JP6294023B2 - 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

In the photolithography development process of the semiconductor manufacturing process, an alkaline solution (for example, a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (hereinafter also referred to as TMAH)) is mainly used as a developer from the viewpoint of cost. It is coming. When the alkali solubility of the photosensitive resin composition is insufficient, problems such as a long development process and a decrease in pattern resolution may occur.
Therefore, the alkali solubility of the photosensitive resin composition is one of the important characteristics of the photosensitive resin composition.

  When a resin film is applied 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 inner angle formed by the side surface with respect to the formation surface) in the cured relief pattern) is important. One of the physical properties. 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, Patent Documents 1 to 3 mentioned above do not describe the alkali solubility of the photosensitive resin composition and the cured relief pattern cross-sectional angle. As a result of investigation by the present inventor, there is no composition that satisfies both that the photosensitive resin composition has sufficient alkali solubility and a sufficiently large cured relief pattern cross-sectional angle, and there is room for improvement (described later). See comparative example).

  Therefore, the present invention is capable of low-temperature curing (for example, curing at 200 ° C.), the photosensitive resin composition has sufficient alkali solubility, and has an excellent cured relief pattern shape (that is, a cured relief pattern cross-sectional angle). A photosensitive resin composition containing a phenolic resin, a cured relief pattern produced using the photosensitive resin composition, a production method thereof, and the cured relief pattern. It is an object to provide a semiconductor device and a display device having a cured film.

｛式中、ａは、２又は３の整数であり、ｂは、０〜２の整数であり、２≦（ａ＋ｂ）≦４であり、Ｒ₁は、炭素数１〜２０の１価の有機基、ハロゲン原子、ニトロ基及びシアノ基から成る群から選ばれる１価の置換基を表し、ｂが２である場合には、２つのＲ₁は、互いに同一であるか、又は異なっていてよく、そしてＸは、不飽和結合を有していてもよい炭素数２〜１０の２価の鎖状脂肪族炭化水素基、炭素数３〜２０の２価の脂環式炭化水素基、下記一般式（２）：

（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、及び芳香族基を有する２価の有機基から成る群から選ばれる２価の有機基を表す。｝
で表される繰り返し単位を有する、上記［１］に記載のポジ型感光性樹脂組成物。
［３］
前記一般式（１）において、Ｘは、下記一般式（３）：

｛式中、Ｒ₂、Ｒ₃、Ｒ₄及びＲ₅は、それぞれ独立に、水素原子、炭素数１〜１０の１価の脂肪族炭化水素基、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いる炭素数１〜１０の１価の脂肪族炭化水素基であり、ｎ₁は、０〜４の整数であり、Ｒ₆は、ハロゲン原子、水酸基又は１価の有機基であり、ｎ₁が１である場合には、Ｒ₆は、水酸基、又は水酸基を有する１価の有機基であり、そしてｎ₁が２〜４の整数である場合には、Ｒ₆の少なくとも１つは、水酸基、又は水酸基を有する１価の有機基であり、かつ複数のＲ₆は、それぞれ同一であるか、又は異なっていてよい。｝で表される２価の基、及び／又は下記一般式（４）：

｛式中、Ｒ₇、Ｒ₈、Ｒ₉及びＲ₁₀は、それぞれ独立に、水素原子、炭素数１〜１０の１価の脂肪族炭化水素基、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いる炭素数１〜１０の１価の脂肪族炭化水素基を表し、そしてＹ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（２）：

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

で表される２価の基から成る群から選ばれる２価の有機基である。｝で表される２価の基を含む、上記［２］に記載のポジ型感光性樹脂組成物。
［４］
前記一般式（１）において、Ｘは、下記一般式（６）：

で表される２価の有機基を含む、上記［２］又は［３］に記載のポジ型感光性樹脂組成物。
［５］
前記一般式（１）において、Ｘは、下記一般式（７）：

で表される２価の有機基を含む、上記［２］〜［４］のいずれか１項に記載のポジ型感光性樹脂組成物。
［６］
前記多価フェノール樹脂が、下記一般式（８）：

｛式中、Ｒ₁₁は、炭化水素基及びアルコキシ基から成る群から選ばれる炭素数１〜１０の１価の基であり、ｎ₂は、２又は３の整数であり、ｎ₃は、０〜２の整数であり、ｍ₁は、１〜５００の整数であり、２≦（ｎ₂＋ｎ₃）≦４であり、そしてｎ₃が２である場合には、２つのＲ₁₁は、互いに同一であるか、又は異なっていてよい。｝で表される構造及び下記一般式（９）：

｛式中、Ｒ₁₂及びＲ₁₃は、それぞれ独立に、炭化水素基及びアルコキシ基から選ばれる炭素数１〜１０の１価の基であり、ｎ₄は、２又は３の整数であり、ｎ₅は、０〜２の整数であり、ｎ₆は、０〜３の整数であり、ｍ₂は、１〜５００の整数であり、２≦（ｎ₄＋ｎ₅）≦４であり、ｎ₅が２である場合には、２つのＲ₁₂は、互いに同一であるか、又は異なっていてよく、そしてｎ₆が２〜３である場合には、複数のＲ₁₃は、互いに同一であるか、又は異なっていてよい。｝で表される構造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［１］〜［５］のいずれか１項に記載のポジ型感光性樹脂組成物。
［７］
前記多価フェノール樹脂が、多価フェノール類とアルデヒド類との反応生成物を含む、上記［１］に記載のポジ型感光性樹脂組成物。
［８］
前記多価フェノール類が、２価フェノール類及び３価フェノール類の一方又は両方を含む、上記［７］に記載のポジ型感光性樹脂組成物。
［９］
前記（Ａ）フェノール樹脂が、（Ａ２）不飽和炭化水素基を有する化合物で変性していない非変性フェノール樹脂、を更に含む、上記［１］〜［８］のいずれか１項に記載のポジ型感光性樹脂組成物。
［１０］
前記（Ａ１）変性多価フェノール樹脂の前記（Ａ２）非変性フェノール樹脂に対する質量比が５／９５〜９５／５である、上記［９］に記載のポジ型感光性樹脂組成物。
［１１］
前記（Ｂ）光により酸を生成する化合物がｏ−キノンジアジド化合物である、上記［１］〜［１０］のいずれか１項に記載のポジ型感光性樹脂組成物。
［１２］
熱により酸を生成する化合物を更に含む、上記［１］〜［１１］のいずれか一項に記載のポジ型感光性樹脂組成物。
［１３］
前記（Ａ）フェノール樹脂１００質量部に対して、前記（Ｂ）光により酸を生成する化合物３〜１００質量部を含む、上記［１］〜［１２］のいずれか一項に記載のポジ型感光性樹脂組成物。
［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、前記半導体装置。
［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、前記表示体装置。 The present invention has the following configuration.
[1]
(A) phenolic resin,
(B) a compound that generates an acid by light, and
(C) a thermal crosslinking agent,
Including
The positive photosensitive resin composition, wherein the (A) phenol resin comprises (A1) a modified polyphenol resin obtained by modifying a polyphenol resin with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms. object.
[2]
The polyhydric phenol resin has the following general formula (1):

{In the formula, a is an integer of 2 or 3, b is an integer of 0 to 2, 2 ≦ (a + b) ≦ 4, and R ₁ is a monovalent organic compound having 1 to 20 carbon atoms. Represents a monovalent substituent selected from the group consisting of a group, a halogen atom, a nitro group and a cyano group, and when b is 2, the two R _{1 s} 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 (2):

(In the formula, p is an integer of 1 to 10.)
A divalent organic group selected from the group consisting of a divalent alkylene oxide group represented by the formula (1) and a divalent organic group having an aromatic group. }
The positive photosensitive resin composition according to the above [1], which has a repeating unit represented by
[3]
In the general formula (1), X represents the following general formula (3):

{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. 1 is a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and n ₁ is an integer of 0 to 4, and R ₆ is a halogen atom, a hydroxyl group or a monovalent organic group. , N ₁ is 1, R ₆ is a hydroxyl group or a monovalent organic group having a hydroxyl group, and when n ₁ is an integer of 2 to 4, at least one of R ₆ Is a hydroxyl group or a monovalent organic group having a hydroxyl group, and the plurality of R ₆ may be the same or different. } And / or the following general formula (4):

{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. Represents a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms that is substituted with Y, and Y is a single bond or a chain aliphatic hydrocarbon having 1 to 10 carbon atoms that may be substituted with a fluorine atom Group, an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, the following general formula (2):

(In the formula, p is an integer of 1 to 10.)
And an alkylene oxide group represented by the following formula (5):

A divalent organic group selected from the group consisting of divalent groups represented by the formula: } The positive photosensitive resin composition as described in said [2] containing the bivalent group represented by these.
[4]
In the general formula (1), X represents the following general formula (6):

The positive photosensitive resin composition according to the above [2] or [3], comprising a divalent organic group represented by the formula:
[5]
In the general formula (1), X represents the following general formula (7):

The positive photosensitive resin composition of any one of said [2]-[4] containing the bivalent organic group represented by these.
[6]
The polyhydric phenol resin has the following general formula (8):

{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 an integer of 2 or 3, and n ₃ is 0 When m ₁ is an integer from ₁ to 500, 2 ≦ (n ₂ + n ₃ ) ≦ 4, and n ₃ is 2, two R ₁₁ are They may be the same or different. } And the following general formula (9):

{In the formula, R ₁₂ and R ₁₃ are each independently a monovalent group having 1 to 10 carbon atoms selected from a hydrocarbon group and an alkoxy group; n ₄ is an integer of 2 or 3; 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 When R 2 is 2, two R ₁₂ may be the same as or different from each other, and when n ₆ is 2 to 3, are a plurality of R ₁₃ the same as each other? Or different. } The positive photosensitive resin composition according to any one of [1] to [5] above, comprising a phenol resin having both of the structures represented by
[7]
The positive photosensitive resin composition according to the above [1], wherein the polyhydric phenol resin contains a reaction product of polyhydric phenols and aldehydes.
[8]
The positive photosensitive resin composition according to [7] above, wherein the polyhydric phenol contains one or both of a dihydric phenol and a trihydric phenol.
[9]
The positive electrode according to any one of the above [1] to [8], wherein the (A) phenol resin further comprises (A2) a non-modified phenol resin not modified with a compound having an unsaturated hydrocarbon group. Type photosensitive resin composition.
[10]
The positive photosensitive resin composition according to [9] above, wherein the mass ratio of the (A1) modified polyhydric phenol resin to the (A2) non-modified phenol resin is 5/95 to 95/5.
[11]
(B) The positive photosensitive resin composition according to any one of [1] to [10], wherein the compound that generates an acid by light is an o-quinonediazide compound.
[12]
The positive photosensitive resin composition according to any one of [1] to [11], further including a compound that generates an acid by heat.
[13]
Positive type as described in any one of said [1]-[12] containing 3-100 mass parts of said (B) compounds which produce | generate an acid with light with respect to 100 mass parts of (A) phenol resins. Photosensitive resin composition.
[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 the exposed portion with a developer to obtain a relief pattern; and (4) heat-treating the relief pattern;
A method for producing a cured relief pattern.
[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 according to the above [15].

  According to the present invention, curing at a low temperature (for example, 200 ° C.) is possible, the photosensitive resin composition has sufficient alkali solubility, and has an excellent cured relief pattern shape (that is, a cured relief pattern cross-sectional angle is large). Photosensitive resin composition containing a specific phenol resin that gives a cured film, a cured relief pattern produced using the photosensitive resin composition, a method for producing the same, and a semiconductor having the cured relief pattern as a cured film A device and a display device can be provided.

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

<Photosensitive resin composition>
The positive photosensitive resin composition provided by one embodiment of the present invention is:
(A) phenol resin (in this disclosure, sometimes referred to as “component (A)”),
(B) a compound that generates an acid by light (also referred to as “component (B)” in the present disclosure), and
(C) a thermal crosslinking agent (also referred to as “component (C)” in the present disclosure),
including. (A) A phenol resin is a modified polyphenol resin obtained by modifying (A1) a polyhydric phenol resin with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms (in this disclosure, “(A1) Also referred to as “hydric phenol resin”.
Hereinafter, each component will be described in order.

[(A) Phenolic resin]
(A) A phenol resin (component (A)) means a resin having a repeating unit having a phenolic hydroxyl group. (A) The phenol resin contains (A1) a modified polyphenol resin. Typically, (A1) modified polyphenol resin is
(A1) Reaction between a polyhydric phenol and a compound having an unsaturated hydrocarbon group (more specifically, a compound having 4 to 100 carbon atoms) (hereinafter also referred to as “unsaturated hydrocarbon group-containing compound”). Products (hereinafter also referred to as “unsaturated hydrocarbon group-modified polyhydric phenol derivatives”) and polycondensation products of aldehydes (hereinafter referred to as “(a1) unsaturated hydrocarbon group-modified polyhydric phenol derivatives and aldehydes”) Also referred to as a "condensation polymerization product"), or
(A2) A reaction product of a polyhydric phenol resin and an unsaturated hydrocarbon group-containing compound.

  In the present disclosure, phenols means a compound having a phenolic hydroxyl group and derivatives thereof, and monovalent phenols mean a compound having one phenolic hydroxyl group and derivatives thereof, and polyhydric phenols are It means a compound having two or more phenolic hydroxyl groups and a derivative thereof. In the present disclosure, the phenol resin means a resin having a repeating unit derived from the above phenols, and the monovalent phenol resin means 50 mol% or more of the repeating units derived from the above monovalent phenols based on the total repeating units. The polyphenol resin means a resin containing 50 mol% or more of the repeating units derived from the polyhydric phenols based on the total repeating units.

  (A1) The modified polyhydric phenol resin does not undergo cyclization as in the case of using a polyimide precursor or a polybenzoxazole precursor at the time of thermosetting, so that the temperature is low (for example, 250 ° C. or lower, more typically 200 ° C. C. or less) is possible.

  In the photosensitive resin composition of the present embodiment, by using (A1) a modified polyhydric phenol resin, for example, a modified phenol resin obtained by modifying a monohydric phenol resin with a compound having an unsaturated hydrocarbon group (hereinafter, Compared to the case of using "modified monohydric phenol resin"), the resin has higher alkali solubility, which is one of the important characteristics required for photosensitive resin compositions for semiconductor protective films and insulating films. Further, there is an advantage that the cross-section angle of the cured relief pattern, which is one of important characteristics required for the semiconductor protective film and insulating film, is large.

  A phenol resin having a phenolic hydroxyl group is soluble in an alkaline solution as a developer, and a polyhydric phenol resin has a larger number of phenolic hydroxyl groups in the molecule than a monovalent phenol resin, and the hydroxyl group concentration of the resin is higher. high. For these reasons, it is presumed that the modified polyhydric phenol resin is more soluble in an alkaline solution than the modified monohydric phenol resin.

In addition, the mechanism by which the modified polyhydric phenol resin can give a larger sectional angle of the cured relief pattern than the modified monohydric phenol resin is not clear, but is considered as follows.
When phenolic resin is used for semiconductor protective film and insulating film, pattern sagging during heat curing is likely to occur (that is, the sectional angle of the cured relief pattern is reduced). If the softening point of the phenol resin is lower than the temperature at which the crosslinking agent of the composition starts to be crosslinked, the melt viscosity of the composition may be lowered.
When the number of phenolic hydroxyl groups in the phenolic resin is large, the phenolic hydroxyl group and the hydrogen atom of the molecule or other molecule form a hydrogen bond, and a state in which the intramolecular / between molecules of the phenolic resin are artificially bridged Therefore, it is presumed that the melt viscosity of the composition does not decrease, pattern sagging is suppressed, and the cross-sectional angle increases.

  In this embodiment, the weight average molecular weight of (A1) modified polyhydric phenol resin 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 the thermophysical properties and mechanical properties of the cured film, and on the other hand, from the viewpoint of alkali solubility of the photosensitive resin composition, may be 100,000 or less. preferable. 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.

(A1) Polycondensation product of unsaturated hydrocarbon group-modified polyhydric phenol derivative and aldehyde (a1) Polycondensation product of unsaturated hydrocarbon group-modified polyhydric phenol derivative and aldehyde And an unsaturated hydrocarbon group-containing compound are reacted to prepare an unsaturated hydrocarbon group-modified polyphenol derivative, and then the unsaturated hydrocarbon group-modified polyphenol derivative and an aldehyde are polycondensed. Generate.

  The polyhydric phenols are not limited as long as they are dihydric or higher phenols, but include one or both of dihydric phenols and trihydric phenols from the viewpoint of the degree of polymerization of the produced phenol resin and cost. Preferably, it consists of one or both of these.

  Examples of dihydric phenols that can be used in the present embodiment include catechol, resorcin, hydroquinone, 3-methylcatechol, 4-methylcatechol, 2-methylresorcinol, 4-methylresorcinol, methylhydroquinone, 3-ethyl. Catechol, 4-ethylcatechol, 2-ethylresorcinol, 4-ethylresorcinol, ethylhydroquinone, n-propylhydroquinone, isopropylhydroquinone, t-butylhydroquinone, 4-n-hexylresorcinol, 4-hexanoylresorcinol, 3,5- Dimethylcatechol, 2,5-dimethylresorcinol, 2,3-diethylhydroquinone, 2,5-dimethylhydroquinone, 3,5-diethylcatechol, 2,5-diethylreso Sinol, 2,5-diethylhydroquinone, 3,5-diisopropylcatechol, 2,5-diisopropylresorcinol, 2,3-diisopropylhydroquinone, 2,5-diisopropylhydroquinone, 3,5-di-t-butylcatechol, 2, Examples include (poly) alkyl-substituted dihydric phenols such as 5-di-t-butylresorcinol, 2,3-di-t-butylhydroquinone, and 2,5-di-t-butylhydroquinone.

  Examples of the trivalent phenols that can be used in the present embodiment include pyrogallol, phloroglucinol, 1,2,4-benzenetriol, and the like.

  The above polyhydric phenols are used singly or in combination of two or more.

  The unsaturated hydrocarbon group of the unsaturated hydrocarbon group-containing compound preferably contains two or more unsaturated groups from the viewpoint of adhesion of the cured film and thermal shock resistance. Further, from the viewpoint of compatibility with the resin composition and the flexibility of the cured film, the unsaturated hydrocarbon group-containing compound has 4 to 100 carbon atoms, preferably 8 to 80 carbon atoms, 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, epoxidized polybutadiene, linoleyl alcohol, oleyl alcohol, unsaturated fatty acid, and unsaturated fatty acid ester. . 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, an ester of an unsaturated fatty acid having 8 to 30 carbon atoms and a monovalent to trivalent alcohol having 1 to 10 carbon atoms is more preferable, and an unsaturated fatty acid having 8 to 30 carbon atoms and a trivalent alcohol are preferable. Especially preferred are esters with glycerin.

  Esters of unsaturated fatty acids having 8 to 30 carbon atoms and glycerin are commercially available as vegetable oils. The vegetable oil can be a non-drying oil having an iodine value of 100 or less, a semi-drying oil of more than 100 and less than 130, or a drying oil of 130 or more. Non-drying oils include, for example, olive oil, Asa seed oil, cashew oil, potato oil, camellia oil, castor oil, and peanut oil. Examples of semi-drying oils include corn oil, cottonseed oil, and sesame oil. Examples of the drying oil include paulownia oil, linseed oil, soybean oil, walnut oil, safflower oil, sunflower oil, camellia oil and coconut oil. Moreover, you may use the processed vegetable oil obtained by processing these vegetable oils.

  Among the above vegetable oils, it is preferable to use a non-drying oil from the viewpoint of preventing gelation accompanying the progress of excessive reaction and improving the yield in the reaction between the polyhydric phenols or the polyhydric phenol resin and the vegetable oil. On the other hand, it is preferable to use drying oil from the viewpoint of improving the adhesion, mechanical properties and thermal shock resistance of the cured film. 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 unsaturated hydrocarbon group-containing compounds are used singly or in combination of two or more.
The reaction between the polyhydric phenols and the unsaturated hydrocarbon group-containing compound is preferably performed at 50 to 130 ° C. From the viewpoint of improving the flexibility of the cured film, the reaction ratio between the polyhydric phenols and the unsaturated hydrocarbon group-containing compound is 1 to 100 unsaturated hydrocarbon group-containing compounds with respect to 100 parts by mass of the polyhydric phenols. It is preferable that it is a mass part, 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.

  The (A1) modified polyhydric phenol resin is produced by polycondensation of the unsaturated hydrocarbon group-modified polyhydric phenol derivative produced by the above reaction with aldehydes.

  Examples of aldehydes include 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 It is selected from '-4,4'-benzophenone tetracarboxylic acid. In addition, a formaldehyde precursor such as paraformaldehyde or trioxane may be used in the reaction. These are used singly or in combination of two or more.

  The reaction between the aldehyde 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. 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 (A1) a modified polyphenol resin. In the reaction, a solvent such as toluene, xylene, or methanol can be used.

  In the reaction of the aldehydes with the unsaturated hydrocarbon group-modified phenol derivative, a component other than the unsaturated hydrocarbon group-modified polyhydric phenol derivative and aldehydes may be further reacted within a range that does not impair the purpose of the present invention. Also good. For example, (A1) modified polyhydric phenol resin can also be obtained by polycondensing the above-mentioned unsaturated hydrocarbon group-modified phenol derivative with aldehydes together with compounds other than phenols such as m-xylene. In this case, from the viewpoint of improving the alkali solubility of the photosensitive resin composition and the cross-sectional angle of the cured relief pattern, the molar ratio of the compound other than phenols to 1 mol of the unsaturated hydrocarbon group-modified polyphenol derivative is 0. Is preferably less than .5.

(A2) Reaction product of polyhydric phenol resin and unsaturated hydrocarbon group-containing compound (A1) The modified polyhydric phenol resin can also be obtained by reacting a polyhydric phenol resin with an unsaturated hydrocarbon group-containing compound. it can.
Here, the polyhydric phenol resin is not limited as long as it is a resin using a dihydric or higher phenol as a monomer. From the viewpoint of the elongation of the cured film, it is represented by (a2-1) general formula (1). A phenol resin having a repeating unit (in the present disclosure, sometimes referred to as “(a2-1) polyhydric phenol resin”), and from the viewpoint of cost, (a2-2) a polyhydric phenol and It is preferably a polycondensation product with aldehydes (also referred to as “(a2-2) polyhydric phenol resin” in the present disclosure).

｛式中、ａは、２又は３の整数であり、ｂは、０〜２の整数であり、２≦（ａ＋ｂ）≦４であり、Ｒ₁は、炭素数１〜２０の１価の有機基、ハロゲン原子、ニトロ基及びシアノ基から成る群から選ばれる１価の置換基を表し、ｂが２である場合には、２つのＲ₁は、互いに同一であるか、又は異なっていてよく、そしてＸは、不飽和結合を有していてもよい炭素数２〜１０の２価の鎖状脂肪族炭化水素基、炭素数３〜２０の２価の脂環式炭化水素基、下記一般式（２）：

（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、及び芳香族基を有する２価の有機基から成る群から選ばれる２価の有機基を表す。｝
で表される繰り返し単位を有することが好ましい。本発明の目的を損なわない範囲で（ａ２−１）多価フェノール樹脂が一般式（１）で表される繰り返し単位以外の繰り返し単位を有することは排除しないが、典型的には、（ａ２−１）多価フェノール樹脂が有する繰り返し単位は一般式（１）で表される繰り返し単位からなることができる。 (A2-1) Phenolic resin having a repeating unit represented by the general formula (1) In the present embodiment, the polyhydric phenol resin is represented by the following general formula (1):

{In the formula, a is an integer of 2 or 3, b is an integer of 0 to 2, 2 ≦ (a + b) ≦ 4, and R ₁ is a monovalent organic compound having 1 to 20 carbon atoms. Represents a monovalent substituent selected from the group consisting of a group, a halogen atom, a nitro group and a cyano group, and when b is 2, the two R _{1 s} 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 (2):

(In the formula, p is an integer of 1 to 10.)
A divalent organic group selected from the group consisting of a divalent alkylene oxide group represented by the formula (1) and a divalent organic group having an aromatic group. }
It is preferable to have a repeating unit represented by It is not excluded that the (a2-1) polyhydric phenol resin has a repeating unit other than the repeating unit represented by the general formula (1) as long as the object of the present invention is not impaired. 1) The repeating unit which polyhydric phenol resin has can consist of a repeating unit represented by General formula (1).

｛式中、Ｒ₁₄、Ｒ₁₅及びＲ₁₆は、それぞれ独立に、水素原子、不飽和結合を有していてもよい炭素数１〜１０の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を表し、そしてＲ₁₇は、不飽和結合を有していてもよい炭素数１〜１０の２価の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を表す。｝ In the general formula (1), R ₁ is not limited as long as it is a monovalent substituent selected from the group consisting of a monovalent organic group having 1 to 20 carbon atoms, a halogen atom, a nitro group, and a cyano group. From the viewpoint of alkali solubility, a halogen atom, a nitro group, a cyano group, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have an unsaturated bond, an aromatic hydrocarbon group having 6 to 20 carbon atoms, And a monovalent substituent selected from the group consisting of four groups represented by the following general formula (10).

{In the formula, 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, or a C 3-20 Represents an 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. Represents 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. }

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

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

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

｛式中、Ｒ₂、Ｒ₃、Ｒ₄及びＲ₅は、それぞれ独立に、水素原子、炭素数１〜１０の１価の脂肪族炭化水素基、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いる炭素数１〜１０の１価の脂肪族炭化水素基であり、ｎ₁は、０〜４の整数であり、Ｒ₆は、ハロゲン原子、水酸基又は１価の有機基であり、ｎ₁が１である場合には、Ｒ₆は、水酸基、又は水酸基を有する１価の有機基であり、そしてｎ₁が２〜４の整数である場合には、Ｒ₆の少なくとも１つは、水酸基、又は水酸基を有する１価の有機基であり、かつ複数のＲ₆は、それぞれ同一であるか、又は異なっていてよい。｝

｛式中、Ｒ₇、Ｒ₈、Ｒ₉及びＲ₁₀は、それぞれ独立に、水素原子、炭素数１〜１０の１価の脂肪族炭化水素基、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いる炭素数１〜１０の１価の脂肪族炭化水素基を表し、そしてＹ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（２）：

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

で表される２価の基から成る群から選ばれる２価の有機基である。｝ In the embodiment, in the above general formula (1), X is a divalent chain aliphatic hydrocarbon group having 2 to 10 carbon atoms which may have an unsaturated bond, 2 having 3 to 20 carbon atoms. A divalent organic group selected from the group consisting of a divalent alicyclic hydrocarbon group, a divalent alkylene oxide group represented by the general formula (2), and a divalent organic group having an aromatic group. . Among these divalent organic groups, from the viewpoint of the toughness of the cured film, X preferably contains at least one of the organic groups represented by the following general formulas (3) and (4). More preferably, it is at least one of the organic groups represented by the following general formulas (3) and (4).

{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. 1 is a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and n ₁ is an integer of 0 to 4, and R ₆ is a halogen atom, a hydroxyl group or a monovalent organic group. , N ₁ is 1, R ₆ is a hydroxyl group or a monovalent organic group having a hydroxyl group, and when n ₁ is an integer of 2 to 4, at least one of R ₆ Is a hydroxyl group or a monovalent organic group having a hydroxyl group, and the plurality of R ₆ may be the same or different. }

{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. Represents a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms that is substituted with Y, and Y is a single bond or a chain aliphatic hydrocarbon having 1 to 10 carbon atoms that may be substituted with a fluorine atom Group, an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, the following general formula (2):

(In the formula, p is an integer of 1 to 10.)
And an alkylene oxide group represented by the following formula (5):

A divalent organic group selected from the group consisting of divalent groups represented by the formula: }

  In the above general formula (4), Y is represented by a single bond, an alkylene oxide group represented by the above general formula (2), and the above formula (5) from the viewpoint of the elongation of the cured film. Of the divalent groups, divalent organic groups selected from ester groups, amide groups and sulfonyl groups are preferred.

In the embodiment, in the general formula (1), X preferably includes a divalent organic group represented by the general formula (3) or (4), and is represented by the general formula (4). The divalent organic group is more preferably a divalent organic group represented by the following general formula (6) from the viewpoint of the elongation of the cured film, and further represented by the following general formula (7). It is particularly preferable to contain a divalent organic group.

  In the general formula (1), it is preferable that the ratio of the portion containing the phenolic hydroxyl group and the portion represented by X is determined particularly from the viewpoint of elongation. More specifically, the proportion of the site represented by X is preferably 20% by mass or more based on the total mass of the structure represented by the general formula (1) from the viewpoint of elongation, More preferably, it is at least mass%. On the other hand, the above ratio is preferably 80% by mass or less, and more preferably 70% by mass or less, from the viewpoint of alkali solubility of the composition and stress of the cured film.

｛式中、Ｒ₁₁は、炭化水素基及びアルコキシ基から成る群から選ばれる炭素数１〜１０の１価の基であり、ｎ₂は、２又は３の整数であり、ｎ₃は、０〜２の整数であり、ｍ₁は、１〜５００の整数であり、２≦（ｎ₂＋ｎ₃）≦４であり、そしてｎ₃が２である場合には、２つのＲ₁₁は、互いに同一であるか、又は異なっていてよい。｝

｛式中、Ｒ₁₂及びＲ₁₃は、それぞれ独立に、炭化水素基及びアルコキシ基から選ばれる炭素数１〜１０の１価の基であり、ｎ₄は、２又は３の整数であり、ｎ₅は、０〜２の整数であり、ｎ₆は、０〜３の整数であり、ｍ₂は、１〜５００の整数であり、２≦（ｎ₄＋ｎ₅）≦４であり、ｎ₅が２である場合には、２つのＲ₁₂は、互いに同一であるか、又は異なっていてよく、そしてｎ₆が２〜３である場合には、複数のＲ₁₃は、互いに同一であるか、又は異なっていてよい。｝ Moreover, the polyhydric phenol resin which has a repeating unit represented by the said General formula (1) is a structure represented by following General formula (8) from a viewpoint of the alkali solubility of a composition, and the elongation of a cured film. And it is particularly preferred that both have the structure represented by the following general formula (9) in the same resin skeleton.

{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 an integer of 2 or 3, and n ₃ is 0 When m ₁ is an integer from ₁ to 500, 2 ≦ (n ₂ + n ₃ ) ≦ 4, and n ₃ is 2, two R ₁₁ are They may be the same or different. }

{In the formula, R ₁₂ and R ₁₃ are each independently a monovalent group having 1 to 10 carbon atoms selected from a hydrocarbon group and an alkoxy group; n ₄ is an integer of 2 or 3; 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 When R 2 is 2, two R ₁₂ may be the same as or different from each other, and when n ₆ is 2 to 3, are a plurality of R ₁₃ the same as each other? Or different. }

M ₂ of the general formula (8) m ₁ and the general formula in (9) in represents the total number of the respective repeating units in the backbone of the polyhydric phenol resin, and toughness of the film after curing, alkali From the viewpoint of solubility in an aqueous solution, each is independently an integer between 1 and 500, the lower limit is preferably 2, more preferably 3, and the upper limit is preferably 450. Yes, more preferably 400, and even more preferably 350. m ₁ and m ₂ are each independently preferably 1 or more from the viewpoint of the toughness of the cured film, and are preferably 500 or less from the viewpoint of solubility in an alkaline aqueous solution. Moreover, the position in the polymer of the repeating unit represented by the said General formula (8) and the repeating unit represented by the said General formula (9) can be a block, random, or these combination.

(A2-1) When the polyhydric phenol resin has both the structure represented by the general formula (8) and the structure represented by the general formula (9) in the same resin skeleton, the general formula (8) The higher the molar ratio of the structure represented by, the better the physical properties of the cured film and the better the heat resistance, while the higher the molar ratio of the structure represented by the general formula (9), The alkali solubility is good and the pattern shape after curing is excellent. Therefore, the range of the ratio of the structure represented by the general formula (8) to the structure represented by the general formula (9) is m ₁ / m ₂ = 90/10 to 20/80. From the viewpoint of the above, m ₁ / m ₂ = 80/20 to 40/60 is more preferable from the viewpoint of physical properties and alkali solubility of the cured film, and m ₁ / m ₂ = 70/30 to 50/50 is the cured film. It is particularly preferable from the viewpoints of physical properties, pattern shape, and alkali solubility.

  Typically, the (a2-1) polyhydric phenol resin can be synthesized by polymerizing a phenol and a copolymer component. Specifically, the copolymer component includes a compound having an aldehyde group (for example, a compound that decomposes to produce an aldehyde compound such as trioxane), a compound having a ketone group, and two methylol groups in the molecule. And a compound having one or more compounds selected from the group consisting of a compound having two alkoxymethyl groups in the molecule, and a compound having two haloalkyl groups in the molecule. The copolymer component is preferably a component comprising at least one of these. For example, 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, (a2-1) A monohydric phenol resin can be obtained. From the viewpoint of reaction control and the stability of the obtained phenolic resin and photosensitive resin composition, the charged molar ratio of phenols and copolymerization component is preferably 5: 1 to 1.01: 1. More preferably, the ratio is 5: 1 to 1.1: 1.

  (A2-1) Examples of phenols that can be used to obtain a polyhydric phenol resin include resorcinol, xylenol, catechol, methyl catechol, ethyl catechol, hexyl catechol, benzyl catechol, nitrobenzyl catechol, methyl resorcinol, ethyl resorcinol, Hexyl resorcinol, benzyl resorcinol, nitrobenzyl resorcinol, hydroquinone, caffeic acid, dihydroxybenzoic acid, methyl dihydroxybenzoate, ethyl dihydroxybenzoate, butyl dihydroxybenzoate, propyl dihydroxybenzoate, benzyl dihydroxybenzoate, dihydroxybenzamide, dihydroxybenzaldehyde , Dihydroxyacetophenone, dihydroxybenzophenone, dihydroxy Benzonitrile, N- (dihydroxyphenyl) -5-norbornene-2,3-dicarboximide, N- (dihydroxyphenyl) -5-methyl-5-norbornene-2,3-dicarboximide, nitrocatechol, fluorocatechol Chlorocatechol, bromocatechol, trifluoromethylcatechol, nitroresorcinol, fluororesorcinol, chlororesorcinol, bromoresorcinol, trifluoromethylresorcinol, pyrogallol, phloroglucinol, 1,2,4-trihydroxybenzene, trihydroxybenzoic acid, Methyl trihydroxybenzoate, ethyl trihydroxybenzoate, butyl trihydroxybenzoate, propyl trihydroxybenzoate, benzyl trihydroxybenzoate, trihydride Carboxymethyl benzamide, trihydroxy benzaldehyde, trihydroxy acetophenone, trihydroxybenzophenone, trihydroxy benzonitrile and the like.

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

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

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

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

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

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

  (A2-1) A polyhydric phenol resin is obtained by condensing the above-mentioned phenols with the above-mentioned copolymerization component by dehydration, dehydrohalogenation or dealcoholization, or polymerizing them while cleaving unsaturated bonds. However, a catalyst may be used during the polymerization. Examples of the catalyst include an acidic catalyst and an alkaline catalyst. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, methanesulfonic acid, p-toluenesulfonic acid, dimethyl sulfuric acid, diethyl sulfuric acid, acetic acid, oxalic acid, 1-hydroxyethylidene-1,1. Examples include '-diphosphonic acid, zinc acetate, boron trifluoride, boron trifluoride / phenol complex, boron trifluoride / ether complex, and the like. On the other hand, examples of the alkaline catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, triethylamine, pyridine, 4-N, N-dimethylaminopyridine, piperidine, Piperazine, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, Ammonia, hexamethylenetetramine and the like can be mentioned.

  In the embodiment, (a2-1) the amount of the catalyst used for obtaining the polyhydric phenol resin is based on the number of moles of the aldehyde compound, ketone compound, methylol compound, alkoxymethyl compound, diene compound or haloalkyl compound. The range is preferably 0.01 mol% to 100 mol%.

  (A2-1) When performing the synthesis reaction of polyhydric phenol resin, an organic solvent can be used as needed. Specific examples of the organic solvent that can be used include, but are not limited to, bis (2-methoxyethyl) ether, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol. Examples include dimethyl ether, cyclohexanone, cyclopentanone, toluene, xylene, γ-butyrolactone, N-methyl-2-pyrrolidone and the like. The amount of these organic solvents to be used is usually 10 parts by mass to 1000 parts by mass, preferably 20 parts by mass to 500 parts by mass, when the total mass of the charged raw materials is 100 parts by mass. In the synthesis reaction of (A) phenol resin, the reaction temperature is usually preferably 40 ° C to 250 ° C, more preferably 100 ° C to 200 ° C, and the reaction time is approximately 1 hour. 10 hours is preferable.

(A2-2) Polycondensation product of polyhydric phenols and aldehydes In the present embodiment, the polyhydric phenol resin is also preferably a polycondensation product of polyhydric phenols and aldehydes.

  (A2-2) The polycondensation of the polyhydric phenol resin is performed in the presence of a catalyst such as an acid or a base. As the polyhydric phenols, the polyhydric phenols described above as the raw material of (a1) can be used, and as the aldehydes, the aldehydes described above as the raw material of (a1) can be similarly used. The presence of condensation components other than polyhydric phenols and aldehydes is not excluded as long as the object of the present invention is not impaired. The condensation reaction can also be carried out in the same manner as the reaction between the aldehydes (a1) and the unsaturated hydrocarbon group-modified phenol derivative.

  (A2-1) A polyhydric phenol resin and / or (a2-2) a polyhydric phenol resin can be reacted with an unsaturated hydrocarbon group-containing compound to obtain (A1) a modified polyhydric phenol resin. This reaction is usually preferably carried out at 50 to 130 ° C. Moreover, the reaction rate of (a2-1) polyhydric phenol resin and / or (a2-2) polyhydric phenol resin and an unsaturated hydrocarbon group containing compound is from a viewpoint of improving the flexibility of a cured film, ( It is preferable that it is 1-100 mass parts of unsaturated hydrocarbon group containing compounds with respect to a total of 100 mass parts of a2-1) polyhydric phenol resin and (a2-2) polyhydric phenol resin, and it is 2-70 mass parts. More preferably, it is more preferably 5 to 50 parts by mass. 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. At this time, if necessary, p-toluenesulfonic acid, trifluoromethanesulfonic acid or the like may be used as a catalyst. In addition, solvents, such as toluene, xylene, methanol, tetrahydrofuran, can be used for reaction.

  (A) The phenol resin is a non-modified phenol resin (hereinafter referred to as “(A2) not modified with a compound having an unsaturated hydrocarbon group” for the purpose of improving the solubility in an alkaline solution as a developer. )) Also referred to as “non-modified phenolic resin”. (A2) Examples of non-modified phenol resins include polyhydroxystyrene and hydroxystyrene resins such as copolymers containing hydroxystyrene as a monomer unit, and condensation or cocondensation of phenols and aldehydes under a catalyst. And a novolak-type phenol resin, a polybenzoxazole precursor such as poly (hydroxyamide), poly (hydroxyphenylene) ether, and polynaphthol. (A2) Non-modified phenol resin may be comprised only by 1 type in resin illustrated above, and may be comprised including 2 or more types.

  Among these, a novolac type phenol resin is preferable because of its low price, high development contrast, and small volume shrinkage upon curing. In addition, hydroxystyrene resins are also preferred because of their excellent electrical properties (insulating properties) and small volume shrinkage during curing.

  (A2) Non-modified phenol resins include polycondensation products of phenols and aldehydes. The polycondensation is performed in the presence of a catalyst such as an acid or a base. A phenol resin obtained when an acid catalyst is used is particularly referred to as a novolak type phenol resin. Specific examples of novolak resins include phenol / formaldehyde novolak resins, cresol / formaldehyde novolak resins, xylylenol / formaldehyde novolak resins, resorcinol / formaldehyde novolak resins and phenol-naphthol / formaldehyde novolak resins.

  (A2) Phenols used for obtaining a non-modified phenol resin include phenol derivatives such as 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, Alkylphenols such as 3,5-trimethylphenol and 3,4,5-trimethylphenol, alkoxyphenols such as methoxyphenol and 2-methoxy-4-methylphenol, alkenylphenols such as vinylphenol and allylphenol, benzylphenol, etc. Aralkylphenol, alkoxycarbonylphenol such as methoxycarbonylphenol, arylcarbonylphenol such as benzoyloxyphenol, halogenated phenol such as chlorophenol, polyhydroxybenzene such as catechol, resorcinol and pyrogallol, bisphenol such as bisphenol A and bisphenol F, α -Or naphthol derivatives such as β-naphthol, hydroxyalkylphenols such as p-hydroxyphenyl-2-ethanol, p-hydroxyphenyl-3-propanol and p-hydroxyphenyl-4-butanol, hydroxyalkylcresols such as hydroxyethylcresol, Bisphenol monoethylene oxide adduct, bisphenol monopropylene oxide adduct, etc. Alcoholic hydroxyl group-containing phenol derivatives, p-hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid, p-hydroxyphenylbutanoic acid, p-hydroxycinnamic acid, hydroxybenzoic acid, hydroxyphenylbenzoic acid, hydroxyphenoxybenzoic acid and diphenol Examples include carboxyl group-containing phenol derivatives such as acids. Further, methylolated products of the above phenol derivatives such as bishydroxymethyl-p-cresol may be used as the phenol derivative.

  Furthermore, (A2) non-modified phenol resin may be a product obtained by polycondensation of the above phenols with aldehydes together with compounds other than phenols such as m-xylene. In this case, from the viewpoint of improving the alkali solubility of the photosensitive resin composition and the cross-sectional angle of the cured relief pattern, the molar ratio of the compound other than the phenols to the phenols used for the condensation polymerization is less than 0.5. And preferred.

  The above-mentioned phenols and compounds other than phenols are used singly or in combination of two or more.

  As the hydroxystyrene-based resin, for example, an ethylenically unsaturated double bond of hydroxystyrene introduced with a protecting group is polymerized (that is, vinyl polymerization) in the presence of a catalyst (that is, a radical initiator), and further deprotected. What is obtained by this can be used. Further, branch type poly (hydroxystyrene) such as PHS-B (trade name of DuPont) may be used.

  Here, as the protective group for hydroxystyrene, conventionally known ones such as an alkyl group and a silyl group can be used. Also, vinyl group-containing monomers such as styrene, (meth) acrylic acid, and (meth) acrylic acid esters can be copolymerized with hydroxystyrene introduced with a protective group.

  The molecular weight of the (A2) non-modified phenolic resin is a weight average molecular weight in consideration of solubility in an alkaline aqueous solution and a balance between photosensitivity (sensitivity and resolution) and mechanical properties (elongation at break, elastic modulus and residual stress). It is preferably 500 to 150,000, more preferably 500 to 100,000, and particularly preferably 1,000 to 50,000.

  The (A) phenol resin may be composed of (A1) a modified polyphenol resin and any (A2) non-modified phenol resin, or may further contain an additional phenol resin (for example, a modified monohydric phenol resin). From the viewpoint of obtaining the desired effect of the present invention, the ratio of (A1) modified polyhydric phenol resin to 100% by mass of (A) phenol resin is preferably 5% by mass or more, more preferably 10% by mass or more. is there. The proportion may be 100% by mass, but may be 95% by mass or less, or 90% by mass or less. When (A2) non-modified phenol resin is used, the ratio of (A2) non-modified phenol resin to 100% by mass of (A) phenol resin is preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably. Is 95% by mass or less, more preferably 90% by mass or less.

  When (A1) modified polyhydric phenol resin and (A2) non-modified phenol resin are used in combination, the sensitivity and resolution when forming a resist pattern, and the adhesion, mechanical properties and thermal shock of the resist pattern after curing From the point of property, the ratio M (A1) / M (mass M (A1) of the (A1) modified polyhydric phenol resin to the mass M (A2) of the (A2) non-modified phenol resin in the photosensitive resin composition ( A2) is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, and particularly preferably 15/85 to 85/15.

[(B) Compound that generates acid by light]
(B) A compound that generates an acid by light (component (B)) is used as a photosensitizer. In the positive photosensitive resin composition of the present embodiment, such a component (B) has a function of generating an acid by light irradiation and increasing the solubility of the light irradiated portion in an alkaline aqueous solution. As the component (B), a compound generally called a photoacid generator can be used. Specific examples of the component (B) include o-quinonediazide compounds, aryldiazonium salts, diaryliodonium salts, and triarylsulfonium salts. Of these, o-quinonediazide compounds are preferred because of their high sensitivity.

  As the o-quinonediazide compound, for example, a compound obtained by subjecting o-quinonediazidesulfonyl chloride to a hydroxy compound, an amino compound or the like in the presence of a dehydrochlorinating agent can be used.

  Examples of the o-quinonediazidesulfonyl chloride used in the reaction include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, and naphthoquinone-1,2-diazide-4- A sulfonyl chloride is mentioned.

  Examples of the hydroxy compound used in the reaction include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- ( 4-hydroxyphenyl) -1-methylethyl} phenyl] ethane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetra Hydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,2 ′, 3′-pentahydroxybenzophenone, 2,3,4,3 ′, 4 ′, 5′-hexahydroxy Benzophenone, bis (2,3,4-trihydroxyphenyl) methane, bis (2,3,4-tri Droxyphenyl) propane, 4b, 5,9b, 10-tetrahydro-1,3,6,8-tetrahydroxy-5,10-dimethylindeno [2,1-a] indene, tris (4-hydroxyphenyl) Examples include methane and tris (4-hydroxyphenyl) ethane.

  Examples of the amino compound used in the reaction include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4 ′. -Diaminodiphenyl sulfide, o-aminophenol, m-aminophenol, p-aminophenol, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, Bis (3-amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) Sulfone, bis (3-amino-4-hydroxypheny ) Hexafluoropropane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane and the like.

  Examples of the dehydrochlorinating agent used in the reaction include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like. Moreover, as a reaction solvent, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, N-methylpyrrolidone, or the like is used.

  o-quinonediazidosulfonyl chloride and hydroxy compound and / or amino compound are blended so that the total number of moles of hydroxy group and amino group is 0.5 to 1 per mole of o-quinonediazidesulfonyl chloride. It is preferred that A preferred blending ratio of the dehydrochlorinating agent and o-quinonediazide sulfonyl chloride is in the range of 0.95 / 1 molar equivalent to 1 / 0.95 molar equivalent.

  The preferable reaction temperature of the above reaction is 0 to 40 ° C., and the preferable reaction time is 1 to 10 hours.

  The blending amount of the component (B) is preferably 3 to 100 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of the difference in dissolution rate between the exposed part and the unexposed part and the allowable range of sensitivity. 50 mass parts is more preferable, and 5-30 mass parts is especially preferable.

[(C) Thermal crosslinking agent]
(C) As the thermal crosslinking agent (component (C)), a compound capable of forming a bridge structure by reacting with the component (A) when the photosensitive resin film after pattern formation is cured by heating is used. it can. By using the component (C), curing at a low temperature is possible, and generation of a brittle cured film and melting at the time of curing of the photosensitive resin film can be prevented. As the component (C), specifically, a compound having a phenolic hydroxyl group, a compound having a hydroxymethylamino group and / or an alkoxymethylamino group, a compound having an epoxy group, and the like are preferable.

  Regarding the component (C), the “compound having a phenolic hydroxyl group” does not include the (A1) modified polyhydric phenol resin. That is, (C) is not a polymer (including oligomer). The compound having a phenolic hydroxyl group as the component (C) can not only serve as a thermal cross-linking agent but also increase the dissolution rate of the exposed area when developing with an alkaline aqueous solution, thereby improving the sensitivity. The molecular weight of such a compound having a phenolic hydroxyl group is preferably 2000 or less. In consideration of the solubility in an aqueous alkali solution and the balance between the photosensitive properties and the mechanical properties, the number average molecular weight is preferably 94 to 2000, more preferably 108 to 2000, and particularly preferably 108 to 1500.

｛式中、Ｗは単結合又は２価の有機基を示し、Ｒ₁₈、Ｒ₁₉、Ｒ₂₀及びＲ₂₁はそれぞれ独立に水素原子又は１価の有機基を示し、ｒ１及びｒ２はそれぞれ独立に１〜３の整数を示し、ｒ３及びｒ４はそれぞれ独立に０〜４の整数を示し、１≦（ｒ１＋ｒ３）≦４であり、そして１≦（ｒ２＋ｒ４）≦４である。｝
で表される化合物が、露光部の溶解促進効果と感光性樹脂膜の硬化時の溶融を防止する効果とのバランスに優れることから、特に好ましい。 As the compound having a phenolic hydroxyl group, conventionally known compounds can be used, and the following general formula (11):

{Wherein W represents a single bond or a divalent organic group, R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ each independently represents a hydrogen atom or a monovalent organic group, and r 1 and r 2 each independently An integer of 1 to 3, r3 and r4 each independently represents an integer of 0 to 4, 1 ≦ (r1 + r3) ≦ 4, and 1 ≦ (r2 + r4) ≦ 4. }
Is particularly preferable because it is excellent in the balance between the effect of promoting the dissolution of the exposed portion and the effect of preventing the melting of the photosensitive resin film upon curing.

｛式中、Ｚは、単結合、アルキレン基（例えば炭素原子数が１〜１０のアルキレン基）、アルキリデン基（例えば炭素数が２〜１０のアルキリデン基）、それらの水素原子の一部又は全部をハロゲン原子で置換した基、スルホニル基、カルボニル基、エーテル結合、チオエーテル結合又はアミド結合を示し、Ｒ₂₂は、水素原子、ヒドロキシル基、アルキル基又はハロアルキル基を示し、ｌは１〜１０の整数を示し、複数存在する場合のＲ₂₂は互いに同一でも異なっていてもよい。｝
で表される２価の有機基であることが好ましい。 In General Formula (11), the compound in which W is a single bond is a biphenol (dihydroxybiphenyl) derivative. Examples of the divalent organic group represented by W include an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group and a propylene group, an alkylidene group having 2 to 10 carbon atoms such as an ethylidene group, and a phenylene group. An arylene group having 6 to 30 carbon atoms, such as a group in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with a halogen atom such as a fluorine atom, a sulfonyl group, a carbonyl group, an ether bond, a thioether bond, an amide bond Etc. Among these, W represents the following general formula (12):

{In the formula, Z is a single bond, an alkylene group (for example, an alkylene group having 1 to 10 carbon atoms), an alkylidene group (for example, an alkylidene group having 2 to 10 carbon atoms), or a part or all of these hydrogen atoms. Represents a group substituted with a halogen atom, a sulfonyl group, a carbonyl group, an ether bond, a thioether bond or an amide bond, R ₂₂ represents a hydrogen atom, a hydroxyl group, an alkyl group or a haloalkyl group, and l is an integer of 1 to 10 And when there are a plurality of R _{22 s} , they may be the same or different. }
It is preferable that it is a divalent organic group represented by these.

  Examples of the compound having a hydroxymethylamino group and / or an alkoxymethylamino group include (poly) (N-hydroxymethyl) melamine, (poly) (N-hydroxymethyl) glycoluril, and (poly) (N-hydroxymethyl) benzoguanamine. And nitrogen-containing compounds such as (poly) (N-hydroxymethyl) urea, and nitrogen-containing compounds obtained by alkylating all or part of the methylol groups of these compounds. Here, examples of the alkyl group introduced by alkyl etherification include a methyl group, an ethyl group, a butyl group, or a mixture thereof, and may contain an oligomer component that is partially self-condensed. Specific examples include hexakis (methoxymethyl) melamine, hexakis (butoxymethyl) melamine, tetrakis (methoxymethyl) glycoluril, tetrakis (butoxymethyl) glycoluril, tetrakis (methoxymethyl) urea and the like.

  A conventionally well-known thing can be used as a compound which has an epoxy group. Specific examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, glycidyl amine, heterocyclic epoxy resin, polyalkylene glycol diglycidyl ether. Can be mentioned.

  Further, as the component (C), in addition to the above, hydroxymethyl such as bis [3,4-bis (hydroxymethyl) phenyl] ether and 1,3,5-tris (1-hydroxy-1-methylethyl) benzene Aromatic compounds having a group, compounds having a maleimide group such as bis (4-maleimidophenyl) methane and 2,2-bis [4- (4′-maleimidophenoxy) phenyl] propane, compounds having a norbornene skeleton, polyfunctional An acrylate compound, a compound having an oxetanyl group, a compound having a vinyl group, or a blocked isocyanate compound can be used.

  Among the components (C) described above, from the viewpoint of improving sensitivity and heat resistance of the cured film, a compound having a phenolic hydroxyl group, and a compound having a hydroxymethylamino group and / or an alkoxymethylamino group are preferable. From the viewpoint of further improving the resolution and elongation of the coating film, a compound having a hydroxymethylamino group and / or an alkoxymethylamino group is more preferable, and an alkoxymethylamino group obtained by alkyl etherifying all or part of the hydroxymethylamino group is preferable. A compound having an alkoxymethylamino group obtained by alkylating all of the hydroxymethylamino groups is most preferable.

｛式中、Ｒ₂₃〜Ｒ₂₈は、それぞれ独立に炭素数１〜１０のアルキル基を示す。｝
で表される化合物が好ましい。 Among the compounds having an alkoxymethylamino group obtained by alkylating all the hydroxymethylamino groups, the following general formula (13):

{Wherein, R ₂₃ to R ₂₈ represents an alkyl group having 1 to 10 carbon atoms independently. }
The compound represented by these is preferable.

  The blending amount of the component (C) is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of development time, the allowable width of the unexposed part residual film rate, and the characteristics of the cured film 2-30 mass parts is more preferable, and 3-25 mass parts is especially preferable. Moreover, the thermal crosslinking agent mentioned above is used individually by 1 type or in combination of 2 or more types.

[solvent]
The positive 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 these, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ- from the viewpoints of the solubility of the resin, the stability of the resin composition, and the adhesion of the cured film to the substrate. Butyrolactone, propylene 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]
In the photosensitive resin composition of the present invention, various types such as a silane coupling agent, a surfactant or a leveling agent, a thermal acid generator, a dissolution accelerator, a dissolution inhibitor, an acrylic resin, an elastomer, and a dye are included as necessary. Additives can be included.

(Silane coupling agent)
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 Corporation: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydi Methoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyl Trimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyl Dimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-methyl Captobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N- (3-triethoxysilylpropyl) urea (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name LS3610, manufactured by Asmax Co., Ltd .: 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-methoxydipropoxysil Propyl) 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 (manufactured by Azmax Corporation: Product name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.1) aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.2), 2- (trimethoxysilylethyl) ) Pyridine (manufactured by Azmax Co., Ltd .: trade name SIT8396.0), 2- (triethoxysilylethyl) pyridine, 2- (dimethoxysilylmethylethyl) pyridine, 2- (diethoxysilylmethylethyl) pyridine, (3-tri Ethoxysilylpropyl) -t-butylcarbamate, (3-glycidoxypropyl) triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxy , 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-butoxyaluminoxytrieto Xysilane, bis (pentadionato) titanium-O, O'-bis (oxyethyl) -aminopropyltriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilane Diol, n-butylsiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethyl Phenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol 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 the storage stability of the photosensitive resin composition, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy (p-tolyl) silane, diphenylsilanediol, Dimethoxydiphenylsilane, diethoxydiphenylsilane, 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.

(Surfactant or leveling agent)
By blending a surfactant or a leveling agent into the above-mentioned positive photosensitive resin composition, coating properties such as striation (film thickness unevenness) can be prevented and developability can be improved. Examples of such a surfactant or leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenol ether. Commercially available products include Megafax F171, F173, R-08 (Dainippon Ink Chemical Co., Ltd., trade name), Florard FC430, FC431 (Sumitomo 3M Limited, trade name), organosiloxane polymers KP341, KBM303, KBM403. KBM803 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.).

  When using surfactant or a leveling agent, 0.001-5 mass parts is preferable with respect to 100 mass parts of (A) phenol resin, and 0.01-3 mass parts is more preferable.

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

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

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

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

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

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

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

(Dissolution promoter)
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.

(Dissolution inhibitor)
As the dissolution inhibitor, (A) a compound that inhibits the solubility of the phenol resin in an alkaline aqueous solution can be used. Dissolution inhibitors are used to control residual film thickness, development time and contrast. Specific examples thereof include diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium bromide, diphenyliodonium chloride, diphenyliodonium iodide and the like. In the case of using a dissolution inhibitor, the blending amount is preferably 0.01 to 20 parts by weight, and 0.01 to 15 parts by weight with respect to 100 parts by weight of the phenol resin (A), from the viewpoint of sensitivity and an allowable range of development time. Is more preferable, and 0.05 to 10 parts by mass is particularly preferable.

(acrylic resin)
By using an acrylic resin, the thermal shock resistance can be improved while maintaining good photosensitive characteristics.

｛式中、Ｒ₂₉は水素原子又はメチル基を表し、そしてＲ₃₀は炭素数４〜２０のアルキル基を表す。｝

｛式中、Ｒ₂₉は水素原子又はメチル基を表す。｝

｛式中、Ｒ₂₉は水素原子又はメチル基を表し、そしてＲ₃₁は１級、２級又は３級のアミノ基を有する１価の有機基を表す。｝
で表される繰り返し単位の１種又は２種以上を有するアクリル樹脂が好ましい。 As the acrylic resin, the following general formulas (14) to (16):

{In the formula, R ₂₉ represents a hydrogen atom or a methyl group, and R ₃₀ represents an alkyl group having 4 to 20 carbon atoms. }

{Wherein R ₂₉ represents a hydrogen atom or a methyl group. }

{In the formula, R ₂₉ represents a hydrogen atom or a methyl group, and R ₃₁ represents a monovalent organic group having a primary, secondary, or tertiary amino group. }
The acrylic resin which has 1 type or 2 types or more of the repeating unit represented by these is preferable.

  Among them, by using an acrylic resin having the repeating unit represented by the general formula (14) and the repeating unit represented by the general formula (15), the thermal shock resistance can be maintained while maintaining good photosensitive characteristics. Since it can improve, it is more preferable. Further, from the viewpoint of further improving the compatibility with (A) phenolic resin, the adhesion of the cured film to the substrate, mechanical properties and thermal shock resistance, the repeating unit represented by the general formula (14), the general formula It is more preferable to use an acrylic resin having the repeating unit represented by (15) and the repeating unit represented by the general formula (16).

When the acrylic resin has a repeating unit represented by the general formula (14), R ₃₀ is preferably an alkyl group having 4 to 16 carbon atoms from the viewpoint of improving sensitivity, resolution, and thermal shock resistance of the cured film. An alkyl group having 4 carbon atoms (particularly an n-butyl group) is more preferred. (Meth) acrylic acid alkyl ester is mentioned as a polymerizable monomer which gives the repeating unit represented by General formula (14).

｛式中、Ｒ₂₉及びＲ₃₀はそれぞれ一般式（１４）に関して上述したものと同様に定義される。｝
で表される化合物等が挙げられる。 Examples of the (meth) acrylic acid alkyl ester include the following general formula (17):

{Wherein R ₂₉ and R ₃₀ are each defined in the same manner as described above with reference to general formula (14). }
The compound etc. which are represented by these are mentioned.

  Examples of the polymerizable monomer represented by the general formula (17) include (meth) acrylic acid butyl ester, (meth) acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, and (meth) acrylic acid heptyl. Ester, (Meth) acrylic acid octyl ester, (meth) acrylic acid nonyl ester, (meth) acrylic acid decyl ester, (meth) acrylic acid undecyl ester, (meth) acrylic acid dodecyl ester, (meth) acrylic acid tridecyl ester Ester, (meth) acrylic acid tetradecyl ester, (meth) acrylic acid pentadecyl ester, (meth) acrylic acid hexadecyl ester, (meth) acrylic acid heptadecyl ester, (meth) acrylic acid octadecyl ester, (meth) acrylic Acid nonadecyl ester, (meth) acyl Le acid eicosyl ester and the like. These polymerizable monomers are used alone or in combination of two or more.

  Moreover, acrylic acid and methacrylic acid are mentioned as a polymerizable monomer which gives the repeating unit represented by General formula (15).

  Examples of the polymerizable monomer that gives the repeating unit represented by the general formula (16) include aminoethyl (meth) acrylate, N-methylaminoethyl (meth) acrylate, and N, N-dimethylaminoethyl (meth). Acrylate, N-ethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, aminopropyl (meth) acrylate, N-methylaminopropyl (meth) acrylate, N, N-dimethylaminopropyl (meth) Acrylate, N-ethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, aminoethyl (meth) acrylamide, N-methylaminoethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) Acrylamide, N- Tylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, aminopropyl (meth) acrylamide, N-methylaminopropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N- Ethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, piperidin-4-yl (meth) acrylate, 1-methylpiperidin-4-yl (meth) acrylate, 2,2,6,6- Tetramethylpiperidin-4-yl (meth) acrylate, 1,2,2,6,6-pentamethylpiperidin-4-yl (meth) acrylate, (piperidin-4-yl) methyl (meth) acrylate, 2- ( Piperidin-4-yl) ethyl (meta Acrylate, and the like. These polymerizable monomers are used alone or in combination of two or more.

  Among these, piperidine-4 is a polymerizable monomer that gives a repeating unit represented by the general formula (16) from the viewpoint of further improving the adhesion of the cured film to the substrate, mechanical properties, and thermal shock resistance. -Yl (meth) acrylate, 1-methylpiperidin-4-yl (meth) acrylate, 2,2,6,6-tetramethylpiperidin-4-yl (meth) acrylate, 1,2,2,6,6- Examples include pentamethylpiperidin-4-yl (meth) acrylate, (piperidin-4-yl) methyl (meth) acrylate, and 2- (piperidin-4-yl) ethyl (meth) acrylate. Among these, 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate is FA-711MM, and 2,2,6,6-tetramethylpiperidin-4-yl methacrylate is FA-712HM. (Both manufactured by Hitachi Chemical Co., Ltd.) are preferably used. These polymerizable monomers are used alone or in combination of two or more.

  The composition ratio of the repeating unit represented by the general formula (14) is preferably 50 to 95 mol%, more preferably 60 to 90 mol%, based on the total amount of repeating units of the acrylic resin. It is especially preferable that it is 70-85 mol%. When the composition ratio of the repeating unit represented by the general formula (14) is 50 to 95 mol%, the thermal shock resistance of the cured film of the positive photosensitive resin composition can be further improved.

  The composition ratio of the repeating unit represented by the general formula (15) is preferably 5 to 35 mol%, more preferably 10 to 30 mol%, based on the total amount of repeating units of the acrylic resin. It is preferably 15 to 25 mol%, particularly preferably. When the composition ratio of the repeating unit represented by the general formula (15) is 5 to 35 mol%, the compatibility between the acrylic resin and the (A) phenol resin, and the developability of the positive photosensitive resin composition. Can be further improved.

  Further, from the viewpoint of further improving the compatibility between the acrylic resin and the (A) phenol resin, the adhesion of the cured film to the substrate, the mechanical properties, and the thermal shock resistance, it is represented by the above general formulas (14) and (15). And a repeating unit represented by the general formula (16) are more preferable. By making the repeating unit of an acrylic resin into said combination, interaction with an acrylic resin and (A) phenol resin becomes favorable, and compatibility improves more.

  The composition ratio in the case of having the repeating unit represented by the general formula (16) is preferably 0.3 to 10 mol%, and 0.4 to 6 mol% with respect to the total amount of repeating units of the acrylic resin. It is more preferable that it is 0.5-5 mol%.

  The weight average molecular weight of the acrylic resin is preferably 2,000 to 100,000, more preferably 3,000 to 60,000, particularly preferably 5,000 to 50,000. Most preferably, it is 4,000 to 40,000. If the weight average molecular weight is less than 2,000, the thermal shock resistance of the cured film tends to decrease, and if it exceeds 100,000, the compatibility and developability between the acrylic resin and the (A) phenol resin tend to decrease.

  The blending amount of the acrylic resin is preferably 1 to 50 parts by mass, and 3 to 30 parts by mass with respect to 100 parts by mass of the total amount of (A) phenolic resin, from the viewpoints of adhesion, mechanical properties, thermal shock resistance, and photosensitive properties. Is more preferable, and 5 to 20 parts by mass is particularly preferable.

(Elastomer)
The positive photosensitive resin composition can further contain an elastomer. Thereby, the cured film obtained becomes further excellent in terms of flexibility, and the mechanical properties and thermal shock resistance of the cured film can be further improved. A conventionally known elastomer can be used as the elastomer, but the glass transition temperature (Tg) of the polymer constituting the elastomer is preferably 20 ° C. or lower.

  Examples of such elastomers include styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, and silicone elastomers. The elastomer may be a fine particle elastomer. These elastomers can be used alone or in combination of two or more. As a compounding quantity of an elastomer, 1-50 mass parts is preferable with respect to 100 mass parts of (A) phenol resin, 3-40 mass parts is more preferable, and 5-30 mass parts is still more preferable.

(dye)
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.

<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 method for producing a cured relief pattern, comprising: a step of removing an exposed portion with a developer to obtain a relief pattern; and (4) a step of heat-treating the relief pattern. 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 carried out using a developer by selecting from methods such as dipping, paddle, and rotary spraying. By developing, the exposed portion can be eluted and removed from the applied photosensitive resin layer to obtain a relief pattern.

  Developers include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide. An aqueous solution such as quaternary ammonium salts such as quaternary ammonium salts, and a water-soluble organic solvent such as methanol and ethanol, or an aqueous solution to which an appropriate amount of a surfactant is added 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 positive photosensitive resin composition provided by the present invention has an advantage that sufficient film physical properties (for example, reflow treatment applicability) can be realized even when cured at a low temperature such as the above temperature.

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

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

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

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

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

[Synthesis Example 1]
<Synthesis of phenol resin (A-1)>
121. Resorcinol 88.1 g (0.8 mol), 4,4′-bis (methoxymethyl) biphenyl (hereinafter also referred to as “BMMB”) in a separable flask with a Dean-Stark device having a capacity of 0.5 liters. 2 g (0.5 mol), diethyl sulfate 3.9 g (0.025 mol), and diethylene glycol dimethyl ether 140 g were mixed and stirred at 70 ° C. to dissolve the solid matter.

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

  Next, the reaction vessel was cooled in the atmosphere, and 100 g of tetrahydrofuran was separately added thereto and stirred. The reaction diluted solution was dropped into 4 L of water under high-speed stirring to disperse and precipitate the resin, which was recovered, appropriately washed with water, dehydrated and then vacuum dried to obtain a phenol resin that is a copolymer of resorcinol / BMMB. Obtained in 70% yield. The weight average molecular weight calculated | required by standard polystyrene conversion of GPC method of this phenol resin was 13,000.

  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.

  100 g of the obtained phenol resin, 30 g of linseed oil and 0.1 g of trifluoromethanesulfonic acid were mixed and reacted at 120 ° C. for 2 hours. The reaction liquid was cooled to room temperature to obtain an unsaturated hydrocarbon group-containing compound-modified phenol resin (A-1) obtained by reacting a phenol resin condensed with resorcinol / BMMB and an unsaturated hydrocarbon group-containing compound. The weight average molecular weight calculated | required by standard polystyrene conversion of this GPC method of A-1 was 8,000.

[Synthesis Example 2]
<Synthesis of phenol resin (A-2)>
Synthesis was carried out in the same manner as in Synthesis Example 1 using 100.9 g (0.8 mol) of phloroglucinol instead of resorcinol in Synthesis Example 1, and a phenol resin condensed with phloroglucinol / BMMB and an unsaturated hydrocarbon group. An unsaturated hydrocarbon group-containing compound-modified phenol resin (A-2) obtained by reacting the containing compound was obtained. The weight average molecular weight calculated | required by standard polystyrene conversion of this GPC method of A-2 was 15,000.

[Synthesis Example 3]
<Synthesis of phenol resin (A-3)>
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 resorcinol in Synthesis Example 1, and methyl 3,5-dihydroxybenzoate / BMMB was obtained. An unsaturated hydrocarbon group-containing compound-modified phenol resin (A-3) was obtained by reacting a condensed phenol resin with an unsaturated hydrocarbon group-containing compound. The weight average molecular weight calculated | required by standard polystyrene conversion of GPC method of this A-3 was 13,000.

[Synthesis Example 4]
<Synthesis of phenol resin (A-4)>
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, and the unsaturated hydrocarbon group-containing compound was reacted with a phenol resin condensed with resorcinol / BMMB / 2,6-bis (hydroxymethyl) -p-cresol. A hydrocarbon group-containing compound-modified phenol resin (A-4) was obtained with a yield of 77%. The weight average molecular weight calculated | required by standard polystyrene conversion of GPC method of this A-4 was 9,900.

[Synthesis Example 5]
<Synthesis of phenol resin (A-5)>
Phenol / resorcinol mixture {(molar ratio) = 50/50} 100 parts by weight, linseed oil 43 parts by weight and trifluoromethanesulfonic acid 0.1 part by weight were mixed and stirred at 120 ° C. for 2 hours to produce a vegetable oil modified phenol / A resorcinol derivative was obtained. Next, 130 g of vegetable oil-modified phenol / resorcinol derivative, 16.3 g of paraformaldehyde and 1.0 g of oxalic acid were mixed and stirred at 90 ° C. for 3 hours for reaction. Next, after raising the temperature to 120 ° C. and stirring under reduced pressure for 3 hours, the reaction solution is cooled to room temperature under atmospheric pressure, and the reaction product is a vegetable oil-modified phenol / resorcinol / formaldehyde resin (also referred to as phenol / resorcinol novolak). ) (A-5) was obtained. The weight average molecular weight calculated | required by standard polystyrene conversion of this GPC method of A-5 was 16,000.

[Synthesis Example 6]
<Synthesis of phenol resin (A-6)>
100 parts by mass of resorcinol, 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 vegetable oil-modified phenol / resorcinol derivative. Next, 130 g of a vegetable oil-modified resorcinol derivative, 16.3 g of paraformaldehyde and 1.0 g of oxalic acid were mixed and stirred at 90 ° C. for 3 hours for reaction. Next, after raising the temperature to 120 ° C. and stirring under reduced pressure for 3 hours, the reaction solution was cooled to room temperature under atmospheric pressure, and the reaction product vegetable oil-modified resorcinol / formaldehyde resin (also referred to as resorcinol novolak) (A- 6) was obtained. The weight average molecular weight calculated | required by standard polystyrene conversion of this GPC method of A-6 was 17,000.

[Synthesis Example 7]
<Synthesis of phenol resin (A-7)>
Resorcinol / catechol mixture {(molar ratio) = 50/50} 100 parts by weight, 43 parts by weight of linseed oil and 0.1 part by weight of trifluoromethanesulfonic acid were mixed and stirred at 120 ° C. for 2 hours to obtain a vegetable oil-modified resorcinol / A catechol derivative was obtained. Next, 130 g of vegetable oil-modified resorcinol / catechol derivative, 16.3 g of paraformaldehyde and 1.0 g of oxalic acid were mixed and stirred at 90 ° C. for 3 hours for reaction. Next, after raising the temperature to 120 ° C. and stirring under reduced pressure for 3 hours, the reaction solution is cooled to room temperature under atmospheric pressure, and the reaction product vegetable oil-modified resorcinol / catechol / formaldehyde resin (also referred to as resorcinol / catechol novolak). ) (A-7) was obtained. The weight average molecular weight calculated | required by standard polystyrene conversion of GPC method of this A-7 was 17,000.

[Synthesis Example 8]
<Synthesis of phenol resin (A-8)>
100 parts by mass of pyrogallol, 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 vegetable oil-modified pyrogallol derivative. Next, 130 g of vegetable oil-modified pyrogallol derivative, 16.3 g of paraformaldehyde, and 1.0 g of oxalic acid were mixed and reacted at 90 ° C. for 3 hours. Next, after heating to 120 ° C. and stirring under reduced pressure for 3 hours, the reaction solution was cooled to room temperature under atmospheric pressure, and the reaction product, vegetable oil-modified pyrogallol / formaldehyde resin (also called pyrogallol novolac) (A- 8) was obtained. The weight average molecular weight calculated | required by standard polystyrene conversion of this GPC method of A-6 was 18,000.

[Synthesis Example 9]
<Synthesis of phenol resin (A-10)>
Phenolic 75.3 g (0.8 mol), 4,4′-bis (methoxymethyl) biphenyl (hereinafter also referred to as “BMMB”) in a separable flask with a Dean-Stark apparatus of 0.5 liter capacity 121. 2 g (0.5 mol), diethyl sulfate 3.9 g (0.025 mol), and diethylene glycol dimethyl ether 140 g were mixed and stirred at 70 ° C. to dissolve the solid matter.

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

  Next, the reaction vessel was cooled in the atmosphere, and 100 g of tetrahydrofuran was separately added thereto and stirred. The reaction diluted solution was dropped into 4 L of water under high-speed stirring to disperse and precipitate the resin, which was recovered, appropriately washed with water, dehydrated and then vacuum dried to give a phenol / BMMB condensed phenol resin (A-10) Was obtained in a yield of 70%. The weight average molecular weight calculated | required by standard polystyrene conversion of GPC method of this A-10 was 7,000.

[Synthesis Example 10]
<Synthesis of phenol resin (A-11)>
100 parts by weight of phenol, 43 parts by weight of linseed oil and 0.1 parts by weight of trifluoromethanesulfonic acid were mixed and stirred at 120 ° C. for 2 hours to obtain a vegetable oil-modified phenol derivative. Next, 130 g of a vegetable 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 for reaction. Next, after raising the temperature to 120 ° C. and stirring under reduced pressure for 3 hours, the reaction solution was cooled to room temperature under atmospheric pressure, and the reaction product vegetable oil-modified phenol / formaldehyde resin (also referred to as phenol novolac) (A- 11) was obtained. The weight average molecular weight calculated | required by standard polystyrene conversion of this GPC method of A-11 was 16,000.

<Alkali solubility evaluation>
Resins A-1 to A-8, A-10 and A-11 obtained in Synthesis Examples 1 to 10 alone, and these resins and phenol resins not modified with a compound having an unsaturated hydrocarbon group (EP -4020G) was dissolved in γ-butyrolactone so that the solid concentration was 37% by mass. The obtained resin solution is spin-coated on a silicon wafer, and the silicon wafer coated with the spin coat film is pre-baked on a hot plate at 120 ° C. for 180 seconds to form a coating film having a thickness of 10 μm. did. The film thickness was measured with a film thickness measuring device (Lambda Ace) manufactured by Dainippon Screen Mfg. Next, after the film was dipped in a TMAH aqueous solution (AZ300MIF manufactured by AZ Electronic Materials Co., Ltd.) having a temperature of 2.38% by mass and a liquid temperature of 23.0 ° C., the film thickness was measured again, and the dissolution rate of the coating film was calculated. Those having a dissolution rate of 0.01 μm / sec or more at this time were evaluated as an alkali solubility evaluation “◯”, and those having a dissolution rate of less than 0.01 μm / sec were evaluated as an alkali solubility evaluation “x”. The obtained results are shown in Table 1.

表１に記載の組成は、以下のとおりである。

The composition described in Table 1 is as follows.

<(A) Phenolic resin>
A-1: An unsaturated hydrocarbon group-containing compound-modified phenol resin obtained by reacting a resorcinol / BMMB-condensed phenol resin with an unsaturated hydrocarbon group-containing compound, polystyrene-reduced weight average molecular weight (Mw) = 8,000
A-2: Phenol resin condensed with phloroglucinol / BMMB and unsaturated hydrocarbon group-containing compound-modified phenol resin obtained by reacting an unsaturated hydrocarbon group-containing compound, polystyrene equivalent weight average molecular weight (Mw) = 15,000
A-3: Unsaturated hydrocarbon group-containing compound-modified phenol resin obtained by reacting a phenol resin condensed with methyl 3,5-dihydroxybenzoate / BMMB and an unsaturated hydrocarbon group-containing compound, polystyrene-reduced weight average molecular weight (Mw) = 13,000
A-4: Unsaturated hydrocarbon group-containing compound-modified phenol resin obtained by reacting a resorcinol / BMMB / 2,6-bis (hydroxymethyl) -p-cresol condensed phenol resin with an unsaturated hydrocarbon group-containing compound, polystyrene Equivalent weight average molecular weight (Mw) = 9,900
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) = 16,000
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) = 17,000
A-7: Compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms (drying oil) modified phenol resin, polystyrene equivalent weight average molecular weight (Mw) = 17,000
A-8: Compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms (drying oil) modified phenolic resin, polystyrene equivalent weight average molecular weight (Mw) = 18,000
A-9: Cresol novolak resin (cresol / formaldehyde novolak resin, m-cresol / p-cresol (molar ratio) = 60/40, weight average molecular weight in terms of polystyrene = 10,600, manufactured by Asahi Organic Materials Co., Ltd., trade name “ EP4020G ")
A-10: Phenol resin condensed with phenol / BMMB, polystyrene equivalent weight average molecular weight (Mw) = 7,000
A-11: Compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms (drying oil) modified phenol resin, polystyrene equivalent weight average molecular weight (Mw) = 16,000

<Measurement of cured relief pattern cross-sectional angle>
The photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 4 were spin coated on a silicon wafer, and the silicon wafer and the spin coat film were pre-baked on a hot plate at 120 ° C. for 180 seconds on a hot plate. A coating film having a thickness of 10 μm was formed. This coating film was exposed by irradiating an i-line with an exposure amount of 500 mJ / cm ² through a reticle with a test pattern using a stepper NSR2005i8A (manufactured by Nikon Corporation) having an exposure wavelength of i-line (365 nm). Next, it is developed with a developing machine (D-SPIN) at 23 ° C. using a 2.38% tetramethylammonium hydroxide aqueous solution AZ-300MIF (manufactured by AZ Electronic Materials) and rinsed with pure water. In a vertical curing furnace VF200B (manufactured by Koyo Thermo System Co., Ltd.), the curing furnace was charged at 130 ° C. in a nitrogen atmosphere, cured at 130 ° C. for 1 hour, and then heated from 130 ° C. to 200 ° C. at a rate of 5 ° C./min. A cured relief pattern was obtained by curing at 200 ° C. for 1 hour. 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 side wall 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. The obtained results are shown in Table 3.
The evaluation criteria are as follows. The results are listed in Table 2.
○: The cured relief pattern cross-sectional angle when evaluated by the above method is 40 degrees or more.
(Triangle | delta): The hardening relief pattern cross-section angle at the time of evaluating by the said method is more than 20 degree | times and less than 40 degree | times.
X: The cured relief pattern cross-sectional angle when evaluated by the above method is 20 degrees or less.
-: Since alkali solubility was insufficient and a relief pattern could not be formed after development, the evaluation was not possible.

[Example 1]
As shown in Table 2, 100 mass parts of phenol resin (A-1), 10 mass parts of photoacid generator (B-1), and 10 mass parts of cross-linking agent (C-1) had a viscosity after filtration of the composition. A positive photosensitive resin composition was prepared by dissolving in a solvent γ-butyrolactone so as to have 1.2 Pas and filtering through 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 3.

[Examples 2 to 10, Comparative Examples 1 to 4]
A composition comprising the components shown in Table 2 was prepared in the same manner as in Example 1, and the properties of the composition and its cured film were measured in the same manner as in Example 1. The obtained results are shown in Table 3.

  The composition described in Table 2 is as follows.

<(A) Phenolic resin>
See description in Table 1.

（式中、Ｑの内８３％が以下の：

で表される構造であり、残余が水素原子である。） <(B) Photoacid generator>
B-1: Photoacid generator represented by the following formula:

(Wherein 83% of Q is the following:

The remainder is a hydrogen atom. )

<(C) Crosslinking agent>
C-1: 1,1-bis {3,5-bis (methoxymethyl) -4-hydroxyphenyl} methane (manufactured by Honshu Chemical Industry Co., Ltd., trade name: TMOM-pp-BPF)
<(D) Additive (thermal acid generator)>
D-1: Tri-p-tolylsulfonium trifluoromethanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.)

  As can be seen from the results shown in Tables 1 to 3, in each example, low temperature curing (200 ° C.) is possible, the photosensitive resin composition has sufficient alkali solubility, and has a cured relief pattern shape. An excellent cured film (that is, a large cured relief pattern cross-sectional angle) can be formed. Therefore, according to the present invention, it is possible to provide an interlayer insulating film, a surface protective film and the like for a semiconductor element that are excellent in these various characteristics.

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

Claims (17)

(A) phenolic resin,
(B) a compound that generates an acid by light, and
(C) a thermal crosslinking agent,
Including
The positive photosensitive resin composition, wherein the (A) phenol resin comprises (A1) a modified polyphenol resin obtained by modifying a polyphenol resin with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms. object. The polyhydric phenol resin has the following general formula (1):

{In the formula, a is an integer of 2 or 3, b is an integer of 0 to 2, 2 ≦ (a + b) ≦ 4, and R ₁ is a monovalent organic compound having 1 to 20 carbon atoms. Represents a monovalent substituent selected from the group consisting of a group, a halogen atom, a nitro group and a cyano group, and when b is 2, the two R _{1 s} 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 (2):

(In the formula, p is an integer of 1 to 10.)
A divalent organic group selected from the group consisting of a divalent alkylene oxide group represented by the formula (1) and a divalent organic group having an aromatic group. }
The positive photosensitive resin composition of Claim 1 which has a repeating unit represented by these. In the general formula (1), X represents the following general formula (3):

{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. 1 is a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and n ₁ is an integer of 0 to 4, and R ₆ is a halogen atom, a hydroxyl group or a monovalent organic group. , N ₁ is 1, R ₆ is a hydroxyl group or a monovalent organic group having a hydroxyl group, and when n ₁ is an integer of 2 to 4, at least one of R ₆ Is a hydroxyl group or a monovalent organic group having a hydroxyl group, and the plurality of R ₆ may be the same or different. } And / or the following general formula (4):

{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. Represents a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms that is substituted with Y, and Y is a single bond or a chain having 1 to 10 carbon atoms that may be substituted with a fluorine atom -Like aliphatic hydrocarbon group, an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, the following general formula (2):

(In the formula, p is an integer of 1 to 10.)
And an alkylene oxide group represented by the following formula (5):

In a divalent group selected from the group consisting of divalent groups represented. } The positive photosensitive resin composition of Claim 2 containing the bivalent group represented by these. In the general formula (1), X represents the following general formula (6):

The positive photosensitive resin composition of Claim 2 or 3 containing the bivalent organic group represented by these. In the general formula (1), X represents the following general formula (7):

The positive photosensitive resin composition of any one of Claims 2-4 containing the bivalent organic group represented by these. The polyhydric phenol resin has the following general formula (8):

{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 an integer of 2 or 3, and n ₃ is 0 When m ₁ is an integer from ₁ to 500, 2 ≦ (n ₂ + n ₃ ) ≦ 4, and n ₃ is 2, two R ₁₁ are They may be the same or different. } And the following general formula (9):

{In the formula, R ₁₂ and R ₁₃ are each independently a monovalent group having 1 to 10 carbon atoms selected from a hydrocarbon group and an alkoxy group; n ₄ is an integer of 2 or 3; 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 When R 2 is 2, two R ₁₂ may be the same as or different from each other, and when n ₆ is 2 to 3, are a plurality of R ₁₃ the same as each other? Or different. } The positive photosensitive resin composition of any one of Claims 1-5 containing the phenol resin which has both the structures represented by} in the same resin frame | skeleton.   The positive photosensitive resin composition according to claim 1, wherein the polyhydric phenol resin contains a reaction product of polyhydric phenols and aldehydes.   The positive photosensitive resin composition according to claim 7, wherein the polyhydric phenol contains one or both of a dihydric phenol and a trihydric phenol.   The positive photosensitive resin according to any one of claims 1 to 8, wherein the (A) phenol resin further comprises (A2) a non-modified phenol resin not modified with a compound having an unsaturated hydrocarbon group. Resin composition.   The positive photosensitive resin composition according to claim 9, wherein a mass ratio of the (A1) modified polyhydric phenol resin to the (A2) non-modified phenol resin is 5/95 to 95/5.   The positive photosensitive resin composition according to any one of claims 1 to 10, wherein (B) the compound that generates an acid by light is an o-quinonediazide compound.   The positive photosensitive resin composition according to any one of claims 1 to 11, further comprising a compound that generates an acid by heat.   The positive photosensitive resin according to any one of claims 1 to 12, comprising 3 to 100 parts by mass of the compound (B) that generates an acid by light with respect to 100 parts by mass of the (A) phenol resin. Composition. The following steps:
(1) The process of forming the photosensitive resin layer containing the photosensitive resin composition as described in any one of Claims 1-13 on a board | substrate,
(2) a step of exposing the photosensitive resin layer;
(3) removing the exposed portion with a developer to obtain a relief pattern; and (4) heat-treating the relief pattern;
A method for producing a cured relief pattern.   A cured relief pattern produced by the method according to claim 14.   A semiconductor device comprising a semiconductor element and a cured film provided on the semiconductor element, wherein the cured film is the cured relief pattern according to claim 15.   A display device comprising a display element and a cured film provided on the display element, wherein the cured film is the cured relief pattern according to claim 15.