalent organic group having an aromatic ring having 6 to 20 carbon atoms which may have a substituent And a monovalent organic group selected from the group consisting of
In the case where there are a plurality of organic groups, P ₄ may be the same or different, and k2 is an integer of 1 to 2. }
The photosensitive resin composition as described in said [1] containing the compound represented by these.
[5]
The compound (B) is represented by the following general formula (5):

{Wherein P ₁ is a single bond, or may have a substituent and may have an unsaturated bond, a C1-C30 k 3 -valent chain aliphatic hydrocarbon Group, k3-valent alicyclic hydrocarbon group having 3 to 30 carbon atoms which may have a substituent, and k3-valent having an aromatic ring having 6 to 30 carbon atoms which may have a substituent A trivalent organic group selected from the group consisting of:
P ₆ and P ₇ are each independently a hydrogen atom, or a monovalent chain aliphatic group having 1 to 10 carbon atoms which may have a substituent and may have an unsaturated bond A hydrocarbon group, a monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms which may have a substituent, and an aromatic ring having 6 to 10 carbon atoms which may have a substituent; A monovalent organic group selected from the group consisting of a monovalent organic group, the plurality of P ₆ and P ₇ may be the same or different, and k3 is an integer of 2 to 4. }
The photosensitive resin composition as described in said [1] containing the compound represented by these.
[6]
The photosensitive resin composition according to any one of the above [1] to [5], wherein the (A) phenol resin contains at least one phenol resin selected from the group consisting of novolak and polyhydroxystyrene. .
[7]
The (A) phenol resin is represented by the following general formula (6):

{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. 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 chain aliphatic hydrocarbon group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, General formula (7):

(Wherein p is an integer of 1 to 10), and selected from the group consisting of a divalent alkylene oxide group represented by: and a divalent organic group having an aromatic ring having 6 to 12 carbon atoms. A divalent organic group. } The photosensitive resin composition as described in any one of said [1]-[5] containing the phenol resin which has a repeating unit represented by these.
[8]
Said (A) phenol resin contains the phenol resin which has a repeating unit represented by the said General formula (6), X in the said General formula (6) is following General formula (8):

{Wherein R ₂ , R ₃ , R ₄ and R ₅ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a part or all of the hydrogen atoms are fluorine atoms. in a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms comprising optionally substituted, an integer of n ₁ is 0 to 4, R ₆ where n ₁ is an integer of 1 to 4, the A halogen atom, a hydroxyl group, or a monovalent organic group having 1 to 12 carbon atoms, at least one R ₆ is a hydroxyl group, and a plurality of R _{6 s} when n ₁ is an integer of 2 to 4 may be the same as each other Or they may be different. } And the following general formula (9):

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

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

A divalent group selected from the group consisting of divalent groups represented by the formula: } The photosensitive resin composition as described in said [7] containing the bivalent organic group selected from the group which consists of bivalent group represented by these.
[9]
Said (A) phenol resin contains the phenol resin which has a repeating unit represented by the said General formula (6), X in the said General formula (6) is following formula (11):

The photosensitive resin composition as described in said [7] or [8] containing the bivalent organic group represented by these.
[10]
Said (A) phenol resin contains the phenol resin which has a repeating unit represented by the said General formula (6), X in the said General formula (6) is following formula (12):

The photosensitive resin composition as described in any one of said [7]-[9] containing the bivalent organic group represented by these.
[11]
The (A) phenol resin is represented by the following general formula (13):

{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 (14):

{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 photosensitive resin composition as described in any one of said [7]-[10] containing the phenol resin which has both the repeating units represented by} in the same resin frame | skeleton.
[12]
The above [1], containing 0.01 to 20 parts by mass of the compound (B) and 0.1 to 70 parts by mass of the photoacid generator (C) with respect to 100 parts by mass of the (A) phenol resin. -The photosensitive resin composition as described in any one of [11].
[13]
The photosensitive resin composition according to any one of [1] to [12], wherein the (C) photoacid generator includes an o-quinonediazide compound.
[14]
The following steps:
(1) The process of forming the photosensitive resin layer containing the photosensitive resin composition as described in any one of said [1]-[13] on a board | substrate,
(2) a step of exposing the photosensitive resin layer;
(3) removing exposed or unexposed areas with a developer to obtain a relief pattern; and (4) heat treating the relief pattern;
A method for producing a cured relief pattern.
[15]
A cured relief pattern produced by the method described in [14] above.
[16]
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 [15].
[17]
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 described in [15] above.

  According to the present invention, photosensitivity containing a phenol resin that can be cured at a low temperature (for example, 200 ° C.) and can form a cured film having an excellent cured relief pattern shape (ie, a cured relief pattern having a large cross-sectional angle) It is possible to provide a resin composition, a cured relief pattern produced using the photosensitive resin composition, a production method thereof, and a semiconductor device and a display device having the cured relief pattern as a cured film.

  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.

<Photosensitive resin composition>
The photosensitive resin composition provided by one embodiment of the present invention is:
(A) phenolic resin,
(B) a compound having 2 to 150 carbon atoms having at least one functional group selected from the group consisting of a carboxy group, an ester bond, an amide bond, a urethane bond and a urea bond, and a carboxyl group as a molecule. At least one compound selected from the group consisting of acid anhydrides of 2 to 150 carbon atoms having 2 to 4 therein (also referred to as “(B) compound” in the present disclosure), and (C) photoacid Generator,
Containing. Hereinafter, each component will be described in order. In the present disclosure, among various compounds described as components other than the (B) compound, those included in the definition of the (B) compound are treated as acting also as the (B) compound, (B) It shall also be included in the compounding quantity of a compound.

[(A) Phenolic resin]
The phenol resin in this embodiment means a resin having 50% or more of repeating units having a phenolic hydroxyl group based on all repeating units. (A) The phenolic resin does not undergo structural changes that cause the polyimide precursor to cyclize (imidize) during thermosetting, and therefore can be cured at a low temperature (for example, 250 ° C. or lower, preferably 200 ° C. or lower). Has the advantage.

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 heat resistance of the cured film (glass transition temperature, 5% weight reduction temperature, etc.), while, from the viewpoint of alkali solubility of the photosensitive resin composition, It is preferable that it is 100,000 or less.
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.

｛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価の置換基であり、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、そしてＸは、不飽和結合を有していてもよい炭素数２〜１０の２価の鎖状脂肪族炭化水素基、炭素数３〜２０の２価の脂環式炭化水素基、下記一般式（７）：

（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６〜１２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価の有機基である。｝
で表される繰り返し単位を有するフェノール樹脂、及び炭素数４〜１００の不飽和炭化水素基を有する化合物で変性されたフェノール樹脂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ことが好ましい。（Ａ）フェノール樹脂は、より好ましくは、ノボラック、ポリヒドロキシスチレン、上記一般式（６）で表される繰り返し単位を有するフェノール樹脂、及び炭素数４〜１００の不飽和炭化水素基を有する化合物で変性されたフェノール樹脂から選択される少なくとも１種のフェノール樹脂からなる。 (A) A phenol resin is a novolak, polyhydroxystyrene, following General formula (6) from the viewpoint of the solubility to aqueous alkali solution, the sensitivity and resolution at the time of forming a resist pattern, and the residual stress of a cured film.

{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. 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 chain aliphatic hydrocarbon group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, General formula (7):

(Wherein p is an integer of 1 to 10), and selected from the group consisting of a divalent alkylene oxide group represented by: and a divalent organic group having an aromatic ring having 6 to 12 carbon atoms. A divalent organic group. }
It is preferable to include at least one phenol resin selected from a phenol resin having a repeating unit represented by the formula (1) and a phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms. (A) The phenol resin is more preferably a novolak, polyhydroxystyrene, a phenol resin having a repeating unit represented by the general formula (6), and a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms. It consists of at least 1 type of phenol resin selected from the modified phenol resin.

(Novolac)
In the present disclosure, novolak means all polymers obtained by condensing phenols and formaldehyde in the presence of a catalyst. Generally, a novolak can be obtained by condensing less than 1 mol of formaldehyde with respect to 1 mol of phenols. In the present disclosure, the phenol means a compound having a phenolic hydroxyl group and a derivative thereof. 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.

  The weight average molecular weight of the novolak is preferably 700 to 100,000, more preferably 1,500 to 80,000, still more preferably 2,000 to 50,000. The weight average molecular weight is preferably 700 or more from the viewpoint of heat resistance of the cured film, while it is preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition.

(Polyhydroxystyrene)
In the present disclosure, polyhydroxystyrene means all polymers containing hydroxystyrene as a polymerized unit. Preferable examples of polyhydroxystyrene include polyparavinylphenol. Polyparavinylphenol means all polymers containing paravinylphenol as polymerized units. Accordingly, polymer units other than hydroxystyrene (for example, paravinylphenol) can be used to constitute polyhydroxystyrene (for example, polyparavinylphenol) unless the object of the present invention is contrary. 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 heat resistance. The polymerized units other than hydroxystyrene (for example, paravinylphenol) can be any polymerized unit that can be copolymerized with hydroxystyrene (for example, paravinylphenol). Examples of the copolymer component that gives a polymer unit other than hydroxystyrene (for example, paravinylphenol) include, but are not limited to, methyl acrylate, methyl methacrylate, hydroxyethyl acrylate, butyl methacrylate, octyl acrylate, and 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 Recall 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 Esters of acrylic acid such as methacrylate, 1-phenylethylene-1,2-dimethacrylate, pentaerythritol tetramethacrylate, trimethylolpropane trimethacrylate, 1,5-pentanediol dimethacrylate and 1,4-benzenediol dimethacrylate; Examples include styrene and substituted styrene such as 2-methylstyrene and vinyltoluene; vinyl ester monomers such as vinyl acrylate and vinyl methacrylate; and o-vinylphenol, m-vinylphenol, and the like.

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

  The weight average molecular weight of polyhydroxystyrene is preferably 700 to 100,000, more preferably 1,500 to 80,000, still more preferably 2,000 to 50,000. The weight average molecular weight is preferably 700 or more from the viewpoint of heat resistance of the cured film, while it is preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition.

｛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価の置換基であり、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よく、そしてＸは、不飽和結合を有していてもよい炭素数２〜１０の２価の鎖状脂肪族炭化水素基、炭素数３〜２０の２価の脂環式炭化水素基、下記一般式（７）：

（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６〜１２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価の有機基である。｝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もまた好ましい。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点で特に有利である。フェノール樹脂分子中に存在する上記繰り返し単位は、１種又は２種以上の組合せであることができる。 (Phenol resin having a repeating unit represented by the general formula (6))
In this embodiment, the (A) phenol resin is represented by the following general formula (6):

{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. 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, the plurality of R ₁ may be the same or different from each other And X is a divalent chain aliphatic hydrocarbon group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, Formula (7):

(Wherein p is an integer of 1 to 10), and selected from the group consisting of a divalent alkylene oxide group represented by: and a divalent organic group having an aromatic ring having 6 to 12 carbon atoms. A divalent organic group. It is also preferable to include a phenol resin having a repeating unit represented by: 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. This is particularly advantageous. The repeating unit present in the phenol resin molecule may be one type or a combination of two or more types.

｛式中、Ｒ₁₄、Ｒ₁₅及びＲ₁₆は、各々独立に、水素原子、不飽和結合を有していてもよい炭素数１〜１０の鎖状脂肪族炭化水素基、炭素数３〜２０の脂環式炭化水素基、又は炭素数６〜２０の芳香族炭化水素基であり、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価の鎖状脂肪族炭化水素基、炭素数３〜２０の２価の脂環式炭化水素基、又は炭素数６〜２０の２価の芳香族炭化水素基である。｝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 (6), R ₁ represents a monovalent organic group having 1 to 20 carbon atoms, a halogen atom, a nitro group, and cyano from the viewpoint of reactivity when synthesizing the resin according to the general formula (6). A monovalent substituent selected from the group consisting of groups. R ₁ is a halogen atom, a nitro group, a cyano group, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have an unsaturated bond, or an aromatic group having 6 to 20 carbon atoms from the viewpoint of alkali solubility. A hydrocarbon group and the following general formula (15):

{Wherein R ₁₄ , R ₁₅ and R ₁₆ are each independently a hydrogen atom, a C 1-10 chain aliphatic hydrocarbon group which may have an unsaturated bond, C 3-20 A alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ₁₇ is a divalent chain fatty acid having 1 to 10 carbon atoms which may have an unsaturated bond. An aromatic hydrocarbon group, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 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 (6), a is an integer of 1 to 3, but 2 is preferable from the viewpoint of alkali solubility and the degree of elongation of the cured film. Moreover, when a is 2, the substitution position of hydroxyl groups may be any of ortho, meta, and para positions. When a is 3, the substitution position between the hydroxyl groups may be any of 1,2,3-position, 1,2,4-position, 1,3,5-position, and the like.

  In this embodiment, when a is 1 in the general formula (6), a phenol resin having a repeating unit represented by the general formula (6) (hereinafter referred to as (a1)) in order to improve alkali solubility. A phenolic resin selected from novolak and polyhydroxystyrene (hereinafter also referred to as (a2) resin) can be further mixed with the resin.

  The mixing ratio of the (a1) resin and the (a2) resin is preferably in the range of (a1) / (a2) = 10/90 to 90/10 in mass ratio. This mixing ratio is preferably (a1) / (a2) = 10/90 to 90/10, and (a1) / (a2) = 20 from the viewpoints of solubility in an alkaline aqueous solution and elongation of the cured film. / 80 to 80/20 is more preferable, and (a1) / (a2) = 30/70 to 70/30 is more preferable.

  As the novolak and polyhydroxystyrene as the (a2) resin, the same resins as those described in the above section (Novolak) and (polyhydroxystyrene) can be used.

In the present embodiment, in the general formula (6), b is an integer of 0 to 3, and is preferably 0 or 1 from the viewpoint of alkali solubility and the degree of elongation of the cured film. Moreover, when b is 2 or 3, several R < ₁ > may mutually be same or different.

  Furthermore, in this embodiment, in the general formula (6), a and b satisfy the relationship of 1 ≦ (a + b) ≦ 4.

｛式中、Ｒ₂、Ｒ₃、Ｒ₄及びＲ₅は、各々独立に、水素原子、炭素数１〜１０の１価の脂肪族炭化水素基、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価の脂肪族炭化水素基であり、ｎ₁は０〜４の整数であって、ｎ₁が１〜４の整数である場合のＲ₆は、ハロゲン原子、水酸基、又は炭素数１〜１２の１価の有機基であり、少なくとも１つのＲ₆は水酸基であり、ｎ₁が２〜４の整数である場合の複数のＲ₆は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（９）：

｛式中、Ｒ₇、Ｒ₈、Ｒ₉及びＲ₁₀は、各々独立に、水素原子、炭素数１〜１０の１価の脂肪族炭化水素基、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価の脂肪族炭化水素基であり、Ｗは、単結合、フッ素原子で置換されていてもよい炭素数１〜１０の鎖状脂肪族炭化水素基、フッ素原子で置換されていてもよい炭素数３〜２０の脂環式炭化水素基、下記一般式（７）：

（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（１０）：

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価の有機基を含むことが好ましく、該２価の有機基からなることがより好ましい。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（６）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 (6), X is a C2-C10 bivalent which may have an unsaturated bond from a cured relief pattern shape and the viewpoint of the elongation of a cured film. It has a chain aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, an alkylene oxide group represented by the general formula (7), and an aromatic ring having 6 to 12 carbon atoms. It is a divalent organic group selected from the group consisting of divalent organic groups. Among these divalent organic groups, X represents the following general formula (8) 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 hydrocarbon group having 1 to 10 carbon atoms, or a part or all of the hydrogen atoms are fluorine atoms. in a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms comprising optionally substituted, an integer of n ₁ is 0 to 4, R ₆ where n ₁ is an integer of 1 to 4, the A halogen atom, a hydroxyl group, or a monovalent organic group having 1 to 12 carbon atoms, at least one R ₆ is a hydroxyl group, and a plurality of R _{6 s} when n ₁ is an integer of 2 to 4 may be the same as each other Or they may be different. } And the following general formula (9):

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

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

A divalent organic group selected from the group consisting of divalent groups represented by the formula: } It is preferable to contain the bivalent organic group selected from the group which consists of a bivalent group represented by this, More preferably, it consists of this divalent organic group. 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 (6), 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価の有機基を含むことがより好ましく、さらに下記式（１２）：

で表される２価の有機基を含むことが特に好ましい。 Furthermore, the divalent organic group represented by the general formula (9) is represented by the following formula (11) from the viewpoint of good pattern forming properties of the resin composition and good elongation of the cured film after curing.

It is more preferable that it contains a divalent organic group represented by the following formula (12):

It is especially preferable that the divalent organic group represented by these is included.

  In the structure represented by the general formula (6), X is particularly preferably a structure represented by the formula (11) or (12), and is represented by a structure represented by the formula (11) or (12) in X. The proportion of the portion to be formed is preferably 20% by mass or more, and more preferably 30% by mass or more from the viewpoint of elongation. Although the said ratio may be 100 mass%, from a viewpoint of the alkali solubility of a composition, it is preferable that it is 80 mass% or less, and it is more preferable that it is 70 mass% or less.

｛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は各々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, in the phenol resin which has a structure represented by the said General formula (6), both the structure represented by the following general formula (13) and the structure represented by the following general formula (14) are the same resin frame | skeleton. The structure contained therein is particularly preferable from the viewpoint 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 (13) (14) represents the total number of the respective repeating units in the backbone of the phenolic resin. That is, in the (A) phenol resin, for example, the repeating unit in parentheses in the structure represented by the general formula (13) and the repeating unit in parentheses in the structure represented by the general formula (14) are random. , Blocks or combinations thereof. 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 aqueous alkali 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 preferably from the viewpoint of solubility in an aqueous alkali solution. It is 200 or less, more preferably 175 or less, and still more preferably 150 or less.

In the phenol resin (A) having both the structure represented by the general formula (13) and the structure represented by the general formula (14) in the same resin skeleton, the structure represented by the general formula (13) The higher the molar ratio, the better the film physical properties after curing and the better the heat resistance. On the other hand, the higher the molar ratio of the structure represented by the general formula (14), the better the alkali solubility. Excellent pattern shape after curing. Accordingly, the ratio m ₁ / m ₂ of the structure represented by the general formula (13) to the structure represented by the general formula (14) is preferably 20/80 or more from the viewpoint of film physical properties after curing. More preferably 40/60 or more, particularly preferably 50/50 or more. From the viewpoint of alkali solubility and cured relief pattern shape, it is preferably 90/10 or less, more preferably 80/20 or less, and still more preferably 70 / 30 or less.

The phenol resin having a repeating unit represented by the general formula (6) is typically a phenol and a copolymer component (specifically, a compound having an aldehyde group (an aldehyde compound decomposed like trioxane). 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 compound having two haloalkyl groups in the molecule. One or more compounds selected from the group), and more typically a monomer component comprising these can be synthesized by a polymerization reaction. For example, (A) a phenol resin can be obtained by polymerizing a copolymer component such as an aldehyde compound, a ketone compound, a methylol compound, an alkoxymethyl compound, a diene compound, or a haloalkyl compound with respect to phenols as shown below. . In this case, in the above general formula (6), the moiety represented by the structure in which the OH group and the arbitrary R ₁ group are bonded to the aromatic ring is derived from the phenols, and the moiety 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 (A) phenol resin and photosensitive resin composition, the charged molar ratio of phenols to the above copolymerization component (phenols): (copolymerization component) is 5 : 1 to 1.01: 1 is preferable, and 2.5: 1 to 1.1: 1 is more preferable.

  The weight average molecular weight of the phenol resin having a repeating unit represented by the general formula (6) is preferably 700 to 100,000, more preferably 1,500 to 80,000, and still more preferably 2,000. ~ 50,000. The weight average molecular weight is preferably 700 or more from the viewpoint of heat resistance of the cured film, while it is preferably 100,000 or less from the viewpoint of alkali solubility of the photosensitive resin composition.

  Examples of phenols that can be used to obtain a phenol resin having a repeating unit represented by the general formula (6) include cresol, ethylphenol, propylphenol, butylphenol, amylphenol, cyclohexylphenol, hydroxybiphenyl, 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.

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

  The amount of the catalyst used to obtain the phenol resin having a repeating structure represented by the general formula (6) is the total number of moles of copolymerization components (that is, components other than phenols), preferably aldehyde compounds, ketones 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, methylol compound, alkoxymethyl compound, diene compound and haloalkyl compound.

  When performing the synthetic reaction of the phenol resin which has a repeating structure represented by General formula (6), an organic solvent can be used as needed. Specific examples of organic solvents that can be used include bis (2-methoxyethyl) ether, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, Examples include toluene, xylene, γ-butyrolactone, N-methyl-2-pyrrolidone, but are not limited thereto. The amount of these organic solvents to be used is usually 10 parts by mass to 1000 parts by mass, preferably 20 parts by mass to 500 parts by mass, when the total mass of the charged raw materials is 100 parts by mass. In the synthesis reaction of (A) phenol resin, the reaction temperature is usually preferably 40 ° C to 250 ° C, more preferably 100 ° C to 200 ° C, and the reaction time is approximately 1 hour. 10 hours is preferable.

  In addition, the phenol resin which has a repeating structure represented by General formula (6) is what further polymerized the phenols which do not become a raw material of the structure of the said General formula (6) in the range which does not impair the effect of this invention. It may be. 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 phenols used as a raw material for the (A) phenol resin.

(Phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms)
The phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms is a compound having a phenol and an unsaturated hydrocarbon group having 4 to 100 carbon atoms (hereinafter sometimes referred to simply as “unsaturated hydrocarbon group”). A reaction product (hereinafter also referred to as “unsaturated hydrocarbon group-modified phenol derivative”) and an aldehyde, or a phenol resin and an unsaturated hydrocarbon group-containing compound. It is a reaction product.

  As the phenols, the same materials as those described above as the raw material of the phenol resin having the repeating unit represented by the general formula (6) can be used.

  The unsaturated hydrocarbon group of the unsaturated hydrocarbon group-containing compound preferably contains two or more unsaturated groups from the viewpoint of heat resistance of the cured film. Moreover, from the viewpoint of compatibility when the resin composition is used and the residual stress of the cured film, the unsaturated hydrocarbon group preferably has 4 to 100 carbon atoms, more preferably 8 to 80 carbon atoms, and still more preferably carbon atoms. 10-60.

  Examples of the unsaturated hydrocarbon group-containing compound include unsaturated hydrocarbons having 4 to 100 carbon atoms, polybutadiene having a carboxyl group, unsaturated fatty acids, and unsaturated fatty acid esters. Suitable unsaturated fatty acids from the viewpoint of the flexibility of the cured film include crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, erucic acid, nervonic acid, linoleic acid, α- Examples include 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 preferable from the viewpoints of the degree of elongation of the cured film and the flexibility of the cured film.

  The vegetable oil is usually a non-drying oil containing an ester of glycerin and an unsaturated fatty acid and 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 phenols or phenol resin with 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 between the phenol and the unsaturated hydrocarbon group-containing compound is preferably performed at 50 to 130 ° C. The reaction ratio between the phenol and the unsaturated hydrocarbon group-containing compound is 1 to 100 parts by mass of the unsaturated hydrocarbon group-containing compound with respect to 100 parts by mass of the phenol from the viewpoint of reducing the residual stress of the cured film. Is preferable, and it is more preferable that it is 5-50 mass parts. If the unsaturated hydrocarbon group-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 unsaturated hydrocarbon group-containing compound is produced by polycondensation of an unsaturated hydrocarbon group-modified phenol derivative produced 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 formyl acetate, 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 unsaturated hydrocarbon group-modified phenol derivative 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 the unsaturated hydrocarbon group-containing compound. In the reaction, a solvent such as toluene, xylene, or methanol can be used.

  A phenol resin modified with an unsaturated hydrocarbon group-containing compound can also be obtained by polycondensing the above unsaturated hydrocarbon group-modified phenol derivative with an aldehyde together with a compound other than phenols such as m-xylene. it can. In this case, it is preferable that the charged molar ratio of the compound other than the phenol to the compound obtained by reacting the phenol with the unsaturated hydrocarbon group-containing compound is less than 0.5.

  A phenol resin modified with an unsaturated hydrocarbon group-containing compound can also be obtained by reacting a phenol resin with an unsaturated hydrocarbon group-containing compound. The phenol resin used in this case is a polycondensation product of phenols and aldehydes. In this case, as the phenols and aldehydes, those similar to the above-described phenols and aldehydes can be used, and the phenol resin can be synthesized under the conventionally known conditions as described above.

  Specific examples of phenol resins obtained from phenols and aldehydes suitable for use in forming phenol resins modified with unsaturated hydrocarbon group-containing compounds include phenol / formaldehyde novolac resins and cresol / formaldehyde. Novolak resins, xylyleneol / formaldehyde novolak resins, resorcinol / formaldehyde novolak resins and phenol-naphthol / formaldehyde novolak resins.

  The unsaturated hydrocarbon group-containing compound to be reacted with the phenol resin may be the same as the unsaturated hydrocarbon group-containing compound described above for the production of the unsaturated hydrocarbon group-modified phenol derivative to be reacted with the aldehyde.

  The reaction between the phenol resin and the unsaturated hydrocarbon group-containing compound is usually preferably performed at 50 to 130 ° C. Moreover, the reaction rate of a phenol resin and an unsaturated hydrocarbon group containing compound is an unsaturated hydrocarbon group containing compound 1 with respect to 100 mass parts of phenol resins from a viewpoint of improving the flexibility of a cured film (resist pattern). It is preferable that it is -100 mass parts, It is more preferable that it is 2-70 mass parts, It is still more preferable that it is 5-50 mass parts. If the unsaturated hydrocarbon group-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 curing The heat resistance of the film tends to decrease. In the reaction between the phenol resin and the unsaturated hydrocarbon group-containing compound, p-toluenesulfonic acid, trifluoromethanesulfonic acid, or the like may be used as a catalyst as necessary. 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 further reacting a polybasic acid anhydride with the phenolic hydroxyl group of the phenol resin modified with the unsaturated hydrocarbon 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 aqueous alkali solution (one used as a 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. Polybasic acid anhydrides include, for example, 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, 0.10 to 0.80 mol of polybasic acid anhydride is preferably reacted with 1 mol of phenolic hydroxyl group, more preferably 0.15 to 0.60 mol. 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 molecular weight of the phenol resin modified with the unsaturated hydrocarbon group-containing compound is preferably 1,000 to 100,000 in terms of weight average molecular weight in consideration of solubility in an alkaline aqueous solution and a balance between photosensitive properties and cured film properties. 2,000 to 100,000 are more preferable.

  (A) Among phenol resins, from the viewpoint of the elongation of a cured film, a phenol resin having a repeating unit represented by the general formula (6) (particularly one having a biphenyl structure), and unsaturated having 4 to 100 carbon atoms Phenol resins modified with a compound having a hydrocarbon group (particularly those having a carboxyl group or an ester bond derived from an unsaturated fatty acid or an unsaturated fatty acid ester) are preferred. In the study by the present inventors, specifically, when cured at 200 ° C., the elongation (average value) of the cured film is a phenol resin having a repeating unit represented by the general formula (6) and has a biphenyl structure. And a phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms and having a carboxyl group or an ester bond derived from an unsaturated fatty acid or an unsaturated fatty acid ester, respectively, It was found that the average value was about 20 to 50%, while novolak and polyhydroxystyrene were about 5 to 10% on average. Regarding the mechanism by which a phenol resin having a repeating unit represented by the general formula (6) and a phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms exhibit high elongation. Although it is not certain, it is estimated that the intermolecular interaction acting in / between the polymers is large. That is, the phenol resin having the repeating unit represented by the general formula (6) can have a biphenyl structure in the molecule, and in this case, it is considered that ππ stacking occurs between / in the polymer molecule. On the other hand, a phenol resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms forms a hydrogen bond between a phenolic hydroxyl group and a carboxyl group or ester bond derived from an unsaturated fatty acid or unsaturated fatty acid ester. In this case, it is considered that the inside / between of the polymer molecules are in a pseudo-crosslinked state. These phenomena are presumed to contribute to the development of high elongation of the cured film.

  As (A) phenol resin of this embodiment, phenol modified with the phenol resin which has a repeating unit represented by the said General formula (6), and the said compound which has a C4-C100 unsaturated hydrocarbon group A mixture of at least one phenol resin selected from resins (hereinafter also referred to as (a3) resin) and a phenol resin selected from novolak and polyhydroxystyrene (hereinafter also referred to as (a4) resin) is also preferable. The mixing ratio of the (a3) resin and the (a4) resin is (a3) / (a4) = 5/95 to 95/5 in terms of mass ratio. This mixing ratio is (a3) / (a4) = 5 / 95˜ from the viewpoints of solubility in an aqueous alkali solution, sensitivity and resolution when forming a resist pattern, heat resistance of the cured film, and residual stress. 95/5 is preferable, (a3) / (a4) = 10/90 to 90/10 is more preferable, and (a3) / (a4) = 15/85 to 85/15 is further preferable. As the novolak and polyhydroxystyrene as the (a4) resin, the same resins as those described in the above section (Novolak) and (polyhydroxystyrene) can be used.

[(B) Compound]
In the present embodiment, (B) at least one functional group selected from the group consisting of a carboxy group, an ester bond, an amide bond, a urethane bond, and a urea bond (also referred to as a “hydrogen bond-forming group” in the present disclosure). A compound having 2 to 4 carbon atoms in the molecule and an acid anhydride of the compound having 2 to 4 carbon atoms in the molecule having 2 to 4 carbon atoms. . (B) The hydrogen bond-forming group present in the molecule of the compound may be one type or two or more types.

When the photosensitive resin composition contains the compound (B), the cross-sectional angle of the cured relief pattern can be increased as compared with the case where the compound (B) is not used. The chemical mechanism that increases the cross-sectional angle of the cured relief pattern is not clear, but is considered as follows.
When phenolic resin is used for semiconductor surface protection film applications, the phenolic resin is more prone to pattern sagging during thermal curing than polyimide and polybenzoxazole commonly used in such applications, and the cured relief There is a tendency that the cross-sectional angle of the pattern decreases. This is considered to be because in the case of a phenol resin, a structural change such as cyclization from a polyimide precursor to a polyimide does not occur during thermosetting.

  Even when a thermal crosslinking agent is used as an additive, as the curing starts and heats, the additive that volatilizes before the crosslinking of the crosslinking agent begins to work as a plasticizer, pattern sagging occurs, and the cross-sectional angle Is considered to be smaller.

  On the other hand, when the compound (B) is used, 2 to 4 hydrogen bond-forming groups of the compound in the molecule are phenol resins even in a low temperature region before the crosslinking of the crosslinking agent proceeds. In this state, a hydrogen bond is formed with the hydroxyl group of the resin, and the intramolecular / between molecules of the phenol resin are artificially bridged. For this reason, the fall of the melt viscosity of the photosensitive resin composition is prevented, pattern sagging is suppressed, and it is thought that a cross-sectional angle becomes large.

｛式中、Ｐ₁は、単結合であるか、又は、置換基を有していてもよく不飽和結合を有していてもよい炭素数１〜３０のｋ１価の鎖状脂肪族炭化水素基、置換基を有していてもよい炭素数３〜３０のｋ１価の脂環式炭化水素基、及び置換基を有していてもよい炭素数６〜３０の芳香族環を有するｋ１価の有機基、からなる群から選択されるｋ１価の有機基であり、
Ｐ₂は、水素原子であるか、又は、置換基を有していてもよく不飽和結合を有していてもよい炭素数１〜１０の１価の鎖状脂肪族炭化水素基、置換基を有していてもよい炭素数３〜１０の１価の脂環式炭化水素基、及び置換基を有していてもよい炭素数６〜２０の芳香族環を有する１価の有機基、からなる群から選択される１価の有機基であり、複数のＰ₂は、同一でも異なっていてもよく、そして
ｋ１は２〜４の整数である｝
で表される化合物が好ましく、これらの中でも、組成物のアルカリ溶解性の観点から、下記一般式（２）：

｛Ｐ₁及びｋ１の定義は一般式（１）と同じである。｝
で表される化合物が好ましい。 (B) A compound can contain the C2-C150 compound which has a carboxy group and / or an ester bond 2-4 in a molecule | numerator. As such a compound, from the viewpoint of the cross-sectional angle of the cured pattern, the following general formula (1):

{In the formula, P ₁ is a single bond or a C1-C30 chain aliphatic hydrocarbon which may have a substituent and may have an unsaturated bond. Group, a C3-C30 k1-valent alicyclic hydrocarbon group which may have a substituent, and a K1-valent having a C6-C30 aromatic ring which may have a substituent A k1-valent organic group selected from the group consisting of:
P ₂ is a hydrogen atom, or a monovalent chain aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent and may have an unsaturated bond, a substituent A monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms which may have a monovalent organic group having an aromatic ring having 6 to 20 carbon atoms which may have a substituent, A plurality of P ₂ may be the same or different, and k1 is an integer of 2 to 4}
Of these, the following general formula (2) is preferred from the viewpoint of alkali solubility of the composition:

{Definition of P ₁ and k1 is the same as in the general formula (1). }
The compound represented by these is preferable.

As a specific example of a compound having 2 to 4 ester bonds in the molecule,
(I) Dimethyl succinate, diethyl succinate, dibutyl succinate, dimethyl methyl succinate, diethyl methyl succinate, diisobutyl α-methylglutarate, dibutyl methyl malonate, dimethyl malonate, diethyl malonate, dimethyl ethyl malonate, ethyl malon Diethyl isopropyl, dimethyl isopropylmalonate, diethyl isopropylmalonate, dimethyl butylmalonate, diethyl butylmalonate, dimethyl phenylmalonate, diethyl phenylmalonate, dimethyl diethylmalonate, diethyl diethylmalonate, dimethyl allylmalonate, diethyl allylmalonate , Dimethyl diisobutyl malonate, diethyl diisobutyl malonate, dimethyl dinormal butyl malonate, diethyl dinormal butyl malonate, dimethyl maleate, malein Monooctyl, dioctyl maleate, dibutyl maleate, dibutyl butyl maleate, dimethyl butyl maleate, diethyl butyl maleate, diisopropyl β-methyl glutarate, diallyl ethyl succinate, di-2-ethylhexyl fumarate, dimethyl itaconate, itacon Aliphatic polycarboxylic acid esters such as diethyl acid, dibutyl itaconate, dioctyl citraconic acid, dimethyl citraconic acid,

(B) Dimethyl 1,2-cyclohexanecarboxylate, diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, dimethyl tetrahydrophthalate, diethyl tetrahydrophthalate, dimethyl nadic acid, diethyl nadic acid Aliphatic polycarboxylic acid esters,

(C) (o-, m-, p-) monomethyl phthalate, (o-, m-, p-) monoethyl phthalate, (o-, m-, p-) dimethyl phthalate, (o-, m -, P-) methyl ethyl phthalate, (o-, m-, p-) monoisobutyl phthalate, (o-, m-, p-) mono-normal butyl phthalate, (o-, m-, p-) ) Dimethyl phthalate, (o-, m-, p-) diethyl phthalate, (o-, m-, p-) ethyl isobutyl phthalate, (o-, m-, p-) ethyl normal butyl phthalate, (O-, m-, p-) di-n-propyl phthalate, (o-, m-, p-) diisopropyl phthalate, (o-, m-, p-) di-n-butyl phthalate, (o -, M-, p-) diisobutyl phthalate, (o-, m-, p-) di-n-heptyl phthalate, (o-, m-, p-) Di-2-ethylhexyl phthalate, di-n-octyl (o-, m-, p-) phthalate, dineopentyl (o-, m-, p-) phthalate, (o-, m-, p-) phthalic acid Didecyl, (o-, m-, p-) benzylbutyl phthalate, (o-, m-, p-) diphenyl phthalate, dimethyl naphthalene dicarboxylate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate , Aromatic polycarboxylic acid esters such as dibutyl trimellitic acid,

(D) Different carbon polycarboxylic acid esters such as 3,4-furandicarboxylic acid.

  Among these, from the viewpoint of the cross-sectional angle of the cured pattern, esters of alcohols with one or more selected from succinic acid, phthalic acid, maleic acid, and malonic acid are preferable. These compounds are used alone or in combination of two or more. In the present disclosure, the compound having 2 to 4 ester bonds in the molecule and having 2 to 150 carbon atoms is not a polymer, that is, a polyester that is a polymer formed by bonding a plurality of monomers by ester bonds. Intended to be removed.

  Specific examples of the compound having 2 to 4 carboxy groups in the molecule include succinic acid, oxalic acid, adipic acid, sebacic acid, 1,10-decanedicarboxylic acid, dodecanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid. 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, 1,3-dicarboxymethylcyclohexane, (o-, m-, p-) phthale Acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, sodium 3-sulfoisophthalate, azelaic acid, methylsuccinic acid, octyl Succinic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid 2,6-naphthalenedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, decamethylene carboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-diphenyl sulfone dicarboxylic acid, 4,4′-diphenyl dicarboxylic acid, Malonic acid, methylmalonic acid, dimethylmalonic acid, glutaric acid, α-ketoglutaric acid, 3-methylglutaric acid, pimelic acid, citraconic acid, mesaconic acid, oxaloacetic acid, tartaric acid, tetrahydroxybutanedioic acid, aspartic acid, 1, 1-cyclopropanedicarboxylic acid, glutamic acid, 1-carboxyglutamic acid, aconitic acid, citric acid, isocitric acid, 3,5-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, quinolinic acid, suberic acid, homocysteine, glutathione, 1,2,4-trimetic acid, 1,2,4-naphthalene tricarboxylic acid, 1,2,5-naphthalene tricarboxylic acid, 1,4,5-naphthalene tricarboxylic acid, 2,5,7-naphthalene tricarboxylic acid, 2,6,7-naphthalene tricarboxylic acid, 3,3 ′, 4-diphenyltricarboxylic acid, benzophenone-3,3 ′, 4-tricarboxylic acid, diphenylsulfone-3,3 ′, 4-tricarboxylic acid, diphenylether-3,3 ′, 4-tricarboxylic acid, 2,5-hexanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, benzophenone-2,4,5-tricarboxylic acid, 3,3,4'-benzophenonetricarboxylic acid, 3,4,4'-benzophenonetricarboxylic acid 2,3,4'-diphenyltricarboxylic acid, 2,3,6-pyridinetricarboxylic acid, 3, , 4′-Benzanilide tricarboxylic acid, 1,4,5-naphthalene tricarboxylic acid, 2′-methoxy-3,4,4′-diphenyl ether tricarboxylic acid, 2′-chlorobenzanilide-3,4,4′-tricarboxylic acid Acid, glycolic acid, lactic acid, glyceric acid, tartronic acid, malic acid, toluenticarboxylic acid, 4-neopentirizonyl-1,2,6,7-heptanetetracarboxylic acid, 3-methyl-4-heptenyl-1, 2,5,6-hexanetetracarboxylic acid, 3-methyl-3-heptyl-5-methyl-1,2,6,7-heptene (4) -tetracarboxylic acid, 3-nonyl-4-methylidonyl-1, 2,5,6-hexanetetracarboxylic acid, 3-decylisonyl-1.2,5.6-hexanetetracarboxylic acid, 3-nonyl-1,2,6,7- Putene (4) -tetracarboxylic acid, 3-decynyl-1,2,5,6-hexanetetracarboxylic acid, 3-butyl-3-ethylenyl-1,2,5,6-hexanetetracarboxylic acid, 3-methyl -4-butyridonyl-1,2,6,7-heptanetetracarboxylic acid, 3-methyl-4-butyl-1,2,6,7-heptene (4) -tetracarboxylic acid, 3-methyl-5 Octyl-1,2,6,7-heptene (4) -tetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, butanetetracarboxylic acid, hexahydrophthalic acid, cyclopentanetetracarboxylic acid, tetrahydrophthal Acid, tetrachlorophthalic acid, 1,20-eicosane dicarboxylic acid, 1,24-tetraeicosane dicarboxylic acid, glutaconic acid, 12-hydroxystearic acid, etc. Is mentioned. Among these, succinic acid, malonic acid, fumaric acid, malic acid, phthalic acid, 1,2-cyclohexanedicarboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid from the viewpoint of the sectional angle of the cured pattern and the cost. Acid trimellitic acid, pyromellitic acid, and trimesic acid are preferred. These compounds are used alone or in combination of two or more.

｛式中、Ｐ₃は、置換基を有していてもよく不飽和結合を有していてもよい炭素数１〜３０の（ｋ２×２）価の鎖状脂肪族炭化水素基、置換基を有していてもよい炭素数３〜３０の（ｋ２×２）価の脂環式炭化水素基、及び置換基を有していてもよい炭素数６〜３０の芳香族環を有する（ｋ２×２）価の有機基からなる群から選択される（ｋ２×２）価の有機基であり、
Ｐ₄は、酸素原子であるか、又は、下記一般式（４）：

（Ｐ₅は、水素原子であるか、又は、置換基を有していてもよく不飽和結合を有していてもよい炭素数１〜１０の１価の鎖状脂肪族炭化水素基、置換基を有していてもよい炭素数３〜１０の１価の脂環式炭化水素基、及び置換基を有していてもよい炭素数６〜２０の芳香族環を有する１価の有機基、からなる群から選択される１価の有機基である。）
で表される２価の有機基であり、複数存在する場合のＰ₄は、同一でも異なっていてもよく、そして
ｋ２は１〜２の整数である｝
で表される化合物が好ましい。 As an acid anhydride of a compound having 2 to 4 carbon atoms having 2 to 4 carboxy groups in the molecule, the following general formula (3):

{Wherein P ₃ represents a C 1-30 (k2 × 2) -valent chain aliphatic hydrocarbon group which may have a substituent and may have an unsaturated bond, a substituent A (k2 × 2) -valent alicyclic hydrocarbon group having 3 to 30 carbon atoms which may have an aromatic ring having 6 to 30 carbon atoms which may have a substituent (k2 × 2) a (k2 × 2) valent organic group selected from the group consisting of valent organic groups,
P ₄ is an oxygen atom, or the following general formula (4):

(P ₅ is a hydrogen atom or a monovalent linear aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a well-unsaturated bond may have a substituent, a substituted Monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms which may have a group, and monovalent organic group having an aromatic ring having 6 to 20 carbon atoms which may have a substituent And a monovalent organic group selected from the group consisting of
In the case where there are a plurality of organic groups, P ₄ may be the same or different, and k2 is an integer of 1 to 2}
The compound represented by these is preferable.

  (B) A compound can contain the acid anhydride of the compound which has 2-4 carboxy groups in a molecule | numerator. Specific examples of the acid anhydride of the compound having 2 to 4 carboxy groups in the molecule include the acid anhydrides of specific examples of the compound having 2 to 4 carboxy groups in the molecule. More specifically, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, pentadodecenyl succinic anhydride, octenyl succinic anhydride, tricarbanilic anhydride, maleic anhydride , Hymic acid anhydride, nadic acid anhydride, cis-4-cyclohexene-1,2-dicarboxylic acid anhydride, 1,2-cyclohexanedicarboxylic acid anhydride, norbornene anhydride, 1,2,3,4-butanetetra Carboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, trimellitic anhydride, pyromellitic Acid dianhydride, benzophenone tetracarboxylic dianhydride, nadic acid anhydride, 3,6- Dimethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, 4, 4'-oxydiphthalic anhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, etc. are mentioned. Among these, from the viewpoint of the cross-section angle of the cured pattern and the cost, maleic anhydride, succinic anhydride, phthalic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, 1,2- Cyclohexanedicarboxylic acid anhydride, trimellitic acid anhydride, 4,4′-oxydiphthalic acid anhydride, and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride are preferred. These compounds are used alone or in combination of two or more.

｛式中、Ｐ₁は、単結合であるか、又は、置換基を有していてもよく不飽和結合を有していてもよい炭素数１〜３０のｋ３価の鎖状脂肪族炭化水素基、置換基を有していてもよい炭素数３〜３０のｋ３価の脂環式炭化水素基、及び置換基を有していてもよい炭素数６〜３０の芳香族環を有するｋ３価の有機基、からなる群から選択されるｋ３価の有機基であり、
Ｐ₆及びＰ₇はそれぞれ独立に、水素原子であるか、又は、置換基を有していてもよく不飽和結合を有していてもよい炭素数１〜１０の１価の鎖状脂肪族炭化水素基、置換基を有していてもよい炭素数３〜１０の１価の脂環式炭化水素基、及び置換基を有していてもよい炭素数６〜１０の芳香族環を有する１価の有機基、からなる群から選択される１価の有機基であり、複数のＰ₆及びＰ₇は、それぞれ同一でも異なっていてもよく、そして
ｋ３は２〜４の整数である｝
で表される化合物、及び／又は、
下記一般式（３）：

｛式中、Ｐ₃は、置換基を有していてもよく不飽和結合を有していてもよい炭素数１〜３０の（ｋ２×２）価の鎖状脂肪族炭化水素基、置換基を有していてもよい炭素数３〜３０の（ｋ２×２）価の脂環式炭化水素基、及び置換基を有していてもよい炭素数６〜３０の芳香族環を有する（ｋ２×２）価の有機基からなる群から選択される（ｋ２×２）価の有機基であり、
Ｐ₄は、酸素原子であるか、又は、下記一般式（４）：

（Ｐ₅は、水素原子であるか、又は、置換基を有していてもよく不飽和結合を有していてもよい炭素数１〜１０の１価の鎖状脂肪族炭化水素基、置換基を有していてもよい炭素数３〜１０の１価の脂環式炭化水素基、及び置換基を有していてもよい炭素数６〜２０の芳香族環を有する１価の有機基、からなる群から選択される１価の有機基である。）
で表される２価の有機基であり、複数存在する場合のＰ₄は、同一でも異なっていてもよく、そして
ｋ２は１〜２の整数である。｝
において、Ｐ₄が上記一般式（４）で表される基である化合物であることが好ましい。 (B) A compound can contain a C2-C150 compound which has 2-4 amide bonds in a molecule | numerator. A compound having 2 to 150 carbon atoms having 2 to 4 amide bonds in the molecule is represented by the following general formula (5) from the viewpoint of the cross-sectional angle of the cured pattern:

{Wherein P ₁ is a single bond, or may have a substituent and may have an unsaturated bond, a C1-C30 k 3 -valent chain aliphatic hydrocarbon Group, k3-valent alicyclic hydrocarbon group having 3 to 30 carbon atoms which may have a substituent, and k3-valent having an aromatic ring having 6 to 30 carbon atoms which may have a substituent A trivalent organic group selected from the group consisting of:
P ₆ and P ₇ are each independently a hydrogen atom, or a monovalent chain aliphatic group having 1 to 10 carbon atoms which may have a substituent and may have an unsaturated bond A hydrocarbon group, a monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms which may have a substituent, and an aromatic ring having 6 to 10 carbon atoms which may have a substituent; A monovalent organic group selected from the group consisting of a monovalent organic group, wherein a plurality of P ₆ and P ₇ may be the same or different, and k3 is an integer of 2 to 4}
And / or
The following general formula (3):

{Wherein P ₃ represents a C 1-30 (k2 × 2) -valent chain aliphatic hydrocarbon group which may have a substituent and may have an unsaturated bond, a substituent A (k2 × 2) -valent alicyclic hydrocarbon group having 3 to 30 carbon atoms which may have an aromatic ring having 6 to 30 carbon atoms which may have a substituent (k2 × 2) a (k2 × 2) valent organic group selected from the group consisting of valent organic groups,
P ₄ is an oxygen atom, or the following general formula (4):

(P ₅ is a hydrogen atom or a monovalent linear aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a well-unsaturated bond may have a substituent, a substituted Monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms which may have a group, and monovalent organic group having an aromatic ring having 6 to 20 carbon atoms which may have a substituent And a monovalent organic group selected from the group consisting of
In the case where there are a plurality of organic groups, P ₄ may be the same or different, and k2 is an integer of 1 to 2. }
In the above, it is preferable that P ₄ is a compound represented by the general formula (4).

  Specific examples of the compound having 2 to 4 carbon atoms having 2 to 4 amide bonds in the molecule include the carboxylic acid mentioned above as an example of the compound having 2 to 4 carboxy groups in the molecule and an amine. The compound produced | generated by the dehydration condensation reaction is mentioned. The amine can be at least one amine selected from ammonia, aliphatic amines (saturated and / or unsaturated, optionally having a branched structure), and aromatic amines. Specifically, (o-, m-, p-) phthalic acid diamide, (o-, m-, p-) phthalic acid dianilide, trimellitic acid triamide, trimellitic acid trianilide, pyromellitic acid tetraamide, pyromellitic Acid tetraanilide, naphthalenedicarboxylic acid amide, naphthalenedicarboxylic acid anilide, oxalic acid diamide, oxalic acid dianilide, maleic acid diamide, maleic acid dianilide, malonic acid diamide, malonic acid dianilide, fumaric acid diamide, fumaric acid dianilide, succinic acid diamide, Succinic acid dianilide, itaconic acid dianilide, glutaric acid diamide, glutaric acid dianilide, adipic acid diamide, adipic acid dianilide, trimesic acid triamide, trimesic acid trianilide, citric acid triamide, citric acid trianilide, adivic acid Amides, adibic acid dianilide, suberic acid diamide, suberic acid dianilide, sebacic acid diamide, sebacic acid dianilide, tetradecanedicarboxylic acid diamide, tetradecanedicarboxylic acid dianilide, octadecanedicarboxylic acid diamide, octadecanedicarboxylic acid dianilide, 6-ethylhexadecanedicarboxylic acid diamide, 6-ethylhexadecanedicarboxylic acid dianilide, toluenedicarboxylic acid diamide, toluenedicarboxylic acid dianilide, 4,4'-diphenylmethane diamide, 4,4'-diphenylmethane dianilide, benzenetricarboxylic acid triamide, benzenetricarboxylic acid trianilide, 2,5-thiophene Dicarboxylic acid diamide, 2,5-thiophenedicarboxylic acid dianilide, 1,2-cyclohexanedicarboxylic acid Amide, 1,2-cyclohexanedicarboxylic acid anilide, and the like.

  Among these, from the viewpoint of the cross-section angle and cost of the cured pattern, succinic acid diamide, succinic acid dianilide, 1,2-cyclohexanedicarboxylic acid amide, p-phthalic acid amide, p-phthalic acid anilide, trimellitic acid triamide, and pyro Mellitic acid tetraamide is preferred. These compounds are used alone or in combination of two or more. In the present disclosure, the compound having 2 to 4 carbon atoms having 2 to 4 amide bonds in the molecule is not a polymer, that is, a polyamide which is a polymer formed by bonding a plurality of monomers by amide bonds Intended to be removed.

  (B) A compound can contain a C2-C150 compound which has a urethane bond 2-4 in a molecule | numerator. Specific examples of the compound having 2 to 4 urethane bonds in the molecule include diurethane compounds, triurethane compounds, and tetraurethane compounds. The urethane compound is synthesized by reacting alcohol and isocyanate.

  Examples of the diutane compound include a reaction product of a monoalcohol and a dissocyanate. The monoalcohol can be a chain aliphatic alcohol, an alicyclic alcohol and / or an aromatic alcohol. Examples of the monoalcohol used include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, benzyl alcohol, and cyclohexanol. Examples of the dissocyanate compound used include aliphatic dissocyanates, alicyclic dissocyanates, and aromatic dissocyanates. For example, 4,4′-diphenylmethane disocyanate (MDI), tolylene diisocyanate (TDI). , Naphthalenediocyanate, p-phenylene disocyanate, trans-1,4-cyclohexane disocyanate (CHDI), 1,3-bis- (isocyanatomethyl-benzene), 4,4′-dicyclohexylmethane disocyanate (H12MDI) 1,3-bis- (isocyanatomethyl) -cyclohexane (H6XDI), hexamethylene disociate (HDI), 3-isocyanatomethyl-3,3,5′-trimethylcyclohexyl isocyanate (IPDI), phenylene disocyanate Examples include m-tetramethylxylene disoocyanate (m-TMXDI) and p-tetramethylxylene disoocyanate (p-TMXDI), and in particular, 4,4′-diphenylmethane disoocyanate (MDI) and tolylene diisocyanate (TDI). , Trans-1,4-cyclohexanedisociate (CHDI), and 4,4′-dicyclohexylmethane disocyanate (H12MDI) are preferred.

  Among these, a diurethane compound is preferable from the viewpoint of the cross-sectional angle of the cured pattern. These compounds are used alone or in combination of two or more. In the present disclosure, the compound having 2 to 4 carbon atoms having 2 to 4 urethane bonds in the molecule is not a polymer, that is, a polyurethane which is a polymer formed by bonding a plurality of monomers by urethane bonds. Intended to be removed.

  The compound (B) can include a compound having 2 to 150 carbon atoms having 2 to 4 urea bonds in the molecule. Examples of the compound having 2 to 4 carbon atoms having 2 to 4 urea bonds in the molecule include diurea compounds, triurea compounds, and tetraurea compounds.

  Examples of the diurea compound include a reaction product of a monoamine and a dissocyanate. The monoamine can be an aliphatic amine, an alicyclic amine and / or an aromatic amine. Examples of the monoamine used include octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, oleylamine, aniline, p-toluidine, cyclohexylamine and the like. Further, the disocyanate compound used and preferred examples thereof are the same as those described above as the disociocyanate compound used for the synthesis of the diurethane compound.

  The triurea compound is composed of 2 moles of chain aliphatic, alicyclic or aromatic dissocyanate, 1 mole of chain aliphatic, alicyclic or aromatic diamine, and chain aliphatic, alicyclic or aromatic. A reaction product of 1 mol of an amine and 1 mol of a chain aliphatic, alicyclic or aromatic alcohol. In a base oil, the above compounds are mixed in the above proportions and reacted. Can be obtained.

  Among these, a diurea compound is preferable from the viewpoint of the cross-sectional angle of the cured pattern. These compounds are used alone or in combination of two or more. In the present disclosure, the compound having 2 to 4 urea bonds in the molecule and having 2 to 4 carbon atoms is not a polymer, that is, polyurea which is a polymer formed by bonding a plurality of monomers by urea bonds. Intended to be removed.

  Among the compounds (B), from the viewpoint of the cross-sectional angle of the cured pattern, the compound having 2 to 150 carbon atoms having at least one functional group selected from the group consisting of a carboxy group, an ester bond and an amide bond in the molecule. The compound and at least one compound selected from an acid anhydride of a compound having 2 to 4 carbon atoms having 2 to 4 carboxy groups in the molecule are preferred. From the viewpoint of alkali solubility of the composition, the carboxy group is 2 to 4 compounds having 2 to 4 carbon atoms and at least one compound selected from acid anhydrides of 2 to 150 carbon compounds having 2 to 4 carboxy groups in the molecule are more preferable.

  (B) The compounding quantity of a compound becomes like this. Preferably it is 0.01-20 mass parts with respect to 100 mass parts of (A) phenol resin, More preferably, it is 0.05-10 mass parts, More preferably, it is 0.00. 1 to 5 parts by mass, most preferably 0.5 to 3 parts by mass. When the blending amount is 0.01 parts by mass or more, the effect of increasing the cross-sectional angle of the cured pattern is good. On the other hand, when it is 20 parts by mass or less, the composition has excellent storage stability (that is, during storage). The rate of change in viscosity over time is small). In particular, when the amount of compound (B) is large, it is considered that compound (B) serves as a catalyst, and the phenol resin raw material monomer or oligomer remaining in the composition polymerizes and thickens. In light of avoiding this polymerization well, the amount of the compound (B) is particularly preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and still more preferably 3 parts by mass or less. (B) When the compounding quantity of a compound is 3 mass parts or less, especially advantageous effects are acquired at the point of the said storage stability.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  In this embodiment, when the photosensitive resin composition is a negative type, the blending amount of the (C) photoacid generator with respect to 100 parts by mass of the (A) phenol resin is 0.1 to 70 parts by mass. Preferably, it is 1-40 mass parts. If the blending amount is 0.1 parts by mass or more, the sensitivity improvement effect can be obtained satisfactorily. If the blending amount is 70 parts by mass or less, the mechanical properties of the cured film are good.

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

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

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

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

｛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。｝。

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

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

Further, as the NQD compound, a naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule can be used, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl group. A mixture with an ester compound can also be used.
The NQD compounds may be used alone or in combination of two or more.

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

[solvent]
The photosensitive resin composition in this embodiment can contain a solvent as needed.
Examples of the solvent 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, tetramethyl urea, 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 dimethyl Use 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. Can do. Among them, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene from the viewpoints of resin solubility, resin composition stability, and adhesion to a substrate. Glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenyl glycol, and tetrahydrofurfuryl alcohol are preferred.

  In the photosensitive resin composition of the present invention, the amount of the solvent 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. Preferably it is the range of 125-500 mass parts.

[Additive]
The photosensitive resin composition of the present invention can contain various additives such as a cross-linking agent, a thermal acid generator, a silane coupling agent, a dye, and a dissolution accelerator, if necessary.

  When the relief pattern formed using the photosensitive resin composition of the present invention is heat-cured, the crosslinking agent can be crosslinked with (A) the phenol resin, or the crosslinking agent itself can form a crosslinked network. Refers to a compound. The crosslinking agent has a structure having two or more crosslinking groups in the molecule, and can further improve the thermal properties and mechanical properties of a cured film formed from the photosensitive resin composition.

  Examples of the crosslinking agent include Cymel (registered trademark) 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, which are compounds containing a methylol group and / or an alkoxymethyl group. , 202, 1156, 1158, 1123, 1170, 1174; UFR65, 300; My Coat 102, 105 (Mitsui Cytec Co., Ltd.); Nicalac (registered trademark) MX-270, -280, -290; Nicalac MS-11 Nicalak MW-30, -100, -300, -390, -750 (above, manufactured by Sanwa Chemical Co., Ltd.), DML-OCHP, DML-MBPC, DML-BPC, DML-PEP, DML-34X, DML-PSBP , DML-PTBP, DML-PCHP, DML-POP, DML- FP, DML-MBOC, BisCMP-F, DML-BisOC-Z, DML-BisOCHP-Z, DML-BisOC-P, DMOM-PTBT, TMOM-BP, TMOM-BPA, TML-BPAF-MF (Honshu Chemical) Manufactured by Kogyo 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 (methoxymethyl) ) 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, chain 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 triglyceride Dil ether, ortho secondary butyl phenyl glycidyl ether, 1,6-bis (2,3-epoxypropoxy) naphthalene, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, YDB-340, YDB-412, YDF-2001, YDF- 2004 (trade name, manufactured by Nippon Steel Chemical Co., Ltd.), NC-3000-H, EPPN-501H, EOCN-1020, NC-7000L, EPPN-201L, XD-1000, EOCN-4600 (trade name, Nippon Kayaku Co., Ltd.), Epicoat (registered trademark) 1001, Epicoat 1007, Epicoat 1009, Epicoat 5050, Epicoat 5051, Epicoat 1031S, Epicoat 180S65, Epicoat 157H70, YX-315 75 (above trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EHPE3150, Plaxel G402, PUE101, PUE105 (above trade name, manufactured by Daicel Chemical Industries, Ltd.), Epicron (registered trademark) 830, 850, 1050, N- 680, N-690, N-695, N-770, HP-7200, HP-820, EXA-4850-1000 (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) 70 P, Epolite 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.

  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 The degree is good.

  On the other hand, in another preferred embodiment, the photosensitive resin composition may not contain a crosslinking agent. In the present embodiment, by using the compound (B), it is possible to obtain a good cured relief pattern sectional angle even when, for example, a crosslinking agent is not used.

  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 diaryl iodonium 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 (Azmax Co., Ltd .: product name SLA0599.1) Aminophenyltrimethoxysilane (Azmax 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, isobutylmethylphenol Lucilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n- Examples include, but are not limited to, propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol, and the like. These may be used alone or in combination.

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

  As a compounding quantity in the case of using a silane coupling agent, 0.01-20 mass parts is preferable with respect to 100 mass parts of (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 phenols such as MtrisPC and MtetraPC, TrisP-HAP, TrisP -Non-linear phenols such as PHBA and TrisP-PA (all manufactured by Honshu Chemical Industry Co., Ltd.), 2-5 phenol substitutes of diphenylmethane, 1-5 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-cyclohexyl Examples include compounds obtained by reacting carboxylic anhydrides with a molar ratio of 1: 2, N-hydroxysuccinimide, N-hydroxyphthalimide, N-hydroxy 5-norbornene-2,3-dicarboxylic imide, and the like. It is done. 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.

<Manufacture of photosensitive resin composition>
The photosensitive resin composition of this embodiment includes, for example, the above-mentioned (A) phenol resin, (B) compound, and (C) photoacid generator, and optionally, one or more of the above-mentioned additives. It can manufacture by the method including adding and making it melt | dissolve. Here, the preferable compounding quantity of each component is as above-mentioned.

<Method for producing cured relief pattern>
Another aspect of this 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 step of removing a exposed portion (in the case of a positive type) or an unexposed portion (in the case of a negative type) with a developer to obtain a relief pattern, and (4) a curing step including a step of heat-treating the relief pattern. A method for producing a relief pattern is provided. Although an example of the manufacturing method of a hardening relief pattern is demonstrated below, this invention is not limited to this.

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

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

  Next, the photosensitive resin layer is exposed. As the actinic radiation for exposure, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable. From the viewpoint of pattern resolution and handleability, the light source wavelength is preferably in the g-line, h-line or i-line region of a 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 performed by using a developer and selecting from a method such as an immersion method, a paddle method, and a rotary spray method. By developing, an exposed portion (in the case of a positive type) or an unexposed portion (in the case of a negative type) can be eluted and removed from the applied photosensitive resin layer to obtain a relief pattern.

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

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

  Finally, a cured relief pattern can be obtained by heating the relief pattern thus obtained. The heating temperature is preferably 150 ° C. or higher and lower than 300 ° C., more preferably 250 ° C. or lower, and further preferably 170 ° C. or higher and 220 ° C. or lower. The photosensitive resin composition provided by the present invention has an advantage that sufficient film physical properties (for example, heat resistance of a cured film) can be realized even by curing 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.

<Measurement of cured relief pattern cross-sectional angle>
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 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). After exposure, Examples 39 and 40 and Comparative Examples 9 and 10 described later were reheated on a hot plate at 120 ° C. for 180 seconds. Next, it is developed with a developing machine (D-SPIN) at 23 ° C. using a 2.38% tetramethylammonium hydroxide aqueous solution AZ-300MIF (manufactured by AZ Electronic Materials) and rinsed with pure water. Then, curing was carried out in a vertical curing furnace VF200B (manufactured by Koyo Thermo System Co., Ltd.) under a nitrogen atmosphere at 200 ° C. for 1 hour to obtain a cured relief pattern. Then, the cross-sectional shape of a 100 micrometer space site | part and a 100 micrometer line site | part was observed using SEM (Hitachi High-Technologies company make, model name S-4800). A tangent line L1 to the pattern sidewall was drawn at a position half the height (ie, thickness) of the cured film. The angle formed by the line segment L2 on the image corresponding to the interface between the substrate and the cured film and the tangent line L1 (that is, the cured relief pattern inner angle) was measured as the cured relief pattern cross-sectional angle.
<Viscosity change rate at room temperature for 4 weeks>
Samples obtained by leaving the photosensitive resin compositions of Examples 1 to 44 and Comparative Examples 1 to 13 at room temperature for 3 days are used as prepared samples, and samples that are further left at room temperature for 4 weeks are used as samples after 4 weeks. Viscometer with temperature controller (Viscosity was measured at 23 ° C. using TV-22 manufactured by Toki Sangyo Co., Ltd.
The viscosity change rate at room temperature for 4 weeks was determined by [(viscosity of sample after 4 weeks) − (viscosity of sample after adjustment)] / (viscosity of sample after adjustment) × 100. The results are shown in Table 2 below.

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

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

  Next, the reaction vessel was cooled in the atmosphere, and 100 g of tetrahydrofuran was separately added thereto and stirred. The reaction dilution is dropped into 4 L of water under high-speed stirring to disperse and precipitate the resin, which is recovered, appropriately washed with water, dehydrated and then vacuum-dried, and a copolymer of phloroglucinol / BMMB (phenol resin) (A-1)) was obtained with a yield of 70%. 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 a uniformly dissolved solution was added to the solution using a dropping funnel. The mixture was added dropwise to the separable flask in 1 hour, and stirred for another 2 hours after the addition.

  After completion of the reaction, the same treatment as in Synthesis Example 1 was performed to obtain a copolymer (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, 100 parts by mass of phenol resin (A-1), 3 parts by mass of compound (B-1) having two carboxy groups in the molecule, and 12 parts by mass of photoacid generator (C-1) The positive photosensitive resin composition was prepared by dissolving in 214 parts by mass of the solvent (D-1) and filtering with a 0.1 μm filter. 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 2-38, 41-44, Comparative Examples 1-8, 11-13]
A composition comprising the components shown in Table 1 was prepared in the same manner as in Example 1 to obtain a positive photosensitive resin composition. The properties of this composition were measured in the same manner as in Example 1. The obtained results are shown in Table 2.

[Examples 39 and 40, Comparative Examples 9 and 10]
A composition comprising the components shown in Table 1 was prepared in the same manner as in Example 1 to obtain a negative photosensitive resin composition. The properties of this composition were measured according to the evaluation method described above. The obtained results are shown in Table 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: Novolak resin, polystyrene-equivalent weight average molecular weight (Mw) = 10,600 (product name: EP-4080G, manufactured by Asahi Organic Materials Co., Ltd.)
A-8: Polyparavinylphenol, polystyrene equivalent weight average molecular weight (Mw) = 10,000 (manufactured by Maruzen Petrochemical Co., Ltd., product names: Marcalinker M, S-4)

<(B) Compound (compound having 2 to 4 hydrogen bond-forming groups in the molecule)>
B-1: Malonic acid (dicarboxylic acid) (manufactured by Tokyo Chemical Industry)
B-2: o-phthalic acid (dicarboxylic acid) (manufactured by Tokyo Chemical Industry)
B-3: Trimellitic acid (tricarboxylic acid) (manufactured by Tokyo Chemical Industry)
B-4: Succinic anhydride (dicarboxylic anhydride) (manufactured by Tokyo Chemical Industry)
B-5: p-phthalic acid diamide (carboxylic acid amide) (manufactured by Tokyo Chemical Industry)
B-6: Dimethyl p-phthalate (carboxylic acid ester) (manufactured by Tokyo Chemical Industry)
B-7: Benzoic acid (monocarboxylic acid) (manufactured by Tokyo Chemical Industry)

（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−２：イルガキュア ＰＡＧ１２１（商品名、ＢＡＳＦジャパン社製） <(C) Photoacid generator>
C-1: Photoacid generator represented by the following formula:

(Wherein 83% of Q is the following:

The remainder is a hydrogen atom. )
C-2: Irgacure PAG121 (trade name, manufactured by BASF Japan)

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

<(E) Additive>
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 relief pattern shape is excellent (that is, the cured relief pattern cross-sectional angle is large) to form a cured film. We were able to. Moreover, the Example whose compounding quantity of (B) compound is 3 mass parts or less with respect to 100 mass parts of (A) phenol resin was especially excellent in coexistence with pattern cross-sectional angle after hardening, and storage stability. 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 (11)

The following components (A) to (C):
(A) phenolic resin,
(B) a compound having 2 to 150 carbon atoms having 2 to 4 carboxy groups in the molecule, and (C) a photoacid generator,
Including
(B) the compound of 2 to 150 carbon atoms and having 2 to 4 carboxyl groups in the molecule, 1, 10-decane dicarboxylic acid, dodecane dicarboxylic acid, 1,3-cyclopentane dicarboxylic acid, 1, 3-dicarboxy methylcyclohexane, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethane dicarboxylic acid, 3-sodium sulfoisophthalate, main Chirukohaku acid, octyl succinic acid, 1,5-naphthalene dicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, de Kamechiren dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid , 4,4'-diphenyl dicarboxylic acid, alpha - ketoglutarate, collected by Con acid, mesaconic acid, oxaloacetic acid, Te tiger hydroxybutanoic acid, aspartic acid, 1,1-cyclopropane dicarboxylic acid, glutamic acid, 1-carboxyglutamic acid, aconitic acid, Lee plumb acid, 3,5-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, quinolinic acid , glutathione, 1,2,4-naphthalenetricarboxylic acid, 1,2,5-naphthalenetricarboxylic acid, 1,4,5-naphthalenetricarboxylic acid, 2,5,7-naphthalene Tricarboxylic acid, 2,6,7-naphthalenetricarboxylic acid, 3,3 ′, 4-diphenyltricarboxylic acid, benzophenone-3,3 ′, 4-tricarboxylic acid, diphenylsulfone-3,3 ′, 4-tricarboxylic acid, diphenyl ether -3,3 ', 4-tricarboxylic acid, 1,2,5-hexanetri Rubonic acid, 1,2,4-cyclohexanetricarboxylic acid, benzophenone-2,4,5-tricarboxylic acid, 3,3,4'-benzophenonetricarboxylic acid, 3,4,4'-benzophenonetricarboxylic acid, 2,3, 4'-diphenyltricarboxylic acid, 2,3,6-pyridinetricarboxylic acid, 3,4,4'-benzanilide tricarboxylic acid, 1,4,5-naphthalenetricarboxylic acid, 2'-methoxy-3,4,4 ' - diphenylether tricarboxylic acid, 2'-chloro-benzanilide -3,4,4'- tricarboxylic acid, tartronic acid, preparative Le entry carboxylic acid, 4-neopentyl lyso sulfonyl -1,2,6,7- heptanoic tetracarboxylic acid 3-methyl-4-heptenyl-1,2,5,6-hexanetetracarboxylic acid, 3-methyl-3-heptyl-5-methyl- 1,2,6,7-heptene (4) -tetracarboxylic acid, 3-nonyl-4-methylidonyl-1,2,5,6-hexanetetracarboxylic acid, 3-decylisonyl-1.2,5.6 Hexanetetracarboxylic acid, 3-nonyl-1,2,6,7-heptene (4) -tetracarboxylic acid, 3-decynyl-1,2,5,6-hexanetetracarboxylic acid, 3-butyl-3-ethylenyl -1,2,5,6-hexanetetracarboxylic acid, 3-methyl-4-butylidonyl-1,2,6,7-heptanetetracarboxylic acid, 3-methyl-4-butyl-1,2,6 7- heptene (4) - tetracarboxylic acid, 3-methyl-5-octyl -1,2,6,7- heptene (4) - tetracarboxylic acid, Te tiger chloro phthalic acid, 1,20- Aiko Sanji carboxylic acid, 1,24-tetraa Co Sanji carboxylic acid, and at least one compound glutaconic acid, or Ranaru group,
Photosensitive resin composition. The (A) phenol resin is represented by the following general formula (6):

{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. 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 chain aliphatic hydrocarbon group having 2 to 10 carbon atoms which may have an unsaturated bond, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, General formula (7):

(Wherein p is an integer of 1 to 10), and selected from the group consisting of a divalent alkylene oxide group represented by: and a divalent organic group having an aromatic ring having 6 to 12 carbon atoms. A divalent organic group. } The photosensitive resin composition of Claim 1 containing the phenol resin which has a repeating unit represented by these. Said (A) phenol resin contains the phenol resin which has a repeating unit represented by the said General formula (6), X in the said General formula (6) is following General formula (8):

{Wherein R ₂ , R ₃ , R ₄ and R ₅ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a part or all of the hydrogen atoms are fluorine atoms. in a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms comprising optionally substituted, an integer of n ₁ is 0 to 4, R ₆ where n ₁ is an integer of 1 to 4, the A halogen atom, a hydroxyl group, or a monovalent organic group having 1 to 12 carbon atoms, at least one R ₆ is a hydroxyl group, and a plurality of R _{6 s} when n ₁ is an integer of 2 to 4 may be the same as each other Or they may be different. } And the following general formula (9):

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

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

A divalent group selected from the group consisting of divalent groups represented by the formula: } The photosensitive resin composition of Claim 2 containing the bivalent organic group selected from the group which consists of a bivalent group represented by these. Said (A) phenol resin contains the phenol resin which has a repeating unit represented by the said General formula (6), X in the said General formula (6) is following formula (11):

The photosensitive resin composition of Claim 2 or 3 containing the bivalent organic group represented by these. Said (A) phenol resin contains the phenol resin which has a repeating unit represented by the said General formula (6), X in the said General formula (6) is following formula (12):

In comprising a divalent organic group represented by the photosensitive resin composition according to any one of claims 2-4. The (A) phenol resin is represented by the following general formula (13):

{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 (14):

{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. } Comprising a phenolic resin having both the repeating units in the same resin skeleton represented by the photosensitive resin composition according to any one of claims 2-5. Wherein (C) a photoacid generator containing o- quinonediazide compound, the photosensitive resin composition according to any one of claims 1-6. It contains 0.01 to 20 parts by mass of the (B) compound and 0.1 to 70 parts by mass of the (C) photoacid generator with respect to 100 parts by mass of the (A) phenol resin. The photosensitive resin composition as described in any one of 7 . The following steps:
(1) The process of forming the photosensitive resin layer containing the photosensitive resin composition as described in any one of Claims 1-8 on a board | substrate,
(2) a step of exposing the photosensitive resin layer;
(3) removing exposed or unexposed areas with a developer to obtain a relief pattern; and (4) heat treating the relief pattern;
A method for producing a cured relief pattern. A method for manufacturing a semiconductor device comprising a semiconductor element and a cured film provided on the semiconductor element,
A method for manufacturing a semiconductor device, comprising: forming a cured film that is a cured relief pattern on a semiconductor element by the method according to claim 9 . A display body device comprising a display body element and a cured film provided on top of the display body element, comprising:
The manufacturing method of a display body apparatus including forming the cured film which is a hardening relief pattern by the method of Claim 9 on the upper part of a semiconductor element.