WO2014046062A1 - Photosensitive resin composition - Google Patents

Description

Photosensitive resin composition

The present invention relates to, for example, an insulating material for electronic parts and a photosensitive resin composition used for forming a relief pattern such as a passivation film, a buffer coat film, and an interlayer insulating film in a semiconductor device.

Conventionally, polyimide resins, polybenzoxazole resins, and the like that have excellent heat resistance, electrical properties, mechanical properties, and the like have been widely used for surface protective films and interlayer insulating films used in semiconductor devices. Since these resins have low solubility in various solvents, they are generally often provided as a composition dissolved in a solvent in the form of a precursor.

By the way, countermeasures for removing organic solvents have been demanded due to the recent increase in environmental problems, and various proposals of heat-resistant photosensitive resin materials that can be developed with an alkaline aqueous solution have been made in the same manner as photoresists.

In particular, various methods have been proposed in which an alkaline aqueous solution-soluble hydroxypolyamide resin that becomes a heat-resistant resin after heat curing is used as a photosensitive resin composition in which a photoacid generator such as a naphthoquinonediazide compound is mixed.

The development mechanism of this photosensitive resin composition is that the naphthoquinonediazide compound (that is, the photosensitive diazoquinone compound) and the polybenzoxazole (PBO) precursor in the unexposed area are exposed to light with a low dissolution rate in an alkaline aqueous solution. This makes use of the fact that the photosensitive diazoquinone compound is chemically changed to an indenecarboxylic acid compound to increase the dissolution rate of the exposed portion in the alkaline aqueous solution. By utilizing the difference in the dissolution rate with respect to the developer between the exposed portion and the unexposed portion, a relief pattern composed of the unexposed portion can be produced.

The above-described composition can form a positive relief pattern by exposure and development with an alkaline aqueous solution. Further, it has thermosetting film characteristics by heating.

By the way, in the manufacturing process of semiconductors and the like, fine processing is currently in progress, and the interval between patterns is becoming shorter. Therefore, when the film reduction during development is increased, in the unexposed area adjacent to the exposed exposed area, the dissolution rate of the unexposed area is low, but the developer contacts the developer not only from the top but also from the side. Therefore, the pattern shape becomes too thin, and the reliability of the semiconductor package is lowered in the manufacturing process of the semiconductor device.

Therefore, development can be performed with almost no unexposed portion dissolved (this phenomenon is said to have a high development residual film ratio, and in this disclosure, a development residual film ratio of 95 to 100% is defined as a high development residual film ratio). Necessary.

However, in the case where the development residual film ratio is increased, a high exposure amount is required for developing the exposed portion (this is said to be low sensitivity).

A system in which a phenol resin is added to a heat-resistant resin precursor is disclosed as a technique for increasing the residual film and increasing sensitivity during development. Specifically, a photosensitive resin composition (Patent Document 1) containing a polyamic acid silyl ester, a diazonaphthoquinone sulfonic acid ester and a phenol novolac resin, a hydroxy polyamide resin, a photosensitive diazonaphthoquinone compound and a specific phenol resin And a photosensitive resin composition (Patent Document 3) containing a hydroxy polyamide resin having a specific structure, a quinonediazide compound, a novolac resin and / or polyhydroxystyrene.

Furthermore, a photosensitive resin composition (Patent Document 4) is proposed in which a polyamide resin having a phenolic hydroxyl group contains a phenol resin, a photosensitive diazoquinone compound, a polyfunctional methylol compound, and a solvent.

Also, a photosensitive resin composition (Patent Document 5) using a hydroxypolyamide having at least one ester or thioester structure in the polymer main skeleton is described as a technique for increasing the residual film and increasing the sensitivity.

Japanese Patent No. 3369344 Japanese Patent No. 3966667 Japanese Patent No. 4548001 Japanese Patent Laid-Open No. 2005-250160 International Publication No. 2011-13587 Pamphlet

However, in the phenol resins described in Patent Documents 1 to 5, although the film surface after coating the resin composition is uniform, the film surface after development is whitened due to low compatibility with the hydroxypolyamide resin. There was a problem that phenomena and surface roughness occurred.
Accordingly, an object of the present invention is to provide a photosensitive resin composition having a high development residual film ratio and high sensitivity, and a uniform surface after development.

As a result of intensive studies and repeated experiments in view of the above-described problems of the prior art, the present inventor has found that the above problems can be solved by using a combination of a hydroxypolyamide derivative and a phenol resin having a specific structure. Invented the invention. That is, the present invention is as follows.

（式中、Ｒ₁及びＲ₂は、それぞれ独立に、炭素数２～６０の２価から８価の有機基を示し、Ｒ₃、Ｒ₄、Ｒ₅及びＲ₆は、それぞれ独立に、水素原子又は炭素数１～２０の１価の有機基を示し、ｄ及びｅは、それぞれ独立に、０～２の整数であって同時に０になることはなく、ｆ及びｇは、それぞれ独立に、０～４の整数であり、そしてｎは正の整数である。）
で表される構造単位を主成分とするポリマーと、
　（ｂ）キノンジアジド化合物と、
　（ｃ）フェノール樹脂と、を含有し、
　該（ｃ）フェノール樹脂が、下記一般式（２），（３），及び（４）、並びに一般式群（５）：

（式中、Ｒ₇及びＲ₈は、それぞれ独立に、炭素数１～１０の１価の有機基を示し、ｈ及びｊは、それぞれ独立に、１～３の整数であり、ｉ及びｋは、それぞれ独立に、０～２の整数であり、１≦（ｈ＋ｉ）≦４、１≦（ｊ＋ｋ）≦４を満たし、ｍ１は０又は正の整数であり、そしてｍ２は正の整数である。）

（式中、Ｒ₉及びＲ₁₀は、それぞれ独立に、炭素数１～１０の１価の有機基を示し、ｌは２又は３であり、ｐは１～３の整数であり、ｏ及びｑは、それぞれ独立に、０～２の整数であり、２≦（ｌ＋ｏ）≦４、１≦（ｐ＋ｑ）≦４を満たし、ｍ３は正の整数であり、そしてｍ４は０又は正の整数である。）

（式中、Ｒ₁₁及びＲ₁₂は、それぞれ独立に、炭素数１～１０の１価の有機基を示し、ｒ及びｕは、それぞれ独立に、１～３の整数であり、ｓ及びｖは、それぞれ独立に、０～２の整数であり、１≦（ｒ＋ｓ）≦４、１≦（ｕ＋ｖ）≦４を満たし、ｍ５は０又は正の整数であり、そしてｍ６は正の整数であり、ｍ１１は正の整数であり、Ｐ₁は、水酸基、カルボキシル基又はアミノ基で置換されていてもよい炭素数１～２０の１価の炭化水素基である。）

｛式中、Ｒ₁₃は、それぞれ独立に、炭素数１～１０の１価の有機基を示し、ｗは１～３の整数であり、ｘは０～２の整数であり、１≦（ｗ＋ｘ）≦４を満たし、ｍ７は正の整数であり、そしてｍ８は０又は正の整数であり、Ｙは、下記式群（５’）：

（Ｐ₄，及びＰ₅は、それぞれ独立に、水素原子、炭素数１～２０のフッ素で置換されていてもよい１価の脂肪族基、又は炭素数６～２０の置換若しくは非置換の１価の芳香族基である。）
から成る群から選ばれる２価の有機基である。｝
から成る群から選択される少なくとも１つで表される構造を有する、ポジ型感光性樹脂組成物。
［２］
　前記フェノール樹脂が、下記一般式（４’）

（式中、Ｒ₁₁及びＲ₁₂は、それぞれ独立に、炭素数１～１０の１価の有機基を示し、ｒ、ｔ及びｕは、それぞれ独立に、１～３の整数であり、ｓ及びｖは、それぞれ独立に、０～２の整数であり、１≦（ｒ＋ｓ）≦４、１≦（ｕ＋ｖ）≦４を満たし、ｍ５は０又は正の整数であり、そしてｍ６は正の整数である。）
で表される構造を有する、上記［１］に記載のポジ型感光性樹脂組成物。
［３］
　前記フェノール樹脂が、前記一般式群（５）から成る群から選択される少なくとも１つで表される構造であって前記Ｙが下記一般式（５’’）：

（Ｐ₄，及びＰ₅は、それぞれ前記式群（５’）において定義したのと同じである。）
で表される構造を有する、上記［１］に記載のポジ型感光性樹脂組成物。
［４］
　前記一般式（１）のＲ₁若しくはＲ₂又はこれらの両者がエステル結合を有する構造である、上記［１］～［３］のいずれか１項に記載のポジ型感光性樹脂組成物。
［５］
　前記一般式（１）のＲ₁又はＲ₂が、下記一般式（６）：

（式中、Ｒ₁₈、Ｒ₁₉及びＲ₂₀は、それぞれ独立に、炭素数２～６０の２価の有機基を示し、Ｒ₁₈、Ｒ₁₉及びＲ₂₀のうち少なくとも１つは、脂環式構造又は脂肪族構造を有し、そしてｍは、０又は１である。）
で表される構造を有する、上記［１］～［４］のいずれか１項に記載のポジ型感光性樹脂組成物。
［６］
　前記一般式（１）のＲ₃又はＲ₄が、下記一般式（７）：

（式中、Ｒ₂₁は炭素数１～１９の１価の有機基を示す。）
で表される構造を有する、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］
　（Ａ）上記［１］～［６］のいずれか１項に記載の感光性樹脂組成物で構成される感光性樹脂層を基板上に形成する工程、
　（Ｂ）該感光性樹脂層を露光する工程、
　（Ｃ）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
　（Ｄ）該レリーフパターンを加熱する工程、
［８］
　上記［７］に記載の方法により製造された、硬化レリーフパターン。
［９］
　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［８］に記載の硬化レリーフパターンである、半導体装置。
［１０］
　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［８］に記載の硬化レリーフパターンである、表示体装置。
［１１］
　ポリイミド及びポリベンゾオキサゾールから成る群から選択される少なくとも１種の樹脂とフェノール樹脂とを含有する硬化膜であって、
　該硬化膜が、下記条件下、
　　プラズマ種：マイクロ波
　　処理ガス：Ｏ₂
　　処理時間：６０秒
のドライエッチング処理後に原子間力顕微鏡（ＡＦＭ）を用いて測定したときに、算術平均表面粗さ：０．５～５．０ｎｍを有する、硬化膜。
［１２］
　空気雰囲気下、２４０℃にて１０時間熱処理したときの重量減少変化率が０．１～３．０％である、上記［１１］に記載の硬化膜。
［１３］
　前記ポリイミド及びポリベンゾオキサゾールから成る群から選択される少なくとも１種の樹脂：１００質量部に対し、前記フェノール樹脂：２０～２００質量部を含有する、上記［１１］又は［１２］に記載の硬化膜。 [1]
(A) The following general formula (1):

(Wherein R ₁ and R ₂ each independently represents a divalent to octavalent organic group having 2 to 60 carbon atoms, and R ₃ , R ₄ , R ₅ and R ₆ are each independently hydrogen. An atom or a monovalent organic group having 1 to 20 carbon atoms, d and e are each independently an integer of 0 to 2 and are not simultaneously 0, and f and g are each independently An integer from 0 to 4, and n is a positive integer.)
A polymer whose main component is a structural unit represented by:
(B) a quinonediazide compound;
(C) a phenol resin,
The (c) phenolic resin has the following general formulas (2), (3), and (4), and general formula group (5):

(Wherein R ₇ and R ₈ each independently represents a monovalent organic group having 1 to 10 carbon atoms, h and j are each independently an integer of 1 to 3, i and k are Each independently represents an integer of 0 to 2, satisfying 1 ≦ (h + i) ≦ 4, 1 ≦ (j + k) ≦ 4, m1 is 0 or a positive integer, and m2 is a positive integer. )

(Wherein R ₉ and R ₁₀ each independently represents a monovalent organic group having 1 to 10 carbon atoms, l is 2 or 3, p is an integer of 1 to 3, o and q Are each independently an integer of 0 to 2, satisfying 2 ≦ (l + o) ≦ 4, 1 ≦ (p + q) ≦ 4, m3 is a positive integer, and m4 is 0 or a positive integer .)

(Wherein R ₁₁ and R ₁₂ each independently represents a monovalent organic group having 1 to 10 carbon atoms, r and u are each independently an integer of 1 to 3, and s and v are Each independently an integer from 0 to 2, satisfying 1 ≦ (r + s) ≦ 4, 1 ≦ (u + v) ≦ 4, m5 is 0 or a positive integer, and m6 is a positive integer, m11 is a positive integer, and P ₁ is a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group, a carboxyl group or an amino group.

{In the formula, each R ₁₃ independently represents a monovalent organic group having 1 to 10 carbon atoms, w is an integer of 1 to 3, x is an integer of 0 to 2, and 1 ≦ (w + x ) ≦ 4, m7 is a positive integer, and m8 is 0 or a positive integer, and Y is the following formula group (5 ′):

(P ₄ and P ₅ are each independently a hydrogen atom, a monovalent aliphatic group which may be substituted with fluorine having 1 to 20 carbon atoms, or substituted or unsubstituted 1 having 6 to 20 carbon atoms. Valent aromatic group.)
A divalent organic group selected from the group consisting of }
A positive photosensitive resin composition having a structure represented by at least one selected from the group consisting of:
[2]
The phenol resin is represented by the following general formula (4 ′)

(Wherein R ₁₁ and R ₁₂ each independently represents a monovalent organic group having 1 to 10 carbon atoms, r, t and u are each independently an integer of 1 to 3; v is each independently an integer of 0 to 2, satisfies 1 ≦ (r + s) ≦ 4, 1 ≦ (u + v) ≦ 4, m5 is 0 or a positive integer, and m6 is a positive integer is there.)
The positive photosensitive resin composition according to the above [1], which has a structure represented by:
[3]
The phenol resin is a structure represented by at least one selected from the group consisting of the general formula group (5), and the Y is represented by the following general formula (5 ″):

(P ₄ and P ₅ are the same as defined in the formula group (5 ′).)
The positive photosensitive resin composition according to the above [1], which has a structure represented by:
[4]
The positive photosensitive resin composition according to any one of [1] to [3] above, wherein R ₁ or R ₂ of the general formula (1) or both of them has a structure having an ester bond.
[5]
R ₁ or R _{2 in} the general formula (1) is represented by the following general formula (6):

(Wherein R ₁₈ , R ₁₉ and R ₂₀ each independently represents a divalent organic group having 2 to 60 carbon atoms, and at least one of R ₁₈ , R ₁₉ and R ₂₀ is alicyclic. Having a structure or an aliphatic structure, and m is 0 or 1.)
The positive photosensitive resin composition according to any one of the above [1] to [4], which has a structure represented by:
[6]
R ₃ or R _{4 in} the general formula (1) is represented by the following general formula (7):

(In the formula, R ₂₁ represents a monovalent organic group having 1 to 19 carbon atoms.)
The positive photosensitive resin composition according to any one of the above [1] to [5], which has a structure represented by:
[7]
(A) forming a photosensitive resin layer composed of the photosensitive resin composition according to any one of [1] to [6] above on a substrate;
(B) a step of exposing the photosensitive resin layer;
(C) removing the exposed portion with a developer to obtain a relief pattern; and (D) heating the relief pattern.
[8]
A cured relief pattern produced by the method according to [7] above.
[9]
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 [8].
[10]
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 the above [8].
[11]
A cured film containing at least one resin selected from the group consisting of polyimide and polybenzoxazole and a phenol resin,
The cured film has the following conditions:
Plasma type: Microwave Processing gas: O ₂
Treatment time: A cured film having an arithmetic average surface roughness of 0.5 to 5.0 nm as measured using an atomic force microscope (AFM) after a dry etching treatment of 60 seconds.
[12]
The cured film as described in [11] above, which has a weight loss change rate of 0.1 to 3.0% when heat-treated at 240 ° C. for 10 hours in an air atmosphere.
[13]
The curing according to [11] or [12] above, wherein the phenol resin: 20 to 200 parts by mass with respect to 100 parts by mass of at least one resin selected from the group consisting of the polyimide and polybenzoxazole film.

According to the present invention, it is possible to provide a photosensitive resin composition having a high development residual film ratio and high sensitivity, which can prevent whitening after development and has a uniform surface.

FIG. 10 is a diagram showing ¹³ C-NMR results of a hydroxypolyamide resin (P-2) obtained in Synthesis Example 6. FIG. 10 is a diagram showing a ¹ H-NMR result of a phenol resin (N-1) obtained in Synthesis Example 8.

Hereinafter, exemplary 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.

（式中、Ｒ₁及びＲ₂は、それぞれ独立に、炭素数２～６０の２価から８価の有機基を示し、Ｒ₃、Ｒ₄、Ｒ₅及びＲ₆は、それぞれ独立に、水素原子又は炭素数１～２０の１価の有機基を示し、ｄ及びｅは、それぞれ独立に、０～２の整数であって同時に０になることはなく、ｆ及びｇは、それぞれ独立に、０～４の整数であり、そしてｎは正の整数である。）
で表される構造単位を主成分とするポリマー（以下、ポリマー（ａ）ともいう）と、（ｂ）キノンジアジド化合物（以下、キノンジアジド化合物（ｂ）ともいう）と、（ｃ）フェノール樹脂（以下、フェノール樹脂（ｃ）ともいう）とを含有する。ここで主成分とは、５０質量％超を意味する。以下これらの構造及びその他の成分について詳細に説明する。なお、本明細書では、特に明記しない限り、一般式において同一符号で表されている構造は、分子中に複数存在する場合に、互いに同一であるか、又は異なっていてもよい。また２種以上の繰り返し単位が示される場合の繰り返し配列は特記がない限り限定されず、ランダム、ブロック及び交互のいずれでもよい。 <Photosensitive resin composition>
In the present embodiment, the photosensitive resin composition has (a) general formula (1):

(Wherein R ₁ and R ₂ each independently represents a divalent to octavalent organic group having 2 to 60 carbon atoms, and R ₃ , R ₄ , R ₅ and R ₆ are each independently hydrogen. An atom or a monovalent organic group having 1 to 20 carbon atoms, d and e are each independently an integer of 0 to 2 and are not simultaneously 0, and f and g are each independently An integer from 0 to 4, and n is a positive integer.)
(B) a quinonediazide compound (hereinafter also referred to as a quinonediazide compound (b)), (c) a phenol resin (hereinafter referred to as a polymer). Phenol resin (also referred to as (c)). Here, the main component means more than 50% by mass. Hereinafter, these structures and other components will be described in detail. In the present specification, unless otherwise specified, when a plurality of structures represented by the same symbol in the general formula are present in a molecule, they may be the same as or different from each other. Further, the repeating arrangement in the case where two or more kinds of repeating units are shown is not limited unless otherwise specified, and may be any of random, block and alternating.

The polymer (a) in the present invention is a polymer mainly composed of a structural unit having a repeating number n in the general formula (1) (also referred to as a structural unit represented by the general formula (1) in the present disclosure). Or it can become a polymer which has an imide ring, an oxazole ring, etc. with a suitable catalyst. The polymer (a) preferably includes a polyamic acid, a polyamic acid ester of a polyimide precursor, and a polyhydroxyamide of a polybenzoxazole precursor. When the polymer (a) becomes a polymer having a ring structure, heat resistance and solvent resistance are dramatically improved. In the polymer (a), the structural unit represented by the general formula (1) may be one type or two or more types. When two or more types of structural units are present, the arrangement of the structural units may be a block or random, and the repeat number n is the total number of repeats of the two or more types of structural units.

The polymer having the structural unit represented by the general formula (1) as a main component is produced from dicarboxylic acid, tricarboxylic acid, tetracarboxylic acid and derivatives thereof and bis (aminophenol), and has a phenol group at the ortho position of the amide bond. A polybenzoxazole (hereinafter also referred to as PBO) precursor having a polyamide structure, or a polyamide structure having a phenol group produced from dicarboxylic acid, tricarboxylic acid, tetracarboxylic acid and derivatives thereof and diaminophenol It is preferable.

The repeating unit represented by the general formula (1) includes, for example, a dicarboxylic acid having a structure of R ₁ (OR ₃ ) _d (COOR ₅ ) _f (COOH) ₂ and R ₂ (NH ₂ ) ₂ (OR ₄ ) _e. (COOR ₆ ) It can be obtained by polycondensation with a diamine having a _g structure.

In the general formula (1), n is not limited as long as it is a positive integer, but is preferably in the range of 1 to 1000, more preferably in the range of 3 to 50, and in the range of 3 to 30 from the viewpoint of developability. Most preferred.

から選ばれる４価の有機基であるビスアミノフェノール化合物等が挙げられる。 The diamine having the R ₂ (NH ₂ ) ₂ (OR ₄ ) _e (COOR ₆ ) _g structure will be described.
For example, as the bisaminophenol compound in which R ₄ is a hydrogen atom and e is 2, for example, 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4 '-Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino -4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2- Bis- (4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2- Su- (4-amino-3-hydroxyphenyl) propane, 4,4′-diamino-3,3′-dihydroxybenzophenone, 3,3′-diamino-4,4′-dihydroxybenzophenone, 4,4′-diamino -3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, And 1,3-diamino-4,6-dihydroxybenzene, and R ₂ is represented by the following formula group:

And a bisaminophenol compound which is a tetravalent organic group selected from:

Among these bisaminophenol compounds, those particularly preferable from the viewpoints of solubility in an alkali developer and heat resistance are compounds in which R ₂ is a tetravalent organic group selected from the above formula group.

Bis (aminophenol) _{(e.g., R 2 (NH 2) 2} (OR 4) e (COOR 6) that R ₂ in _g structures selected from the above expression group) in the bond joining the benzene rings On the other hand, the meta position may be an amino group, the para position may be a hydroxyl group, the meta position may be a hydroxyl group, and the para position may be an amino group. In addition, a hydroxyl group is preferable at the para position.

（式中、Ｘ₃は炭素数２～６０の４価の有機基である。）
で表される分子内に２組の互いにオルト位にあるアミド結合とフェノール性水酸基とを有するジアミン（以下、「分子内にＰＢＯ前駆体構造を有するジアミン」という。）を使用することもできる。 In addition, as the diamine having the R ₂ (NH ₂ ) ₂ (OR ₄ ) _e (COOR ₆ ) _g structure, the following structure:

(Wherein X ₃ is a tetravalent organic group having 2 to 60 carbon atoms.)
It is also possible to use two pairs of diamines having an amide bond in the ortho position and a phenolic hydroxyl group (hereinafter referred to as “diamine having a PBO precursor structure in the molecule”).

X ₃ is not limited as long as it is a tetravalent organic group having 2 to 60 carbon atoms, but is exemplified as a preferred organic group represented by R ₂ described above from the viewpoint of solubility in an alkali developer and heat resistance. A structure is preferred.

More preferable examples of the diamine having a PBO precursor structure in the molecule include the following structures.

As a method for producing the compound represented by the above structure, there can be exemplified a method in which two molecules of nitrobenzoic acid are reacted with the above-described bisaminophenol and then the nitro group is reduced to an amino group.

（式中、Ｙ₃は炭素数２～６０の２価の有機基を示す。）
を有する化合物を使用することができる。 As the diamine having a _{R 2 (NH 2) 2 (} OR 4) e (COOR 6) g structure, the following structure:

(In the formula, Y ₃ represents a divalent organic group having 2 to 60 carbon atoms.)
Can be used.

Y ₃ in the above structure is not limited as long as it is a divalent organic group having 2 to 60 carbon atoms, but from the viewpoint of solubility in an alkali developer and heat resistance, examples of the organic group represented by R ₁ will be described later. Preferably at least one of the listed organic groups.

Preferable examples of such compounds include the following structures.

The above compound can be obtained, for example, by reacting a dicarboxylic acid dichloride compound with two molecules of nitroaminophenol and reducing the nitro group to an amino group.

（式中、Ｙ₄は炭素数４～６０の４価の有機基を示し、そしてＲ₆は炭素数１～２０の１価の炭化水素基を示す。）
を有する化合物が挙げられる。 In addition, as a diamine having an R ₂ (NH ₂ ) ₂ (OR ₄ ) _e (COOR ₆ ) _g structure, a compound having two polyimide precursor structures in the molecule (hereinafter referred to as “PI precursor structure in the molecule”). Can also be used. Examples of such compounds include the following structures:

(Wherein Y ₄ represents a tetravalent organic group having 4 to 60 carbon atoms, and R ₆ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms.)
The compound which has is mentioned.

（Ｒ₆は水素又は炭素数１～２０の１価の炭化水素基を示す。） More specific examples of such compounds include the following structures.

(R ₆ represents hydrogen or a monovalent hydrocarbon group having 1 to 20 carbon atoms.)

As a method for producing a bisaminophenol having a PI precursor structure in the molecule, for example, a tetracarboxylic dianhydride and a dicarboxylic acid ring-opened with a monoalcohol or a monoamine, a hydroxyl group and a nitro An example is a method in which two molecules of aniline having a group are condensed and then the nitro group is reduced.

Next, as a diamine having a raw material R ₂ (NH ₂ ) ₂ (OR ₄ ) _e (COOR ₆ ) _g structure, a diamine in which both e and g are 0 will be described. Such a diamine is advantageous in the case of adjusting the solubility in an alkali developer. Examples of these diamine compounds include aromatic diamines. Aromatic diamines are advantageous from the viewpoint of heat resistance.

Examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 2,2'-bis (4-aminophenyl) propane 2,2'-bis (4-aminophen Nyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4-methyl-2 , 4-bis (4-aminophenyl) -1-pentene, 4-methyl-2,4-bis (4-aminophenyl) -2-pentene, 1,4-bis (α, α-dimethyl-4-amino) Benzyl) benzene, imino-di-p-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4-methyl-2,4-bis (4-aminophenyl) pentane, 5 (or 6)- Amino-1- (4-aminophenyl) -1,3,3-trimethylindane, bis (p-aminophenyl) phosphine oxide, 4,4′-diaminoazobenzene, 4, '-Diaminodiphenylurea, 4,4'-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-amino) Phenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] benzophenone, 4,4′-bis (4-aminophenoxy) diphenylsulfone, 4,4′-bis [4- (Α, α-dimethyl-4-aminobenzyl) phenoxy] benzophenone, 4,4′-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] diphenyl sulfone, 4,4′-diaminobiphenyl, 4,4′-diaminobenzophenone, phenylindanediamine, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3, 3′-dimethyl-4,4′-diaminobiphenyl, o-toluidine sulfone, 2,2-bis (4-aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone, bis (4-aminophenoxyphenyl) Sulfide, 1,4- (4-aminophenoxyphenyl) benzene, 1,3- (4-aminophenoxyphenyl) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4′-di- (3 -Aminophenoxy) diphenyl sulfone, 4,4'-diaminobenzanilide and the like.

In addition, the hydrogen atom of the aromatic nucleus of the aromatic diamine may be substituted with a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a methoxy group, a cyano group, a phenyl group, or the like.

Silicon diamine can also be selected as part or all of the diamine. Examples of silicon diamines include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (4-aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetramethyldi Examples thereof include siloxane, 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetraphenyldisiloxane, and the like.

Next, a dicarboxylic acid having a structure of R ₁ (OR ₃ ) _d (COOR ₅ ) _f (COOH) ₂ will be described.

（式中、Ａ₁は、－ＣＨ₂－、－Ｏ－、－Ｓ－、－ＳＯ₂－、－ＣＯ－、－ＮＨＣＯ－、－Ｃ（ＣＦ₃）₂－、及び単結合からなる群より選ばれる２価の基を示し、環炭素と結合しているｋ個のＬ₁は、それぞれ独立に水素原子、ハロゲン原子、炭化水素基、アミド基、ウレア基、イミド基、及びウレタン基からなる群より選ばれる基を示し、そしてｋ＝４である。）、

（式中、ｎ₁₀は、１～１２の整数である。）、及び

（式中、Ｌ₂、Ｌ₃及びＬ₄は、それぞれ独立に水素原子又はメチル基を示し、そしてＬ₅は、水素原子、メチル基又は水酸基を示す。）。 In R ₁ (OR ₃ ) _d (COOR ₅ ) _f (COOH) ₂ , d = f = 0 may be satisfied. Such a dicarboxylic acid is advantageous in the case of adjusting the solubility in an alkali developer. Examples of R ₁ when d = f = 0 include the following structures.

Wherein A ₁ is selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, and a single bond. Each of k L ₁ bonded to a ring carbon is independently composed of a hydrogen atom, a halogen atom, a hydrocarbon group, an amide group, a urea group, an imide group, and a urethane group. A group selected from the group and k = 4).

(Where n ₁₀ is an integer from 1 to 12), and

(In the formula, L ₂ , L ₃ and L ₄ each independently represent a hydrogen atom or a methyl group, and L ₅ represents a hydrogen atom, a methyl group or a hydroxyl group).

Among the above, a typical compound as a dicarboxylic acid having a tricyclodecane skeleton includes bis (carboxy) tricyclo [5,2,1,02,6] decane. As a production example of the compound, a synthesis example of International Publication No. 2009/081950 pamphlet can be exemplified.

（式中、Ｂは、－ＣＨ₂－、－Ｏ－、－Ｓ－、－ＳＯ₂－、－ＣＯ－、－ＮＨＣＯ－、－Ｃ（ＣＦ₃）₂－、及び－ＣＯＯ－からなる群から選択される２価の基を示す。） Furthermore, as dicarboxylic acid when d = 0 and f = 2 in R ₁ (OR ₃ ) _d (COOR ₅ ) _f (COOH) ₂ , tetracarboxylic dianhydride is replaced with monoalcohol or monoamine, etc. Ring-opened dicarboxylic acids can also be used. Examples of monoalcohol include methanol, ethanol, propanol, isopropanol, butanol, t-butanol, benzyl alcohol, and the like. Examples of monoamines include butylamine and aniline. Examples of the tetracarboxylic dianhydride include compounds represented by the following chemical formula.

Wherein B is selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, and —COO—. Indicates the divalent group selected.)

Alternatively, tetracarboxylic dianhydride can be reacted with bisaminophenol or diamine, and the resulting carboxylic acid residue can be esterified or amidated with a monoalcohol or monoamine.

（式中、Ｘ₅は、少なくとも２個の炭素原子を有する３価又は４価の有機基を示し、Ｒ₅は、炭素数１～２０の１価の炭化水素基を示し、そして、ｎ₁₁は、１又は２の整数である。） In addition, in R ₁ (OR ₃ ) _d (COOR ₅ ) _f (COOH) ₂ , R ₃ is hydrogen, d = 1 or 2, and f = 2. A dicarboxylic acid having an amide bond at the ortho position and a phenolic hydroxyl group can also be used. Examples of such a dicarboxylic acid include compounds represented by the following formula.

Wherein X ₅ represents a trivalent or tetravalent organic group having at least 2 carbon atoms, R ₅ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and n ₁₁ Is an integer of 1 or 2.)

Examples of the method for producing the compound represented by the above formula include the structure of bis (aminophenol) or R ₂ (NH ₂ ) ₂ (OH) having the structure of R ₂ (NH ₂ ) ₂ (OH) ₂ described above. An example is a method in which two molecules of trimellitic acid chloride are reacted with diaminophenol having an acid, and an acid anhydride and an alcohol are further reacted.

As a method of polycondensation of the dicarboxylic acid and bisaminophenol compound (diamine) for synthesizing polyhydroxyamide, diacid chloride is obtained using dicarboxylic acid and thionyl chloride, and then bisamino Examples thereof include a method in which phenol (diamine) is allowed to act or a method in which dicarboxylic acid and bisaminophenol (diamine) are polycondensed with dicyclohexylcarbodiimide. In the method using dicyclohexylcarbodiimide, hydroxybenztriazole can be allowed to act simultaneously.

In the present embodiment, R ₁ and / or R ₂ in the general formula (1) preferably has a structure having an ester bond. The polymer R ₁ and / or R _{2 of} the polymer mainly composed of the structural unit represented by the general formula (1) according to the present embodiment has an ester structure, so that it is compatible with the phenol resin (c) described later. And has a specific effect that the surface condition after development is particularly good. The reason for this is not clear, but the inventor presumes the following reason. The polymer having the structural unit represented by the general formula (1) as a main component has an amide bond, and the bond between the amide and the amide is strong due to the polarity of the amide, and it is easy to associate between the polymers. Compatibility is difficult to increase. On the other hand, the ester and the phenol resin are close in polarity, and the amide bond ratio is relatively reduced, so that the compatibility between the polymer (a) and the phenol resin (c) is increased.

（式中、Ａｒ₁及びＡｒ₂はそれぞれ独立に芳香族基を示す）
が挙げられる。 As an aspect of the ester structure, a structure represented by the following general formula (6) and the following structure:

(In the formula, Ar ₁ and Ar ₂ each independently represent an aromatic group)
Is mentioned.

（式中、Ｒ₁₈、Ｒ₁₉及びＲ₂₀は、それぞれ独立に、炭素数２～６０の２価の有機基を示し、Ｒ₁₈、Ｒ₁₉及びＲ₂₀のうち少なくとも１つは、脂環式構造又は脂肪族構造を有し、そしてｍは、０又は１である。） From the viewpoint of lithography, it is more preferable that R ₁ or R ₂ in the general formula (1) has a structure represented by the following general formula (6).

(Wherein R ₁₈ , R ₁₉ and R ₂₀ each independently represents a divalent organic group having 2 to 60 carbon atoms, and at least one of R ₁₈ , R ₁₉ and R ₂₀ is alicyclic. Having a structure or an aliphatic structure, and m is 0 or 1.)

The structure represented by the general formula (6) includes, for example, (α) a hydroxyl group-containing compound having the structure of R _{18 in} the general formula (6), (β) R ₁₉ in the general formula (6), and It can be obtained by reacting at least one carboxylic acid compound selected from the group consisting of polyvalent carboxylic acids having the structure of R ₂₀ and derivatives thereof.

Hereinafter, the hydroxyl group-containing compound having the structure (α) R ₁₈ will be described.

R ₁₈ is a residue derived from a divalent phenol compound or an alcohol compound. Examples of the hydroxyl group-containing compound having the structure of R ₁₈ include a phenol compound and an alcohol compound. Specific examples of the divalent phenol compound include hydroquinone, resorcinol, 4,4′-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl, 4,4′-dihydroxydiphenylmethane, 4,4′-methylenebis (2-methylphenol). ), 4,4'-methylenebis (2,6-dimethylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 4,4'-ethylidenebisphenol, 4,4'-dihydroxy Diphenylpropane, TM124 (Degussa Japan: trade name), 2,2-bis (4-hydroxyphenyl) butane, 4,4 '-(1,3-dimethylbutylidene) diphenol, 4,4'-(2- Ethylhexylidene) diphenol, hexestrol, 2,2-bis (4-hydroxy-3-methylpheny) ) Propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 1,3-bis [2- (4 -Hydroxyphenyl) -2-propyl] benzene, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 4,4'- Butylidenebis (6-tert-butyl-m-cresol), 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4 ′-(α-methylbenzylidene) bisphenol, 1,3-bis [2- (4- Hydroxyphenyl) -2-propyl] benzene, 9,9-bis (4-hydroxyphenyl) fluorene, 4,4′-dihydroxytetra Phenylmethane, 4,4'-dihydroxydiphenylhexafluoropropane, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl ether, 1,3-bis (4-hydroxyphenoxy) benzene, 4,4'-dihydroxydiphenyl sulfone Bis (4-hydroxyphenyl) sulfide, diphenolic acid and the like.

Also, a phenol compound containing a functional group can be used as the phenol compound. Examples of the functional group include an amide group, an imide group, a urea group, a urethane group, and an ether group.

Specific examples of the divalent alcohol compound include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octane. Diol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol 1,2-nonanediol, 1,2-decanediol, 1,2-dodecanediol, 2,5-hexanediol, cis-2 butene-1,4-diol, 2,2-diethyl-1,3- Propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol 1,5-hexadiene-3,4-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, , 2,4,4-tetramethyl-1,3-cyclobutanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, trans-p- Menthane-3,8-diol, 2,4-dimethoxybenzyl alcohol, butyroin and the like can be mentioned.

As the alcohol compound, an alcohol compound containing a functional group can be used in the same manner as the phenol compound. Examples of the functional group include an amide group, an imide group, a urea group, a urethane group, and an ether group.

Next, (β) at least one carboxylic acid compound selected from the group consisting of polyvalent carboxylic acids having a structure of R ₁₉ and R ₂₀ and derivatives thereof will be described.

The polyvalent carboxylic acid having the structure of R ₁₉ and R ₂₀ can be a divalent carboxylic acid, specifically, the structures listed as examples of R ₁ when d = f = 0 described above. A carboxylic acid having a residue having the same structure as can be used.

In the polymer having the structural unit represented by the general formula (1) as a main component, when R ₁ and / or R ₂ has an ester bond, more preferably R ₁ or R ₂ is the general formula (6). When it has the structure represented, it is advantageous also from a viewpoint of i-line permeability.

In the general formula (6), at least one of R ₁₈ , R _19, and R ₂₀ has an alicyclic structure or an aliphatic structure, particularly from the viewpoint of i-line permeability and high sensitivity. In the present disclosure, “aliphatic” means chain aliphatic unless otherwise specified. In particular, R ₁₈ in the general formula (6) is aromatic, and R ₁₉ and R ₂₀ are both alicyclic structures or aliphatic structures (that is, R ₁₉ and R ₂₀ are aromatic structures). Is preferred). In this case, it is advantageous from the viewpoint of further i-line transmittance and higher sensitivity.

From the viewpoint of solubility in a solvent, R ₁₈ preferably has 2 to 30 carbon atoms, and R ₁₉ and R ₂₀ each preferably have 2 to 15 carbon atoms. R ₁₈ , R _19, and R ₂₀ include at least one group selected from the group consisting of hydrocarbon groups, ether groups, amide groups, imide groups, urea groups, urethane groups, sulfonyl groups, and fluorine-containing groups. Is preferred.

（式中、Ｒ₁₆は炭素数１～１８の２価の炭化水素基を示し、そしてＲ₁₇は、それぞれ独立に、水素原子、又は炭素数１～１７の１価の有機基を示す。）

（式中、Ａ₁は、－ＣＨ₂－、－Ｏ－、－Ｓ－、－ＳＯ₂－、－ＣＯ－、－ＮＨＣＯ－、－Ｃ（ＣＦ₃）₂－、及び単結合からなる群より選ばれる２価の基を示し、Ｌ₁は、水素原子又は炭素数１～６の１価の炭化水素基を示し、ｋ＝４であり、複数存在するＬ₁は同一でも異なっていてもよく、そして、Ｌ₂～Ｌ₄は、それぞれ独立に、水素原子又はメチル基を示し、Ｌ₅は、水素原子、メチル基又は水酸基を示し、ｎ₁₀は、１～１２の整数である。） From the viewpoint of further improving i-line transmittance and lithography performance, R ₁₈ in the general formula (6) is more preferably selected from the structure represented by the following general formula (8), and R ₁₉ and R ₂₀ is more preferably selected from structures represented by the following general formula (9).

(In the formula, R ₁₆ represents a divalent hydrocarbon group having 1 to 18 carbon atoms, and R ₁₇ independently represents a hydrogen atom or a monovalent organic group having 1 to 17 carbon atoms.)

Wherein A ₁ is selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, and a single bond. Represents a divalent group selected, L ₁ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, k = 4, and a plurality of L ₁ may be the same or different L ₂ to L ₄ each independently represents a hydrogen atom or a methyl group, L ₅ represents a hydrogen atom, a methyl group or a hydroxyl group, and n ₁₀ is an integer of 1 to 12.)

The proportion of the ester group-containing structure represented by the general formula (6) in the polymer having the structural unit represented by the general formula (1) as a main component is determined by the solubility in an alkali developer and the resulting resin film machine. From the viewpoint of good physical properties, it is preferably 5 to 80 mol%.

（式中、Ｒ₂₁は炭素原子数１～１９の１価の有機基を示す。）
で表される構造を有することが好ましい。 R ₃ and / or R ₄ in the polymer having the structural unit represented by the general formula (1) as a main component is represented by the following general formula (7):

(In the formula, R ₂₁ represents a monovalent organic group having 1 to 19 carbon atoms.)
It preferably has a structure represented by

The structure of R ₂₁ is not particularly limited, but is preferably an aliphatic, alicyclic or aromatic hydrocarbon group having 1 to 10 carbon atoms, and these hydrogen atoms are chlorine atoms, It may be substituted with one or more selected from a fluorine atom, a bromine atom, a methoxy group, a cyano group, and a phenyl group. From the viewpoint of suppressing the shrinkage during curing, the carbon number of R ₂₁ is 1 to 19, more preferably 1 to 10, more preferably from 1 to 6, as the R _21, more specifically Includes a methyl group, an ethyl group, and a phenyl group.

Of the number of R ₃ and R _{4 in} the polymer whose main component is the structural unit represented by the general formula (1), the ratio of the number of groups represented by the general formula (7) From the viewpoint of good solubility, the content is preferably 0.1 to 10 mol%.

Introducing the group represented by the general formula (7) as R ₃ and / or R ₄ of the polymer having the structural unit represented by the general formula (1) as a main component is the following. The compatibility with the phenol resin (c) is particularly good, and the surface condition after development is particularly good. The reason for this is not clear, but the inventor presumes the following reason. The polymer having the structural unit represented by the general formula (1) as a main component has an amide bond, and the bond between the amide and the amide is strong due to the polarity of the amide, and it is easy to associate between the polymers. Compatibility is difficult to increase. On the other hand, when the ester structure is introduced by the structure of the general formula (7), the ester has a polarity close to that of the phenol resin, and the amide bond ratio is relatively reduced, so that the polymer (a) and the phenol resin ( Compatibility with c) becomes high.

The terminal group of the polymer (a) whose main component is the structural unit represented by the general formula (1) may be sealed with an organic group (hereinafter referred to as “sealing group”).

In the polycondensation of hydroxypolyamide, when the dicarboxylic acid component is used in an excess number of moles compared to the sum of the bisaminophenol component and the diamine component, an amino group or a compound having a hydroxyl group is used as a sealing group. It is preferable to use it. Examples of the compound include aniline, ethynylaniline, norborneneamine, butylamine, propargylamine, ethanol, propargyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, and hydroxyethyl acrylate.

On the other hand, when the sum of the bisaminophenol component and the diamine component is used in an excess number of moles compared to the dicarboxylic acid component, the compound having a blocking group includes an acid anhydride, carboxylic acid, acid chloride, isocyanate. It is preferable to use a compound having a group or the like. Examples of the compound include benzoyl chloride, norbornene dicarboxylic anhydride, norbornene carboxylic acid, ethynyl phthalic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, cyclohexane dicarboxylic anhydride, methylcyclohexane dicarboxylic anhydride Products, cyclohexenedicarboxylic anhydride, methacryloyloxyethyl methacrylate, phenyl isocyanate, mesyl chloride, and tosyl chloride.

The polymer (a) whose main component is the structural unit represented by the general formula (1) is an additional structural unit other than the structural unit represented by the general formula (1) as long as the effects of the present invention are not impaired. May be included. Examples of the additional structural unit include a polyhydroxyimide structure, a polyester structure, and a polyamide structure not containing a hydroxyl group. In the polymer (a), the proportion of the structural unit represented by the general formula (1) is more than 50% by mass, the development residual film ratio is high, the sensitivity is high, the surface after development is uniform, and the cured relief From the viewpoint of obtaining a photosensitive resin composition having a good pattern shape and less likely to corrode metal after etching with a fluorine-based compound gas, it is preferably 75 to 100% by mass, more preferably 90 to 100% by mass. is there.

The weight average molecular weight in terms of polystyrene by gel permeation chromatography (hereinafter also referred to as “GPC”) of the polymer (a) whose main component is the structural unit represented by the general formula (1) is 3,000 to 70, 000 is preferable, and 6,000 to 50,000 is more preferable. The weight average molecular weight is preferably 3,000 or more from the viewpoint of physical properties of the cured relief pattern, and is preferably 70,000 or less from the viewpoint of resolution. As developing solvents for GPC, tetrahydrofuran (hereinafter also referred to as “THF”) and N-methyl-2-pyrrolidone (hereinafter also referred to as “NMP”) are recommended. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from standard organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko.

(B) Quinonediazide compound As the quinonediazide compound (b), various compounds that act as a photoacid generator can be used. Among them, a naphthoquinonediazide compound (NQD compound) is preferable, and among them, it has a 1,2-naphthoquinonediazide structure. Compounds are preferred. Examples of the compound having a 1,2-naphthoquinonediazide structure include 1,2-naphthoquinonediazide-4-sulfonic acid ester of a polyhydroxy compound having a specific structure described in detail below, and 1,2-naphtho of the polyhydroxy compound. Preference is given to at least one NQD compound selected from the group consisting of quinonediazide-5-sulfonic acid esters.

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

Examples of preferable NQD compounds include those represented by the following general formula group.

のいずれかで表されるナフトキノンジアジドスルホン酸エステル基であるが、すべてのＱが同時に水素原子であることはない。） (In the formula, Q is a hydrogen atom, or the following formula group:

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

Further, a naphthoquinone diazide sulfonyl ester compound containing a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule can be used, and a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound can be used. Can also be used in combination.

The blending amount of the quinonediazide compound (b) with respect to the entire alkali-soluble resin is based on 100 parts by mass of the total amount of the polymer (a) having the structural unit represented by the general formula (1) as a main component and the phenol resin (c). 1 to 50 parts by mass is preferable, and 5 to 30 parts by mass is more preferable. When the amount of the quinonediazide compound (b) is 1 part by mass or more, the patterning property of the resin is good, and when it is 50 parts by mass or less, the tensile elongation rate of the cured film is good, and Less development residue (scum).

（式中、Ｒ₇及びＲ₈は、それぞれ独立に、炭素数１～１０の１価の有機基を示し、ｈ及びｊは、それぞれ独立に、１～３の整数であり、ｉ及びｋは、それぞれ独立に、０～２の整数であり、１≦（ｈ＋ｉ）≦４、１≦（ｊ＋ｋ）≦４を満たし、ｍ１は０又は正の整数であり、そしてｍ２は正の整数である。）

（式中、Ｒ₉及びＲ₁₀は、それぞれ独立に、炭素数１～１０の１価の有機基を示し、ｌは２又は３であり、ｐは１～３の整数であり、ｏ及びｑは、それぞれ独立に、０～２の整数であり、２≦（ｌ＋ｏ）≦４、１≦（ｐ＋ｑ）≦４を満たし、ｍ３は正の整数であり、そしてｍ４は０又は正の整数である。）

（式中、Ｒ₁₁及びＲ₁₂は、それぞれ独立に、炭素数１～１０の１価の有機基を示し、ｒ及びｕは、それぞれ独立に、１～３の整数であり、ｓ及びｖは、それぞれ独立に、０～２の整数であり、１≦（ｒ＋ｓ）≦４、１≦（ｕ＋ｖ）≦４を満たし、ｍ５は０又は正の整数であり、そしてｍ６は正の整数であり、ｍ１１は正の整数であり、Ｐ₁は、水酸基、カルボキシル基又はアミノ基で置換されていてもよい炭素数１～２０の１価の炭化水素基である。）

｛式中、Ｒ₁₃は、それぞれ独立に、炭素数１～１０の１価の有機基を示し、ｗは１～３の整数であり、ｘは０～２の整数であり、１≦（ｗ＋ｘ）≦４を満たし、ｍ７は正の整数であり、そしてｍ８は０又は正の整数であり、Ｙは、下記式群（５’）：

（Ｐ₄，及びＰ₅は、それぞれ独立に、水素原子、炭素数１～２０のフッ素で置換されていてもよい１価の脂肪族基、又は炭素数６～２０の置換若しくは非置換の１価の芳香族基である。）
から成る群から選ばれる２価の有機基である。｝ (C) Phenolic resin The phenolic resin (c) in this embodiment is represented by at least one selected from the group consisting of the following general formulas (2), (3) and (4), and the general formula group (5). Has a structure.

(Wherein R ₇ and R ₈ each independently represents a monovalent organic group having 1 to 10 carbon atoms, h and j are each independently an integer of 1 to 3, i and k are Each independently represents an integer of 0 to 2, satisfying 1 ≦ (h + i) ≦ 4, 1 ≦ (j + k) ≦ 4, m1 is 0 or a positive integer, and m2 is a positive integer. )

(Wherein R ₉ and R ₁₀ each independently represents a monovalent organic group having 1 to 10 carbon atoms, l is 2 or 3, p is an integer of 1 to 3, o and q Are each independently an integer of 0 to 2, satisfying 2 ≦ (l + o) ≦ 4, 1 ≦ (p + q) ≦ 4, m3 is a positive integer, and m4 is 0 or a positive integer .)

(Wherein R ₁₁ and R ₁₂ each independently represents a monovalent organic group having 1 to 10 carbon atoms, r and u are each independently an integer of 1 to 3, and s and v are Each independently an integer from 0 to 2, satisfying 1 ≦ (r + s) ≦ 4, 1 ≦ (u + v) ≦ 4, m5 is 0 or a positive integer, and m6 is a positive integer, m11 is a positive integer, and P ₁ is a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group, a carboxyl group or an amino group.

{In the formula, each R ₁₃ independently represents a monovalent organic group having 1 to 10 carbon atoms, w is an integer of 1 to 3, x is an integer of 0 to 2, and 1 ≦ (w + x ) ≦ 4, m7 is a positive integer, and m8 is 0 or a positive integer, and Y is the following formula group (5 ′):

(P ₄ and P ₅ are each independently a hydrogen atom, a monovalent aliphatic group which may be substituted with fluorine having 1 to 20 carbon atoms, or substituted or unsubstituted 1 having 6 to 20 carbon atoms. Valent aromatic group.)
A divalent organic group selected from the group consisting of }

The phenol resin (c) has a dissolution inhibiting effect on the quinonediazide compound (b), while the unexposed portion has a dissolution-inhibiting effect. However, since a general phenol resin such as cresol / formaldehyde novolak resin or phenol / formaldehyde novolak resin has poor compatibility with the polymer (a), the film obtained by coating the photosensitive resin composition is uniform. Even in such a case, there has been a problem that a phenomenon of whitening of the surface occurs in the film after development.

On the other hand, the phenol resin having a structure represented by at least one of the general formulas (2), (3), and (4) and the general formula group (5) has compatibility with the polymer (a). high. Therefore, according to the photosensitive resin composition of the present embodiment, whitening does not occur after development, and a film having a uniform surface can be formed. The whitening after development is caused by phase separation in the film when the compatibility between the polymer (a) and the phenol resin is poor, and the film after development due to the difference in solubility between the polymer (a) and the phenol resin in an alkaline developer. This is thought to be caused by unevenness on the surface. According to this embodiment, the combination of the polymer (a) and the phenol resin (c) prevents these whitening and surface roughness, and can form a uniform surface film. The reason for this is not clear, but the inventor presumes the following reason. In general, the closer the polarity of a substance is, the easier it is to mix, and the polarity of the phenol resin (c) used in the present invention is close to that of the polymer (a), or the phenol resin (c) and the polymer (a) are likely to mix. This is thought to be due to conformation.

The content of the phenol resin (c) in the present embodiment is preferably in the range of 20 to 200 parts by mass with respect to 100 parts by mass of the polymer (a). The content is preferably 20 parts by mass or more from the viewpoint of sensitivity, and preferably 200 parts by mass or less from the viewpoint of heat resistance. The content is more preferably from 50 to 150 parts by weight, and still more preferably from 50 to 100 parts by weight, from the viewpoint of heat resistance.

In general formula (2), from the viewpoint of sensitivity, i and k are each preferably 0 or 1, and R ₇ and R ₈ are each preferably a methyl group or an ethyl group. From the viewpoint of the pattern shape after curing, h and j are preferably 1 or 2, respectively. The total number of m1 and m2 is preferably 5 or more, more preferably 10 or more, still more preferably 20 or more, from the viewpoint of heat resistance, and preferably 300 or less, more preferably 250 or less, from the viewpoint of lithographic properties. More preferably, it is 200 or less. Further, the ratio of m1 to m2 (m1 / m2) is preferably 1/99 or more, more preferably 10/90 or more, still more preferably 20/80 or more, from the viewpoint of alkali solubility. Therefore, it is preferably 90/10 or less, more preferably 80/20 or less, and still more preferably 70/30 or less.

（式中、ｍ９及びｍ１０はそれぞれ独立に０又は正の整数であり、ｍ９及びｍ１０が同時に０になることはなく、ｍ９とｍ１０との合計は一般式（２）中のｍ１に等しく、そしてｍ２は一般式（２）で定義した通りである。） The structure represented by the general formula (2) is more preferably a structure represented by the following formula.

(Where m9 and m10 are each independently 0 or a positive integer, m9 and m10 are not simultaneously 0, the sum of m9 and m10 is equal to m1 in general formula (2), and m2 is as defined in the general formula (2).)

In general formula (3), from the viewpoint of sensitivity, o and q are each preferably 0 or 1, and R ₉ and R ₁₀ are each preferably a methyl group or an ethyl group. From the viewpoint of the pattern shape after curing, l is preferably 2, and p is preferably 1 or 2. When p and q in the structural unit represented by the repeating number m4 are each 1, R ₁₀ is preferably in the meta position or para position with respect to the phenolic hydroxyl group. The total number of m3 and m4 is preferably 5 or more, more preferably 10 or more, and still more preferably 20 or more, from the viewpoint of heat resistance, and preferably 300 or less, more preferably 250 or less, from the viewpoint of lithographic properties. More preferably, it is 200 or less. When l is 2 or 3 and p is 1, the ratio of m3 to m4 (m3 / m4) is preferably 10/90 or more, more preferably 20/80 or more, from the viewpoint of alkali solubility. More preferably, it is 30/70 or more, and from the viewpoint of heat resistance, it is preferably 99/1 or less, more preferably 90/10 or less, and still more preferably 80/20 or less. When l is 3 and p is 2, the m3 / m4 ratio is preferably 10/90 or more, more preferably 20/80 or more, and still more preferably 30/70 or more, from the viewpoint of alkali solubility. From the viewpoint of heat resistance, it is preferably 80/20 or less, more preferably 70/30 or less, and still more preferably 60/40 or less.

（式中、ｍ３及びｍ４は一般式（３）で定義した通りである。） The structure represented by the general formula (3) is more preferably a structure represented by the following formula.

(Wherein m3 and m4 are as defined in general formula (3).)

In general formula (4), from the viewpoint of sensitivity, s and v are preferably 0 or 1, and R ₁₁ and R ₁₂ are each preferably a methyl group or an ethyl group. From the viewpoint of the pattern shape after curing, r and u are each preferably 1 or 2. The total number of m5 and m6 is preferably 5 or more, more preferably 7 or more, still more preferably 10 or more from the viewpoint of heat resistance, and preferably 300 or less, more preferably 250 or less, from the viewpoint of lithographic properties. More preferably, it is 200 or less. Further, the ratio of m5 to m6 (m5 / m6) is preferably 1/99 or more, more preferably 10/90 or more, and further preferably 20/80 or more from the viewpoint of film stress, and from the viewpoint of heat resistance. , Preferably 90/10 or less, more preferably 80/20 or less, still more preferably 70/30 or less. P ₁ is preferably a hydroxyphenyl group from the viewpoint of the surface state after development and the adhesive strength between the cured film and the die attach film. m11 is preferably 1 to 3 from the viewpoint of alkali solubility of the composition.

（式中、Ｒ₁₁及びＲ₁₂は、それぞれ独立に、炭素数１～１０の１価の有機基を示し、ｒ、ｔ及びｕは、それぞれ独立に、１～３の整数であり、ｓ及びｖは、それぞれ独立に、０～２の整数であり、１≦（ｒ＋ｓ）≦４、１≦（ｕ＋ｖ）≦４を満たし、ｍ５は０又は正の整数であり、そしてｍ６は正の整数である。）
　一般式（４’）において、ｓ及びｖは０又は１であることが好ましく、Ｒ₁₁及びＲ₁₂はそれぞれメチル基又はエチル基であることが好ましい。硬化後のパターン形状の観点から、ｒ、ｔ及びｕはそれぞれ１又は２であることが好ましい。ｍ５及びｍ６の合計数は、耐熱性の観点から、好ましくは５以上、より好ましくは７以上、更に好ましくは１０以上であり、リソ性の観点から、好ましくは３００以下、より好ましくは２５０以下、更に好ましくは２００以下である。また、ｍ６に対するｍ５の比（ｍ５／ｍ６）は、膜応力の観点から、好ましくは１／９９以上、より好ましくは１０／９０以上、更に好ましくは２０／８０以上であり、耐熱性の観点から、好ましくは９０／１０以下、より好ましくは８０／２０以下、更に好ましくは７０／３０以下である。 The structure represented by the general formula (4) is more preferably a structure represented by the following general formula (4 ′) particularly from the viewpoint of the sensitivity of the composition and the pattern shape after curing.

(Wherein R ₁₁ and R ₁₂ each independently represents a monovalent organic group having 1 to 10 carbon atoms, r, t and u are each independently an integer of 1 to 3; v is each independently an integer of 0 to 2, satisfies 1 ≦ (r + s) ≦ 4, 1 ≦ (u + v) ≦ 4, m5 is 0 or a positive integer, and m6 is a positive integer is there.)
In the general formula (4 ′), s and v are preferably 0 or 1, and R ₁₁ and R ₁₂ are each preferably a methyl group or an ethyl group. From the viewpoint of the pattern shape after curing, r, t, and u are each preferably 1 or 2. The total number of m5 and m6 is preferably 5 or more, more preferably 7 or more, still more preferably 10 or more from the viewpoint of heat resistance, and preferably 300 or less, more preferably 250 or less, from the viewpoint of lithographic properties. More preferably, it is 200 or less. Further, the ratio of m5 to m6 (m5 / m6) is preferably 1/99 or more, more preferably 10/90 or more, and further preferably 20/80 or more from the viewpoint of film stress, and from the viewpoint of heat resistance. , Preferably 90/10 or less, more preferably 80/20 or less, still more preferably 70/30 or less.

（式中、ｍ５及びｍ６は一般式（４’）で定義した通りである。） The structure represented by the general formula (4 ′) is more preferably a structure represented by the following formula.

(In the formula, m5 and m6 are as defined in the general formula (4 ′).)

In general formula (5), from the viewpoint of sensitivity, x is preferably 0 or 1, and R ₁₃ is preferably a methyl group or an ethyl group. From the viewpoint of the pattern shape after curing, w is preferably 1 or 2. The total number of m7 and m8 is preferably 3 or more, more preferably 5 or more, and still more preferably 10 or more, from the viewpoint of heat resistance, and preferably 300 or less, more preferably 250 or less, from the viewpoint of lithographic properties. More preferably, it is 200 or less. Further, the ratio of m7 to m8 (m7 / m8) is preferably 10/90 or more, more preferably 20/80 or more, still more preferably 30/70 or more from the viewpoint of heat resistance, and from the viewpoint of alkali solubility. Therefore, it is preferably 99/1 or less.

（Ｐ₄，及びＰ₅は、それぞれ上記式群（５’）において定義したのと同じである。）
　Ｐ₄，及びＰ₅は、それぞれ、コストの観点から、メチル基、水素原子であることが好ましい。 In the general formula (5), Y is more preferably a structure represented by the following general formula (5 ″) from the viewpoint of the sensitivity of the composition and the pattern shape after curing.

(P ₄ and P ₅ are the same as defined in the above formula group (5 ′).)
P ₄ and P ₅ are each preferably a methyl group or a hydrogen atom from the viewpoint of cost.

（式中、ｍ７は一般式群（５）で定義した通りである。） Especially, it is more preferable that the structure represented by the general formula group (5) is a structure represented by the following formula.

(In the formula, m7 is as defined in the general formula group (5).)

As a method for synthesizing the phenol resin (c), a method of polycondensing various phenol compounds alone or a mixture thereof with aldehydes such as formalin by a known method, a phenol compound and a polymerization component, A method of synthesizing by a polymerization reaction and a method of synthesizing by a combination thereof are mentioned.

Here, specific examples of the polymerization component include compounds having two methylol groups in the molecule, compounds having two alkoxymethyl groups in the molecule, and compounds having two haloalkyl groups in the molecule. It is done.

Examples of the phenol compound include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3, 4-dimethylphenol, 3,5-dimethylphenol, methylene bisphenol, methylene bis p-cresol, bisphenol A, resorcin, catechol, 2-methyl resorcin, 4-methyl resorcin, m-methoxyphenol, p-methoxyphenol, p-butoxy Phenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, etc., which are used alone or in combination It can be used as a.

In addition to formalin, aldehydes include trioxane, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde and the like, and these can be used alone or as a mixture of a plurality of them.

Examples of the compound having two methylol groups in the molecule include bis (hydroxymethyl) cresol, 2,6-bis (hydroxymethyl) -4-ethylphenol, and 2,6-bis (hydroxymethyl) -4- Propylphenol, 2,6-bis (hydroxymethyl) -4-n-butylphenol, 2,6-bis (hydroxymethyl) -4-tert-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, bis (hydroxymethyl) biphenyl And the like.

Examples of the compound having two alkoxymethyl groups in the molecule include bis (methoxymethyl) 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, Examples include 6-bis (methoxymethyl) -4-t-butoxyphenol and bis (methoxymethyl) biphenyl. The number of carbon atoms of the alkoxymethyl group is preferably 1 to 10, more preferably 1 to 2, and most preferably 1 from the viewpoint of reaction activity.

Examples of the compound having two haloalkyl groups in the molecule include bischloromethylbiphenyl.

The weight average molecular weight of the phenol resin (c) is preferably 1,000 to 50,000, more preferably 2,000 to 20,000. The weight average molecular weight is preferably 1,000 or more from the viewpoint of elongation, and preferably 50,000 or less from the viewpoint of alkali solubility. The weight average molecular weight is a value obtained by standard polystyrene conversion using GPC.

Other Components In the present invention, it is preferable that the above-described various components are dissolved in an organic solvent to form a varnish and used as a solution for the photosensitive resin composition. Examples of such organic solvents include N-methyl-2-pyrrolidone, γ-butyrolactone (hereinafter also referred to as “GBL”), cyclopentanone, cyclohexanone, isophorone, N, N-dimethylacetamide (hereinafter referred to as “DMAc”). ), Dimethylimidazolinone, tetramethylurea, dimethyl sulfoxide, diethylene glycol dimethyl ether (hereinafter also referred to as “DMDG”), diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene Glycol monomethyl ether, dipropylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, milk Butyl, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, diisobutyl ketone, 2-heptanone, 3- Heptanone, 4-heptanone, 5-methyl-3-heptanone, 2-methyl-3-heptanone, 6-methyl-2-heptanone, 2-methyl-4-heptanone, 3-methyl-4-heptanone, 2-octanone, 3-Octanone, 4-octanone, 5-methyl-2-octanone, 2-nonanone, 3-nonanone, 4-nonanone, 5-nonanone, 2-hexylcyclopentanone and the like can be used alone or in combination.

Of these solvents, non-amide solvents are preferred because they have little influence on the photoresist and the like. Specific more preferable examples include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofurfuryl alcohol, 2-heptanone, 2-octanone, 2-nonanone and the like. Can be mentioned. These organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent added is preferably 100 to 100 parts by mass with respect to 100 parts by mass of the total amount of the polymer (a) having the structural unit represented by the general formula (1) as a main component and the phenol resin (c). 2,000 parts by mass. The viscosity of the photosensitive resin composition solution can be controlled by changing the amount of the organic solvent added. The addition amount is more preferably 100 to 1,000 parts by mass. By adjusting the addition amount of the organic solvent, the viscosity becomes suitable for the coating apparatus and the coating thickness, and the production of the cured relief pattern can be facilitated.

The photosensitive resin composition according to the present invention can contain a cross-linking agent for the purpose of enhancing the chemical resistance of the film after curing (photosensitive resin layer), if necessary. Examples of the crosslinking agent include an aromatic compound having a methylol group and / or an alkoxymethyl group, a compound in which the N-position is substituted with a methylol group and / or an alkoxymethyl group, an epoxy compound, an oxetane compound, and an allyl compound. At least one selected compound can be used.

Among these crosslinking agents, at least one compound selected from the group consisting of an aromatic compound having a methylol group and / or an alkoxymethyl group, and a compound in which the N-position is substituted with a methylol group and / or an alkoxymethyl group is present. From the viewpoint of chemical resistance after thermosetting.

A crosslinking agent can be used individually or in mixture of 2 or more types, and the compounding quantity is the polymer (a) and phenol resin (c) which have as a main component the structural unit represented by General formula (1). The total amount is preferably 1 to 100 parts by mass, more preferably 3 to 50 parts by mass with respect to the total amount of 100 parts by mass. When the blending amount is 1 part by mass or more, crosslinking proceeds well and the patterning property becomes good. When the blending amount is 100 parts by mass or less, the mechanical properties after curing are kept good.

In the present invention, a dissolution accelerator can be preferably used. Examples of the dissolution accelerator include carboxylic acid compounds and phenolic compounds.

Examples of carboxylic acid compounds include 3-phenyl lactic acid, 4-hydroxyphenyl lactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid, 2-methoxy-2- ( 1-naphthyl) propionic acid, mandelic acid, atrolactic acid, acetylmandelic acid, α-methoxyphenylacetic acid, 3-phenyllactic acid, 4-hydroxyphenyllactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4 -Hydroxy-3-methoxymandelic acid, 2-methoxy-2- (1-naphthyl) propionic acid, mandelic acid, atrolactic acid, O-acetylmandelic acid, α-methoxyphenylacetic acid, 4-hydroxymandelic acid, 3, 4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid , Mandelic acid, atrolactic acid, O-acetylmandelic acid, α-methoxyphenylacetic acid, O-acetylmandelic acid, α-methoxyphenylacetic acid, hexyl dihydroxybenzenecarboxylate, octyl dihydroxybenzenecarboxylate, dodecyl dihydroxybenzenecarboxylate, Hexyl trihydroxybenzenecarboxylate hexyl gallate and phloroglucinol carboxylate hexyl, octyl trihydroxybenzenecarboxylate octyl gallate and phloroglucinol carboxylate dodecyl trihydroxybenzenecarboxylate dodecyl gallate and Phloroglucinol carboxylate dodecyl, trihydroxybenzenecarboxylate hexadecyl hexadecyl gallate and phloroglucinol carboxylate Xadecyl and the like can be mentioned.

As the phenol compound, a ballast agent used for the photosensitive diazoquinone compound, and a linear phenol compound such as paracumylphenol, bisphenols, resorcinol, or MtrisPC, MtetraPC (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) Non-linear phenolic compounds such as TrisP-HAP, TrisP-PHBA, TrisP-PA (trade name) manufactured by Honshu Chemical Industry Co., Ltd., compounds in which 2 to 5 hydrogen atoms of the phenyl group of diphenylmethane are substituted with hydroxyl groups, 2 , Compounds in which 1 to 5 hydrogen atoms of the phenyl group of 2-diphenylpropane are substituted with hydroxyl groups. By adding the phenol compound, the adhesion of the relief pattern during development can be improved and the generation of residues can be suppressed. In addition, a ballast agent means the phenol compound currently used as a raw material for the above-mentioned photosensitive diazoquinone compound which is a phenol compound in which a part of the phenolic hydrogen atom is converted to naphthoquinonediazide sulfonic acid ester.

The blending amount of the dissolution accelerator is preferably 0 to 50 parts by mass with respect to 100 parts by mass of the total amount of the polymer (a) having the structural unit represented by the general formula (1) as a main component and the phenol resin (c). 1 to 30 parts by mass is preferable. When the blending amount is 50 parts by mass or less, the heat resistance of the film after thermosetting is good. Moreover, when a compounding quantity is 1 mass part or more, the melt | dissolution promotion effect to the developing solution of an exposure part is favorable.

The photosensitive resin composition according to the present invention enhances adhesiveness with alcohol, dye, fragrance, surfactant for improving in-plane uniformity of the coating film, and silicon substrate or copper substrate, if necessary. It is also possible to contain additives such as an adhesion aid for the purpose.

More specifically, the alcohol preferably has 4 to 14 carbon atoms. Specifically, cyclopropylcarbinol, 2-cyclohexen-1-ol, cyclohexanemethanol, 4- Methyl-1-cyclohexanemethanol, 3,4-dimethylcyclohexanol, 4-ethylcyclohexanol, 4-t-butyrocyclohexanol, cyclohexaneethanol, 3-cyclohexyl-1-propanol, 1-cyclohexyl-1-pentanol, 3,3,5-trimethylcyclohexanol, norbornane-2-methanol, cyclooctanol, 2,3,4-trimethyl-3-pentanol, 2,4-hexadien-1-ol, cis-2-hexene-1- All, trans-2-heptene 1-ol, cis-4-hepten-1-ol, cis-3-octen-1-ol, 4-ethyl-1-octyn-3-ol, 2,7-octadienol, 3,6-dimethyl- 1-heptin-3-ol, 3-ethyl-2-methyl-3-pentanol, 2-ethyl-1-hexanol, 2,3-dimethyl-2-hexanol, 2,5-dimethyl-2-hexanol, trans , Cis-2,6-nonadien-1-ol, 1-nonen-3-ol, cis-2-butene-1,4-diol, 2,2-diethyl-1,3-propanediol, 2,4- Diethyl-1,5-pentanediol, 1,5-hexadiene-3,4-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 2,4,7,9-tetramethyl-5 Desin 4,7-diol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,2-cyclohexanediol, trans-p-menthane-3,8-diol, 2,4-dimethoxybenzyl alcohol , Butyroin and the like.

Among these, from the viewpoint of in-plane uniformity after coating, 2,3,4-trimethyl-3-pentanol, 2,4-hexadien-1-ol, cis-2-hexen-1-ol, trans- 2-hepten-1-ol, cis-4-hepten-1-ol, cis-3-octen-1-ol, trans, cis-2,6-nonadien-1-ol, cis-2-butene-1, Hydroxyl group-containing compounds having an unsaturated bond or a branched structure, such as 4-diol and 1,5-hexadiene-3,4-diol, are preferred, and from the viewpoint of adhesion to the substrate, monoalcohols are preferred over diols. Among them, 2,3,4-trimethyl-3-pentanol, 3-ethyl-2-methyl-3-pentanol, and glycerol-α, α'-diallyl ether Preferred.
These hydroxyl group-containing compounds may be used alone or in combination of two or more.

The blending amount in the case of blending the above alcohol is 0.01 with respect to 100 parts by mass of the total amount of the polymer (a) having the structural unit represented by the general formula (1) as a main component and the phenol resin (c). Is preferably 70 parts by weight, more preferably 0.1-50 parts by weight, still more preferably 1-40 parts by weight, and particularly preferably 5-25 parts by weight. When the blending amount of the alcohol is 0.01 parts by mass or more, the development residue in the exposed part decreases, and when it is 70 parts by mass or less, the tensile elongation of the film after curing is good.

Examples of the dye include methyl violet, crystal violet, and malachite green. The blending amount when the dye is blended is 0.1 to 10 with respect to 100 parts by mass of the total amount of the polymer (a) having the structural unit represented by the general formula (1) as a main component and the phenol resin (c). Part by mass is preferred. If the blending amount is 0.1 parts by mass or more, the visualization effect is obtained well, and if it is 10 parts by mass or less, the heat resistance of the film after thermosetting is good.

Examples of the perfume include terpene compounds, and monoterpene compounds and sesquiterpene compounds are preferable from the viewpoint of solubility in solvents.
Specifically, linalool, isophytol, dihydrolinalol, linalool acetate, linalool oxide, geranyl linalool, lavandulol, tetrahydrolabandulol, lavandulol acetate, nerol, nerol acetate, geraniol, citral, geranyl acetate, geranylacetone , Geraniic acid, citral dimethyl acetal, citronellol, citronellal, hydroxycitronellal, dimethyl octanal, citronellyl acid, citronellyl acetate, tageton, artemisia ketone, pregol, isopulegol, menthol, menthol acetate, isomenthol, neomenthol, mentanol , Menthanetriol, menthanetetraol, carbomenthol, menthoxyacetic acid, perillyl alcohol, perilaldehyde Carbeol, piperitol, terpene-4-ol, terpineol, terpineol, dihydroterpineol, sobreol, thymol, borneol, bornyl acetate, isoborneol, isobornyl acetate, cineol, pinol, pinocarbeveol, mirutenol, mirutenal, berbenol, pinoccampe All, camphorsulfonic acid, nerolidol, terpinene, ionone, pinene, camphene, camphorene aldehyde, camphoronic acid, isocamphoronic acid, camphoric acid, abithienoic acid, glycyrrhetinic acid and the like. These terpene compounds may be used alone or in combination of two or more.
When blending the fragrance, the blending amount is 0.1 to 70 with respect to 100 parts by mass of the total amount of the polymer (a) having the structural unit represented by the general formula (1) as a main component and the phenol resin (c). Part by mass is preferable, and 1 to 50 parts by mass is more preferable. If the blending amount is 0.1 parts by mass, the effect of the fragrance can be obtained satisfactorily, and if it is 70 parts by mass or less, the heat resistance of the film after thermosetting is good.

Examples of the surfactant include polyglycols such as polypropylene glycol and polyoxyethylene lauryl ether, and nonionic surfactants composed of derivatives thereof. Further, fluorine-based surfactants such as Fluorard (manufactured by Sumitomo 3M: trade name), Megafuck (manufactured by Dainippon Ink & Chemicals, Inc .: trade name), Lumiflon (trade name, manufactured by Asahi Glass Co., Ltd.), and the like can be mentioned. Furthermore, organic siloxane surfactants such as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name), DBE (manufactured by Chisso Corporation: trade name), granol (manufactured by Kyoeisha Chemical Co., Ltd .: trade name), and the like. By adding the surfactant, it is possible to make it less likely to cause repellency of the coating film at the wafer edge during coating.

The blending amount of the surfactant is preferably 0 to 10 parts by mass with respect to 100 parts by mass of the total amount of the polymer (a) having the structural unit represented by the general formula (1) as a main component and the phenol resin (c). 0.01 to 1 part by mass is more preferable. When the blending amount is 10 parts by mass or less, the heat resistance of the film after thermosetting is good. Moreover, when a compounding quantity is 0.01 mass part or more, the effect which prevents the repelling of said coating film is favorable.

Adhesion aids that improve the adhesion between the cured resist pattern and the silicon substrate or copper substrate include alkylimidazolines, polyhydroxystyrenes, polyvinyl methyl ethers, t-butyl novolacs, epoxy polymers, organosilicon compounds, and triazoles and tetrazoles. And heterocyclic structure compounds such as oxazole, thiazole and imidazole.

An organosilicon compound is a compound containing a monofunctional or higher-functional alkoxyl group and a silanol group, and serves as an adhesion aid for enhancing adhesion to a silicon wafer. The number of carbon atoms of the organosilicon compound is preferably 4 to 30, more preferably 4 to 18, from the viewpoint of solubility in a solvent.

Specific examples of the compound include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name KBM803, manufactured by Chisso Corporation: trade name of Silaace S810), 3-mercaptopropyltriethoxysilane (manufactured by Asmax Co., Ltd .: Trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name LS1375, manufactured by Azmax Co., Ltd .: trade name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Corporation: product) Name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxy Lan, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltri Methoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxy Propoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercapto Tiltriethoxysilane, 4-mercaptobutyltripropoxysilane, N- (3-triethoxysilylpropyl) urea (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name LS3610, product of 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-methoxydipropoxysilylpropyl) 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 Co., Ltd .: trade name SLA 599.0), p-aminophenyltrimethoxysilane (manufactured by Asmax Co., Ltd .: trade name SLA0599.1) aminophenyltrimethoxysilane (manufactured by Asmax Co., Ltd .: trade name SLA0599.2), 2- (trimethoxysilylethyl) Pyridine (manufactured by Azmax Co., Ltd .: trade name SIT83396), 2- (triethoxysilylethyl) pyridine, 2- (dimethoxysilylmethylethyl) pyridine, 2- (diethoxysilylmethylethyl) pyridine, (3-triethoxy Silylpropyl) -t-butylcarbamate, (3-glycidoxypropyl) triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, Tetra -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 (triethoxysilyl) octadiene, bis [3- (triethoxysilyl) propyl] disulfide, bis [3- (triethoxysilyl) propyl] tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane, (Pentadionate) Titanium-O, O'-bis (oxyethyl) -aminopropyltriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butyldiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, Isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, ter -Butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol , Isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol, and the like, but are not limited thereto. These may be used alone or in combination.

Among the organosilicon compounds described above, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy (p-tolyl) silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane are among the above-mentioned organosilicon compounds from the viewpoint of storage stability. , Dimethoxydi-p-tolylsilane, triphenylsilanol, and a silane coupling agent represented by the following structure are preferable.

The organosilicon compounds may be used alone or in combination of two or more. When the organosilicon compound is blended, the blending amount is 1 to 40 with respect to 100 parts by mass of the total amount of the polymer (a) having the structural unit represented by the general formula (1) as a main component and the phenol resin (c). The mass is preferably 2 to 30 parts by mass, more preferably 4 to 20 parts by mass. If the compounding amount of the compound is 1 part by mass or more, the development residue in the exposed part is reduced satisfactorily and the adhesion to the silicon substrate is good. On the other hand, if it is 40 parts by mass or less, the cured film Tensile elongation is good, and shows good adhesion and lithography performance.

（式中、Ｚ₇は、水素原子、炭素原子数１～５の１価の炭化水素基、及びカルボキシル基からなる群から選ばれる基であり、Ｚ₈は、水素原子、ヒドロキシル基、炭素原子数１～５の１価の炭化水素基、及びアミノアルキル基からなる群から選ばれる基である。） Specific examples of the heterocyclic structure compound include 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 1,3-dimethyl-5-pyrazolone, 3,5-dimethylpyrazole, 5,5-dimethylhydantoin, 3- Methyl-5-pyrazolone, 3-methyl-1-phenyl-5-pyrazolone, 2-methylimidazole, 1,10-phenanthroline, phenothiazine, phenoxazine, phenoxatin, mercaptobenzothiazole, mercaptobenzoxazole, methylthiobenzothiazole, dibenzothia Examples include dil disulfide, methylthiobenzimidazole, benzimidazole, phenylmercaptothiazoline, mercaptophenyltetrazole, and mercaptomethyltetrazole. Examples of benzotriazoles include compounds represented by the following general formula.

(Wherein Z ₇ is a group selected from the group consisting of a hydrogen atom, a monovalent hydrocarbon group having 1 to 5 carbon atoms, and a carboxyl group, and Z ₈ is a hydrogen atom, a hydroxyl group, a carbon atom, These are groups selected from the group consisting of monovalent hydrocarbon groups of 1 to 5 and aminoalkyl groups.)

Among the heterocyclic structure compounds, 5-mercapto-1-phenyltetrazole, 1,2,3-benzotriazole, benzothiazole, benzoxazole, benzimidazole, and 2-mercaptobenzoxazole from the viewpoint of sensitivity on a copper substrate A compound selected from the group consisting of:
These heterocyclic structure compounds may be used alone or in combination of two or more.

The compounding amount in the case of compounding the heterocyclic structure compound is 0. 0 with respect to 100 parts by mass of the total amount of the polymer (a) having the structural unit represented by the general formula (1) as a main component and the phenol resin (c). 1 to 30 parts by mass is preferable, and 0.5 to 10 parts by mass is more preferable. When the compounding amount of the heterocyclic structure compound is 0.1 parts by mass or more, the adhesiveness of the heat-cured film to the copper substrate is good, and when it is 30 parts by mass or less, the stability of the composition is good.

<Method for Manufacturing Cured Relief Pattern, Semiconductor Device, and Display Device>
The present invention is also a method for producing a cured relief pattern,
(A) a step of forming a photosensitive resin layer comprising the photosensitive resin composition of the present invention on a substrate;
(B) a step of exposing the photosensitive resin layer;
(C) removing the exposed portion with a developer to obtain a relief pattern; and (D) heating the relief pattern.
A method comprising: The present invention also provides a cured relief pattern produced by the above method. This will be specifically described below.

(A) Step of forming a photosensitive resin layer on a substrate In this step, the photosensitive resin composition of the present invention is spin-coated using a spin coater on a substrate such as a silicon wafer, a ceramic substrate, or an aluminum substrate, Alternatively, it is applied by a coater such as a die coater or a roll coater. This is dried at 50 to 140 ° C. using an oven or a hot plate to remove the solvent, thereby forming a photosensitive resin layer. From the viewpoint of obtaining a coating film having a uniform thickness, the spin coating method using a spin coater is most preferable.

(B) Step of exposing the photosensitive resin layer Next, the substrate obtained above is exposed to actinic radiation using a contact aligner or a stepper through a mask, or a light beam, an electron beam or an ion. Irradiate the line directly.

(C) Step of removing the exposed portion with a developer to obtain a relief pattern Next, development can be performed by selecting from methods such as dipping, paddle, and rotary spraying. By developing, the exposed portion can be eluted and removed from the 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 a quaternary ammonium salt such as quaternary ammonium salt and an aqueous solution to which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added as required can be used. Among these, an aqueous tetramethylammonium hydroxide solution is preferable, and the concentration of the tetramethylammonium hydroxide is preferably 0.5 to 10% by mass, and more preferably 1 to 5% by mass.

(D) Step of heating the relief pattern Subsequently, the obtained relief pattern is cured by heating and heat-resistant curing including a resin having an imide ring, an oxazole ring, or the like (for example, a resin having a polybenzoxazole structure). A relief pattern is formed. As the heating device, an oven furnace, a hot plate, a vertical furnace, a belt conveyor furnace, a pressure oven, or the like can be used. As a heating method, heating by hot air, infrared rays, electromagnetic induction, or the like is recommended. The temperature is preferably 200 to 450 ° C, more preferably 250 to 400 ° C. The heating time is preferably 15 minutes to 8 hours, more preferably 15 minutes to 4 hours. The atmosphere is preferably in an inert gas such as nitrogen or argon.

The present invention also provides 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 of the present invention.
The present invention also provides 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 of the present invention. To do.

Examples of semiconductor device applications include those having a cured film provided on top of a semiconductor element, wherein the cured film is a cured relief pattern comprising a cured film of the above-described photosensitive resin composition. . Examples of the cured film include a passivation film on a semiconductor element, a protective film such as a buffer coat film formed by forming a cured film of the above-described photosensitive resin composition on the passivation film, and a circuit formed on the semiconductor element. Examples thereof include an insulating film such as an interlayer insulating film formed by forming a cured film of the above-described photosensitive resin composition, an α-ray blocking film, a planarizing film, a protrusion (resin post), a partition wall, and the like.

Examples of display device applications include a protective film formed by forming a cured film of the above-described photosensitive resin composition on a display element, an insulating film or a planarizing film for TFT elements or color filters, MVA type liquid crystal Examples thereof include protrusions for display devices, partition walls for organic EL element cathodes, and the like. The use method is based on forming a cured film of the photosensitive resin composition patterned on the substrate on which the display element or color filter is formed according to the semiconductor device application by the above method.
The photosensitive resin composition of the present invention is also useful for applications such as interlayer insulation for multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, liquid crystal alignment films for display devices, and light emitting elements. .

<Curing film>
Another embodiment of the present invention is a cured film containing a phenol resin and at least one resin selected from the group consisting of polyimide and polybenzoxazole,
The cured film has the following conditions:
Plasma type: Microwave Processing gas: O ₂
Treatment time: Arithmetic average surface roughness measured using an atomic force microscope (AFM) after 60 seconds of dry etching treatment (hereinafter sometimes simply referred to as surface roughness): 0.5 to 5.0 nm A cured film is provided. More specifically, the surface roughness is measured by the method described in the Examples section of the present disclosure or a method understood by those skilled in the art to be equivalent thereto.
The cured film is obtained by applying a photosensitive resin layer composed of a positive photosensitive resin composition to a substrate, and then performing exposure, development, and curing. The positive photosensitive resin composition can contain at least one resin selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, a quinonediazide compound, a phenol resin, and a solvent.

By setting the surface roughness within the range, whitening of the cured film can be improved. Although not wishing to be bound by theory, the surface roughness is determined by the compatibility between components in the positive photosensitive resin composition, in particular, the polyimide precursor and / or the polybenzoxazaol precursor, and the phenol resin. It is presumed that it depends on the compatibility.
In order to improve the sensitivity at the time of curing of a positive photosensitive resin composition containing a polyimide precursor and / or a polybenzoxazaol precursor and a phenol resin, it is effective to increase the amount of the phenol resin. However, when the amount of phenol resin is increased, the cured film tends to be whitened. This whitening is presumed to be caused by low compatibility between the polyimide precursor and / or the polybenzoxazaol precursor and the phenol resin.
In order to achieve both sensitivity and whitening prevention, it is effective to appropriately control the type and amount of the phenol resin.
The compatibility between the polyimide precursor and / or polybenzoxazaol precursor and the phenol resin is such that the backbone structure (hydroxyl group, ester group, etc.) of the polyimide precursor and / or polybenzoxazaol precursor, and phenol It is influenced by the skeletal structure (hydroxyl group concentration, hydroxyl group distance, etc.). Therefore, for example, it may be advantageous to use a relatively large amount of a phenol resin having a specific structure.

As examples of components advantageous from the above viewpoint, examples of the polyimide precursor and the polybenzoxazaol precursor include those described above as the polymer (a) in the section <Photosensitive resin composition>. Moreover, as an example of the said phenol resin, what was mentioned above as a phenol resin (c) by the term of the <photosensitive resin composition> can be illustrated. Moreover, as an example of the said solvent, what was mentioned above as an organic solvent by the term of the <photosensitive resin composition> can be illustrated.

That the surface roughness of the cured film after dry etching treatment under the above conditions is 5.0 nm or less can prevent whitening of the cured film after dry etching treatment and improve the yield of the semiconductor process. Show. The lower surface roughness is advantageous, but it may be 0.5 nm or more from the viewpoint of adhesion between the cured film and the mold resin. The surface roughness is more preferably 0.5 nm to 4.5 nm, and particularly preferably 0.5 nm to 4.0 nm.

From the viewpoint of controlling the surface roughness within the above range, the positive photosensitive resin composition is based on at least one resin selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor: 100 parts by mass. The phenolic resin preferably contains 20 to 200 parts by mass, and the phenolic resin contains 50 to 150 parts by mass. The phenol resin content of 20 parts by mass or more is advantageous from the viewpoint of sensitivity during curing, and the content of 200 parts by mass or less prevents heat resistance and further prevents whitening of the cured film. It is advantageous from the viewpoint.

When the cured film is heat-treated at 240 ° C. for 10 hours in an air atmosphere, the weight loss change rate (hereinafter, also simply referred to as “weight loss change rate”) is preferably 0.1 to 3.0%. . In the present disclosure, the weight loss change rate when heat-treated at 240 ° C. for 10 hours in an air atmosphere is a value calculated according to the following formula.
Rate of change in weight loss (%) = {maximum weight during heat treatment (g) −minimum weight during heat treatment (g)} / weight before heat treatment (g) * 100
More specifically, the weight change rate is measured by a method described in the Examples section of the present disclosure or a method understood by those skilled in the art to be equivalent thereto.

In another embodiment of the present invention, it is composed of a positive photosensitive resin composition containing at least one resin selected from a polyimide precursor and a polybenzoxazole precursor, a quinonediazide compound, a phenol resin, and a solvent. A cured film obtained by applying a photosensitive resin layer to a substrate and then performing exposure, development, and curing, and the weight loss change rate is 0 when heat-treated at 240 ° C. for 10 hours in an air atmosphere. Provide a cured film that is 1-3.0%.

The rate of change in weight reduction is an index of sensitivity when the photosensitive resin layer is cured, and depends on the structure of the polyimide precursor and / or polybenzoxazaol precursor and the phenol resin (particularly, the ester structure). The When the cured film is heat-treated at 240 ° C. for 10 hours in an air atmosphere, the weight loss change rate of the cured film is 3.0% or less when the cured film is formed from the photosensitive resin layer, that is, This means that the sensitivity at the time of curing was good. Even in a semiconductor process such as a stacked CSP in which a plurality of chips with a cured film are laminated via a die attach film, gas generated from the cured film during chip lamination It shows that the die attach film peeling considered to be the cause can be prevented. The lower rate of change in weight loss is preferable, but it may be, for example, 0.1% or more. The weight loss change rate is more preferably 0.1 to 2.75%, and particularly preferably 0.1 to 2.5%.

From the viewpoint of controlling the rate of change in weight reduction of the cured film when heat-treated at 240 ° C. for 10 hours in an air atmosphere, the positive photosensitive resin composition comprises a polyimide precursor and a polybenzoxazole precursor. It is preferable to contain 20 to 200 parts by mass of phenol resin and particularly preferably 50 to 150 parts by mass of phenol resin with respect to 100 parts by mass of at least one resin selected from the group. The phenol resin content of 20 parts by mass or more is advantageous from the viewpoint of sensitivity, and the content of 200 parts by mass or less is advantageous from the viewpoint of adhesive strength between the cured film and the die attach film.

Use of a quinonediazide compound is desirable from the viewpoint of improving sensitivity. Specific examples of the quinonediazide compound include those described above in the section <Photosensitive resin composition>. The content of the quinonediazide compound is preferably 1 to 50 parts by mass with respect to a total of 100 parts by mass of at least one resin selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor and a phenol resin, More preferably, it is 5 to 30 parts by mass. When the content is 1 part by mass or more, the sensitivity is good, and when it is 50 parts by mass or less, the adhesive strength between the cured film and the die attach film is good.

The thickness of the cured film of the present disclosure is typically preferably 1 to 50 μm, more preferably 2 to 30 μm, and even more preferably 3 to 20 μm. The thickness of 1 μm or more is advantageous from the viewpoint of the function as a protective film and an insulating film, and the thickness of 50 μm or less is advantageous from the viewpoint of avoiding unnecessary cost increase.

EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example demonstrate this invention concretely, this invention is not limited to this.
In addition, the measurement conditions in an Example are as showing below.

<Weight average molecular weight (Mw)>
It was calculated by GPC in terms of standard polystyrene (organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko KK). The GPC apparatus used and the measurement conditions are as follows:
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40 ° C
Column: Shodex KD-806M Two in series Mobile phase: 0.1 mol / l EtBr / N-methylpyrrolidone Flow rate: 1.0 ml / min.

<Evaluation of patterning characteristics (sensitivity, residual film ratio)>
Preparation of pre-baked film and measurement of film thickness The photosensitive resin composition was spin-coated on a 6-inch silicon wafer with a spin coater (Tokyo Electron Clean Track Mark 8), and pre-baked on a hot plate at 125 ° C. for 180 seconds for evaluation. A working membrane was obtained. The initial film thickness of each composition was adjusted to 5 μm with the resin film thickness after curing at 320 ° C. for 30 minutes. The film thickness was measured with a film thickness measuring device (Lambda Ace manufactured by Dainippon Screen Mfg. Co., Ltd.).
- exposure to this coating film, stepwise change the exposure amount using a stepper (Nikon Corporation NSR2005i8A) having an exposure wavelength of i-line (365 nm) through a test pattern with the reticle to ^{150mJ / cm 2 ~ 800mJ / cm} 2 And exposed.
・ Developing Developed with a developing machine (D-SPIN) at 23 ° C. using 2.38% tetramethylammonium hydroxide aqueous solution AZ-300MIF (manufactured by AZ Electronic Materials) for 80 seconds, rinsed with pure water, and relief A pattern was formed.

[Sensitivity (mJ / cm ² )]
In the coating film produced on the said conditions, the minimum exposure amount which the 100 micrometer square relief pattern of an exposure part can melt | dissolve completely was evaluated as a sensitivity.
[Development residual film ratio (%)]
{(Film thickness after development) / (initial film thickness)} × 100.

<Evaluation of surface condition after development>
The developed film is visually observed. The whitened surface is indicated as “−2”. Using an optical microscope, the film is observed in a dark field at a magnification of 500 times. "-1" indicates that contact marks remain when touched with, and observes the film in a dark field at a magnification of 500 times. The film was observed in a dark field at a magnification of 500 times, and the film having a uniform film with no irregularities on the surface was defined as “+2.”
This whitening after development is caused by phase separation in the film when the compatibility between the polymer (a) and the phenol resin is poor, and the difference in solubility between the polymer (a) and the phenol resin in the alkaline developer is caused by This is a phenomenon that occurs when the film surface is uneven and has irregularities with a period longer than the visible light wavelength range (several hundred nm or more). In addition, contact marks after development have irregularities with a period of less than or equal to the visible light wavelength range after development (several tens to several hundreds of nm) formed on the surface due to phase separation. This occurs when the film is damaged by breaking the part. When the phase separation period is several tens of nanometers or less, contact marks are not generated even when the film surface after development is touched, and the film is uniform.

<Evaluation of surface condition after dry etching of cured film>
[Surface roughness after dry etching]
The photosensitive resin compositions obtained in Examples and Comparative Examples were spin-coated on a 6-inch silicon wafer so that the film thickness after curing was about 10 μm, and prebaked on a hot plate at 120 ° C. for 180 seconds. And a coating film was formed. The film thickness was measured with a film thickness measuring device (Lambda Ace) manufactured by Dainippon Screen Mfg. This coating film was heated at 320 ° C. for 30 minutes in a nitrogen atmosphere to obtain a cured film having a thickness of 10 μm.
Next, the obtained wafer with a cured film was dry-etched using a high-density plasma apparatus (device name: SWP, manufactured by Shinko Seiki Co., Ltd.). The processing conditions are as follows.
Plasma type: Microwave Processing gas: O ₂
Stage temperature: 200 ° C
Treatment time: 60 seconds Subsequently, surface roughness measurement and whitening evaluation of the surface of the cured film subjected to the dry etching treatment were performed.
The surface roughness was measured by using an atomic force microscope (AFM) (device name: Nanopics 1000, manufactured by Seiko Instruments Inc.) to measure the arithmetic average roughness Ra (unit: nm) for a measurement range of 5 μm square. The cantilever was NPX1CTP004, the measurement conditions were Damping Mode, and the scan speed was 50 sec / FRAME. Table 4 shows the measurement results.

[Evaluation of whitening after dry etching]
The whitening evaluation was performed by observing the surface of the dry-etched cured film with an optical microscope (product name: ECLIPSE L200, manufactured by Nikon). Whitening was evaluated according to the following criteria. The evaluation results are shown in Table 4.
Good: No abnormality.
Slightly poor: Whitening is observed in part of the cured film.
Poor: Whitening is observed in many parts of the cured film.

<Die attach film adhesive strength evaluation>
[Die attach film adhesive strength evaluation]
The photosensitive resin compositions obtained in Examples and Comparative Examples were spin-coated on a 6-inch silicon wafer so that the film thickness after curing was about 10 μm, and prebaked on a hot plate at 120 ° C. for 180 seconds. And a coating film was formed. The film thickness was measured with a film thickness measuring device (Lambda Ace) manufactured by Dainippon Screen Mfg. This coating film was heated at 320 ° C. for 30 minutes in a nitrogen atmosphere to obtain a cured film having a thickness of 10 μm. Next, this wafer with a cured film was diced using a dicing saw (device name: DAD3350, manufactured by Disco) to obtain a chip with a cured film having a size of 8.0 mm × 8.0 mm × 0.3 mm.

Subsequently, a die bond film (product name: DF-375, manufactured by Hitachi Chemical Co., Ltd.) was attached to the silicon wafer, and the cured film chip obtained above {size 8.0 mm × 8.0 mm × 0.3 mm (area 64 mm ²⁾ )} Is arranged at a pitch of 80 μm, 4 in the vertical direction and 6 in the horizontal direction, for a total of 24. Crimping was performed (in the order of silicon wafer / die bond film / chip with cured film), followed by baking at 180 ° C. for 1 hour.

Here, in the case of a semiconductor in which chips such as a stacked CSP are stacked, the above-described thermocompression bonding and baking are repeatedly performed. Assuming such a case, thermocompression bonding under conditions of a pressure bonding temperature of 240 ° C., a load of 1.96 N and a pressure bonding time of 10 seconds and baking at 180 ° C. for 1 hour were repeated 10 times in total.

Next, the adhesive strength of the sample consisting of silicon wafer / die bond film / chip with cured film was measured. The adhesive strength was measured using a desktop strength tester (product name: universal bond tester series 4000, manufactured by DAGE) under the condition that the sample was heated to 260 ° C. For each example and comparative example, 24 samples were measured, and the average value was used for the adhesive strength. The adhesive strength was evaluated according to the following criteria. The evaluation results are shown in Table 5.
Good: The average value of adhesive strength is greater than 1N. Bad: The average value of adhesive strength is 1N or less. For samples with an average value of adhesive strength of 1N or less, gas is generated from the cured film during repeated thermocompression bonding and baking. It is estimated that the adhesive strength has decreased.

[Weight change after heat treatment at 240 ° C. for 10 hours]
The sample for this measurement was produced by the following method. The photosensitive resin compositions obtained in Examples and Comparative Examples were spin-coated on a 6-inch silicon wafer substrate provided with an aluminum vapor deposition layer on the outermost surface so that the film thickness after curing was about 10 μm, and 120 ° C. Then, pre-baking was performed on a hot plate for 180 seconds to form a coating film. The film thickness was measured with a film thickness measuring device (Lambda Ace) manufactured by Dainippon Screen Mfg. This coating film was heated at 320 ° C. for 30 minutes in a nitrogen atmosphere to obtain a cured film having a thickness of 10 μm. The obtained cured film was cut to a width of 3 mm with a dicing saw and then peeled from the wafer with a dilute hydrochloric acid aqueous solution to obtain a cured film piece having a thickness of about 10 μm and a width of 3 mm. The weight change rate when this cured film piece was heated at 240 ° C. for 10 hours using a thermal analyzer (manufactured by Shimadzu Corporation, model name: DTG-60) was measured. The measurement conditions were as follows.
Sample length: 10mm
Constant load: 200 g / mm ²
Measurement temperature range: 240 ° C
Temperature increase rate: 0 ° C / min (constant)
Measurement atmosphere: The air weight change rate was calculated from the following formula based on the weight of the cured film measured before and during the heat treatment. Table 5 shows the measurement results.
Weight change rate (%) =
{Maximum weight during heat treatment (g) −Minimum weight during heat treatment (g)} / Weight before heat treatment (g) × 100

[Synthesis Example 1]
<Synthesis of diamine compound>
Under a dry nitrogen stream, 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter also referred to as “6FAP”) was added to 100 mL of acetone and 17.4 g of propylene oxide. (0.3 mol) and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride in 100 mL of acetone was added dropwise thereto. After completion of the dropwise addition, the mixture was reacted at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.

30 g of the solid was placed in a 300 mL GBL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated by confirming that the balloons did not squeeze any more. After completion of the reaction, the catalyst was filtered to remove the palladium compound as a catalyst, and the mixture was concentrated with a rotary evaporator to obtain diamine (1) having the following structure. The obtained solid was used for the reaction as it was.

[Synthesis Example 2]
<Preparation of bis (carboxy) tricyclo [5,2,1,0 ^2,6] decane>
Teflon was attached (registered trademark) of anchor-type agitator, (manufactured by Tokyo Kasei Kogyo Co., Ltd.) to a glass separable three-necked flask, tricyclo [5,2,1,0 ^2,6] decanedimethanol 71. Dissolve 9 g (0.366 mol) in 1 L of acetonitrile, dissolve 256.7 g (1.808 mol) of disodium hydrogen phosphate and 217.1 g (1.809 mol) of sodium dihydrogen phosphate in 1.4 L of ion-exchanged water. I put what I did. To this, 2.8 g (0.0179 mol) of 2,2,6,6-tetramethylpiperidine-1-oxyl (hereinafter also referred to as “TEMPO” manufactured by Tokyo Chemical Industry Co., Ltd.) was added and dissolved by stirring. I let you. 143.2 g (1.267 mol) of 80% sodium chlorite was diluted with 850 mL of ion-exchanged water, and this was added dropwise to the reaction solution. Subsequently, what diluted 3.7 mL of 5 mass% sodium dichlorite aqueous solution with 7 mL of ion-exchange water was dripped at the reaction liquid. This reaction solution was kept at 35 to 38 ° C. by a constant temperature layer and stirred for 20 hours to be reacted.

After the reaction, the reaction solution is cooled to 12 ° C., an aqueous solution in which 75 g of sodium sulfite is dissolved in 300 mL of ion-exchanged water is added dropwise to the reaction solution, the excess sodium chlorite is deactivated, and then with 500 mL of ethyl acetate. Washed. Thereafter, 115 mL of 10% hydrochloric acid was added dropwise to adjust the pH of the reaction solution to 3 to 4, and the precipitate was collected by decantation. This precipitate was dissolved in 200 mL of tetrahydrofuran. The aqueous layer was extracted twice with 500 mL of ethyl acetate and then washed with brine, and the precipitate was dissolved in a tetrahydrofuran solution. These tetrahydrofuran solutions were mixed and dried over anhydrous sodium sulfate. The solution concentrated in an evaporator, followed by drying, to obtain a bis (carboxy) tricyclo [5,2,1,0 ^2,6] white crystalline product with decane 58.4 g (71.1% yield).

[Synthesis Example 3]
<Preparation of bis (chlorocarbonyl) tricyclo [5,2,1,0 ^2,6] decane>
62.5 g (278 mmol) of bis (carboxy) tricyclo [5,2,1,0 ^2,6 ] decane obtained in Synthesis Example 2; 97 mL (1.33 mol) of thionyl chloride; and 0.4 mL (5.0 mmol) of pyridine. The reaction vessel was charged and stirred at 25-50 ° C. for 18 hours for reaction. After completion of the reaction, toluene was added, and the mixture was concentrated by removing excess thionyl chloride by azeotroping with toluene under reduced pressure. Oily bis (chlorocarbonyl) tricyclo [5,2,1,0 ^{2, 6} ] 73.3 g (100% yield) of decane was obtained.

[Synthesis Example 4]
In a 1 L separable flask, 4,4 ′-(1- (2- (4-hydroxyphenyl) -2-propyl) phenyl) ethylidene) bisphenol (manufactured by Honshu Chemical Industry Co., Ltd., trade name: Tris) as a polyhydroxy compound -PA) 30 g (0.0707 mol) of the compound was added, and 47.49 g (0.177 mol) of 1,2-naphthoquinonediazide-4-sulfonyl chloride in an amount corresponding to 83.3 mol% of the OH group of the compound was added thereto. ) Was stirred and dissolved in 300 g of acetone, and the flask was adjusted to 30 ° C. in a thermostatic bath. Next, a solution obtained by dissolving 17.9 g of triethylamine in 18 g of acetone was charged into a dropping funnel and then dropped into the flask over 30 minutes. Stirring was continued for another 30 minutes after completion of the dropping, and then hydrochloric acid was dropped, and stirring was further performed for 30 minutes to complete the reaction. Thereafter, filtration was performed to remove triethylamine hydrochloride. The obtained filtrate was added dropwise with stirring to a 3 L beaker in which 1640 g of pure water and 30 g of hydrochloric acid were mixed and stirred to obtain a precipitate. This precipitate was washed with water, filtered, and then dried under reduced pressure at 40 ° C. for 48 hours to obtain a quinonediazide compound (Q-1).

の構造を有するヒドロキシポリアミド樹脂（Ｐ－１）を得た。 [Synthesis Example 5]
<Synthesis of (a) hydroxy polyamide resin (P-1)>
Under a dry nitrogen stream, 13.6 g (0.0225 mol) of diamine (1) obtained in Synthesis Example 1 and 4-ethynylaniline (trade name: P-APAC, Fuji Photo Film Co., Ltd.) as a terminal blocking agent 0.29 g (0.0025 mol) was dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). To this, 7.75 g (0.025 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride was added together with 30 g of pyridine, and reacted at 60 ° C. for 6 hours. After completion of the reaction, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 50 ° C. for 60 hours, and the following formula:

A hydroxypolyamide resin (P-1) having the following structure was obtained.

The weight average molecular weight (Mw) by GPC of the hydroxypolyamide resin (P-1) synthesized in this way is a single sharp curve of 15,700 in terms of polystyrene, indicating that it is a single composition. confirmed.

[Synthesis Example 6]
<(A) Synthesis of hydroxypolyamide resin (P-2)>
In a 500 mL three-necked flask equipped with a Teflon (registered trademark) vertical stirrer, 3.72 g (0.02 mol) of 4,4-biphenol (manufactured by Tokyo Chemical Industry Co., Ltd.), the bis produced in Synthesis Example 3 ( a chlorocarbonyl) tricyclo [5,2,1,0 ^2,6] decane 47.0 g (0.175 mol) and the solution was stirred and mixed at room temperature (20 ~ 25 ° C. so) the GBL66.9G, separately GBL142.3g A mixture in which 9.49 g (0.12 mol) of pyridine was mixed was dropped from a dropping funnel. The time required for the dropping was 25 minutes, and the maximum reaction solution temperature was 40 ° C.

After the dropwise addition, the reaction solution stirred for 1 hour was added to 2,2-bis (3-amino-4-hydroxyphenyl) in a 2 L separable flask equipped with a separate Teflon (registered trademark) vertical stirrer. -Hexafluoropropane (hereinafter also referred to as "6FAP") 65.9 g (0.18 mol), 14.8 g (0.19 mol) of pyridine, 217 g of GBL and 72.5 g of DMAc were mixed and stirred at room temperature to dissolve, and the reaction The container was immersed in an ice bath and dropped into a solution cooled to −15 ° C. using a dropping funnel. The reaction system was maintained at −15 to 0 ° C. and took 1 hour, and was dropped into the reaction vessel.

After completion of the dropwise addition, the ice bath was removed, the mixture was stirred at 1 ° C. for 1 hour, and 4.74 g (0.06 mol) of pyridine was added. Thereafter, the reaction solution was returned to room temperature, and 24.6 g (0.15 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 11.8 g (0.15 mol) of pyridine were added. The reaction solution was immersed in a hot water bath at 0 ° C. for 24 hours.

（モル比率　ｎ／ｍ　＝　８０／　１０）
の構造を有するヒドロキシポリアミド（Ｐ－２）の粉体を得た。 Ethanol was added to the reaction solution to precipitate a polymer, and then recovered and dissolved in 646 g of GBL. Subsequently, ion exchange was performed with 62.1 g of a cation exchange resin (manufactured by Organo, Amberlyst A21) and 59.6 g of an anion exchange resin (manufactured by Organo, Amberlyst 15). This solution was dropped into 12 L of ion-exchanged water under high-speed stirring, and the polymer was dispersed and precipitated, recovered, appropriately washed with water, dehydrated, and vacuum-dried.

(Molar ratio n / m = 80/10)
A hydroxypolyamide (P-2) powder having the following structure was obtained.

The weight average molecular weight (Mw) by GPC of the hydroxypolyamide resin synthesized in this way is a single sharp curve of 12,700 in terms of polystyrene, confirming that it is a single composition.

FIG. 1 shows the ¹³ C-NMR result of the resulting hydroxypolyamide resin (P-2). A carbon peak derived from the biphenyl skeleton was observed near 138 ppm and 150 ppm, and a peak derived from an ester group was observed near 174 to 176 ppm.

[Synthesis Example 7]
<(A) Synthesis of hydroxypolyamide resin (P-3)>
59 g (0.1 mol) of P-2 prepared in Synthesis Example 6 and triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) To a solution in which 94 g (0.0093 mol) and GBL 240 g were mixed and stirred and dissolved at room temperature, a solution prepared by dissolving 5 g of GBL in 1.3 g (0.0093 mol) of benzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped from a dropping funnel. For 24 hours.

（モル比率　ｎ／ｍ　＝　８０／　１０）
の構造を有するヒドロキシポリアミド樹脂（Ｐ－３）の粉体を得た。 The reaction solution was ion-exchanged with 3.0 g of a cation exchange resin (manufactured by Organo, Amberlyst A21) and 3.0 g of an anion exchange resin (manufactured by Organo, Amberlyst 15). This solution was dropped into 6 L of ion-exchanged water under high-speed stirring, and the polymer was dispersed and precipitated, recovered, washed with water, dehydrated appropriately, and vacuum-dried.

(Molar ratio n / m = 80/10)
A powder of hydroxypolyamide resin (P-3) having the following structure was obtained.

The weight average molecular weight (Mw) by GPC of the hydroxypolyamide resin (P-3) synthesized in this way is a single sharp curve of 12,800 in terms of polystyrene, indicating that it is a single composition. confirmed.

[Synthesis Example 8]
First, the 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 resorcin, 4,4′-bis (methoxymethyl) biphenyl (BMMB) 84.8 g (0.35 mol), p-toluenesulfonic acid 3.81 g (0.02 mol), and propylene glycol monomethyl ether (PGME) 116 g were mixed and stirred at 50 ° C. to dissolve the solid matter. The dissolved mixed solution was heated to 120 ° C. with an oil bath, and generation of methanol was confirmed from the reaction solution. The reaction solution was stirred at 120 ° C. for 3 hours.

（モル比率　ｍ９／ｍ１０／ｍ２＝３０／３０／７０）
の構造を有するフェノール樹脂（Ｎ－１）を得た。合成された樹脂のＧＰＣによる重量平均分子量は、ポリスチレン換算で９，９００であった。 Next, in a separate container, 24.9 g (0.150 mol) of 2,6-bis (hydroxymethyl) -p-cresol and 499 g of PGME were mixed and stirred, and the uniformly dissolved solution was added to the separable solution using a dropping funnel. The solution was added dropwise to the flask in 1 hour, and stirred for another 2 hours after the addition. After completion of the reaction, the reaction vessel was cooled in the atmosphere, and 50 g of PGME was separately added thereto and stirred. The reaction diluted solution is dropped into 8 L of water under high-speed stirring to disperse and precipitate the resin, which is recovered, appropriately washed with water, dehydrated and then vacuum-dried.

(Molar ratio m9 / m10 / m2 = 30/30/70)
A phenol resin (N-1) having the following structure was obtained. The weight average molecular weight by GPC of the synthesized resin was 9,900 in terms of polystyrene.

FIG. 2 shows the ¹ H-NMR result of the obtained phenol resin (N-1).

[Synthesis Example 9]
First, a separable flask having a volume of 1.0 L with a Dean-Stark apparatus was purged with nitrogen, and thereafter, 99.1 g (0.9 mol) of resorcin, 2,6-bis (hydroxymethyl) -p -Cresol 116.4 g (0.7 mol), p-toluenesulfonic acid 3.81 g (0.02 mol) and propylene glycol monomethyl ether (PGME) 116 g were mixed and stirred at 50 ° C. to dissolve the solid matter. The dissolved mixed solution was heated to 120 ° C. with an oil bath, and generation of methanol was confirmed from the reaction solution. The reaction solution was stirred at 120 ° C. for 3 hours.

（モル比率　ｍ３／ｍ４＝５０／５０）
の構造を有するフェノール樹脂（Ｎ－２）を得た。合成された樹脂のＧＰＣによる重量平均分子量は、ポリスチレン換算で９，４００であった。 After completion of the reaction, the reaction vessel was cooled in the atmosphere, and 50 g of PGME was separately added thereto and stirred. The reaction diluted solution is dropped into 8 L of water under high-speed stirring to disperse and precipitate the resin, which is recovered, appropriately washed with water, dehydrated and then vacuum-dried.

(Molar ratio m3 / m4 = 50/50)
A phenol resin (N-2) having the following structure was obtained. The weight average molecular weight by GPC of the synthesized resin was 9,400 in terms of polystyrene.

（モル比率　ｍ５／ｍ６　＝　６０／４０）
の構造を有するフェノール樹脂（Ｎ－３）を得た。合成された樹脂のＧＰＣによる重量平均分子量は、ポリスチレン換算で１０，６００であった。 [Synthesis Example 10]
First, a 1.0 L separable flask equipped with a Dean-Stark apparatus was purged with nitrogen. Thereafter, 51.85 g (0.48 mol) of m-cresol and 34.6 g of p-cresol (0. 32 mol), 86.2 g (0.71 mol) of salicylaldehyde and 2.69 g (0.014 mol) of p-toluenesulfonic acid were mixed and stirred. The dissolved mixed solution was heated to 100 ° C. with an oil bath and stirred for 2 hours, and then stirred at 150 ° C. for 8 hours while appropriately adding dipropylene glycol dimethyl ether. After completion of the reaction, the reaction vessel was cooled in the atmosphere, and 100 g of PGME was separately added thereto and stirred. The reaction diluted solution is dropped into 8 L of water under high-speed stirring to disperse and precipitate the resin, which is recovered, appropriately washed with water, dehydrated and then vacuum-dried.

(Molar ratio m5 / m6 = 60/40)
A phenol resin (N-3) having the structure: The weight average molecular weight by GPC of the synthesized resin was 10,600 in terms of polystyrene.

[Synthesis Example 11]
First, a 1.0 L separable flask equipped with a Dean-Stark apparatus was purged with nitrogen. Then, in this separable flask, 109.0 g (0.8 mol) of 2,3,5-trimethylphenol, salicylaldehyde 42. 73 g (0.35 mol) and 2.69 g (0.014 mol) of p-toluenesulfonic acid were mixed and stirred. The dissolved mixed solution was heated to 100 ° C. with an oil bath and stirred for 2 hours, and then stirred for 8 hours at 150 ° C. while appropriately adding dipropylene glycol dimethyl ether, and then the liquid temperature was cooled to 80 ° C.
Next, 28.4 g of 37% formalin was dropped into the separable flask over 1 hour using a dropping funnel, and the mixture was further stirred for 2 hours after dropping.

（モル比率　Ｍ／Ｎ　＝　５０／５０）
の構造を有するフェノール樹脂（Ｎ－４）を得た。合成された樹脂のＧＰＣによる重量平均分子量は、ポリスチレン換算で９，２００であった。 After completion of the reaction, the reaction vessel was cooled in the atmosphere, and 100 g of PGME was separately added thereto and stirred. The reaction diluted solution is dropped into 8 L of water under high-speed stirring to disperse and precipitate the resin, which is recovered, appropriately washed with water, dehydrated and then vacuum-dried.

(Molar ratio M / N = 50/50)
A phenol resin (N-4) having the following structure was obtained. The weight average molecular weight by GPC of the synthesized resin was 9,200 in terms of polystyrene.

[Synthesis Example 12]
100.9 g (0.8 mol) of phloroglucinol and 121.2 g (4. 5 mol), 3.9 g (0.025 mol) of diethyl sulfuric acid, and 140 g of diethylene glycol dimethyl ether were mixed and stirred at 70 ° C. to dissolve the solid matter, thereby obtaining a mixed solution.

の構造を有するフェノール樹脂（Ｎ－５）を得た。合成された樹脂のＧＰＣによる重量平均分子量は、ポリスチレン換算で１５，０００であった。 The obtained mixed solution was heated to 140 ° C. by 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 to obtain a reaction diluted solution. This reaction diluted solution was dropped into 4 L of water under high-speed stirring to disperse and precipitate the resin, and this precipitate was collected, washed with water as appropriate, dehydrated and then vacuum-dried, and composed of phloroglucinol / BMMB.

A phenol resin (N-5) having the following structure was obtained. The weight average molecular weight by GPC of the synthesized resin was 15,000 in terms of polystyrene.

<Preparation of positive photosensitive resin composition>
[Example 1]
10 g of P-1 produced in Synthesis Example 5 and 2 g of N-1 produced in Synthesis Example 8 were weighed and dissolved in 20 g of GBL together with 1.68 g of the quinonediazide compound Q-1 produced in Synthesis Example 4. The mixture was filtered through a 1 μm filter to prepare a positive photosensitive resin composition.
[Example 2]
10 g of P-1 produced in Synthesis Example 5 and 5 g of N-1 produced in Synthesis Example 8 were weighed and dissolved in 25 g of GBL together with 2.1 g of the quinonediazide compound Q-1 produced in Synthesis Example 4. The mixture was filtered through a 1 μm filter to prepare a positive photosensitive resin composition.
[Example 3]
10 g of P-1 produced in Synthesis Example 5 and 10 g of N-1 produced in Synthesis Example 8 were weighed and dissolved in GBL, 33.3 g together with 2.8 g of the quinonediazide compound Q-1 produced in Synthesis Example 4. Thereafter, the mixture was filtered through a 1 μm filter to prepare a positive photosensitive resin composition.
Type photosensitive resin composition was prepared.
[Example 4]
10 g of P-1 produced in Synthesis Example 5 and 20 g of N-1 produced in Synthesis Example 8 were weighed and dissolved in 50 g of GBL together with 4.2 g of the quinonediazide compound Q-1 produced in Synthesis Example 4. The mixture was filtered through a 1 μm filter to prepare a positive photosensitive resin composition.
[Example 5]
A positive photosensitive resin composition was similarly prepared using N-2 produced in Synthesis Example 9 instead of N-1 used in Example 1.
[Example 6]
A positive photosensitive resin composition was similarly prepared using N-2 produced in Synthesis Example 9 instead of N-1 used in Example 2.
[Example 7]
A positive photosensitive resin composition was similarly prepared using N-2 produced in Synthesis Example 9 instead of N-1 used in Example 3.
[Example 8]
A positive photosensitive resin composition was similarly prepared using N-2 produced in Synthesis Example 9 instead of N-1 used in Example 4.
[Example 9]
Using the phenol resin AEG018 (trade name, phenol component: bisphenol A, aldehyde component: formaldehyde, manufactured by Gunei Chemical Co., Ltd.) instead of N-1 used in Example 1, the same positive photosensitive resin composition was used. A product was prepared.
[Example 10]
Using the phenol resin AEG018 (trade name, phenol component: bisphenol A, aldehyde component: formaldehyde, manufactured by Gunei Chemical Co., Ltd.) instead of N-1 used in Example 2, the positive photosensitive resin composition was similarly used. A product was prepared.

[Example 11]
A positive photosensitive resin composition was similarly used by using phenol resin AEG018 (trade name, phenol component: bisphenol A, aldehyde component: formaldehyde, manufactured by Gunei Chemical Co., Ltd.) instead of N-1 used in Example 3. A product was prepared.
[Example 12]
Using the phenol resin AEG018 (trade name, phenol component: bisphenol A, aldehyde component: formaldehyde, manufactured by Gunei Chemical Co., Ltd.) instead of N-1 used in Example 4, the same positive photosensitive resin composition was used. A product was prepared.
[Example 13]
Instead of N-1 used in Example 1, phenol resin AEG024 (trade name, phenol component: m-cresol / p-cresol ratio = 60/40, aldehyde component: formaldehyde / salicylaldehyde ratio = 70/30, Gunei A positive photosensitive resin composition was prepared in the same manner using Chemicals Co., Ltd.
[Example 14]
Instead of N-1 used in Example 2, phenol resin AEG024 (trade name, phenol component: m-cresol / p-cresol ratio = 60/40, aldehyde component: formaldehyde / salicylaldehyde ratio = 70/30, Gunei A positive photosensitive resin composition was prepared in the same manner using Chemicals Co., Ltd.
[Example 15]
Instead of N-1 used in Example 3, phenol resin AEG024 (trade name, phenol component: m-cresol / p-cresol ratio = 60/40, aldehyde component: formaldehyde / salicylaldehyde ratio = 70/30, Gunei A positive photosensitive resin composition was prepared in the same manner using Chemicals Co., Ltd.
[Example 16]
Instead of N-1 used in Example 4, phenol resin AEG024 (trade name, phenol component: m-cresol / p-cresol ratio = 60/40, aldehyde component: formaldehyde / salicylaldehyde ratio = 70/30, Gunei A positive photosensitive resin composition was prepared in the same manner using Chemicals Co., Ltd.
[Example 17]
A positive photosensitive resin composition was similarly prepared using N-3 produced in Synthesis Example 10 instead of N-1 used in Example 1.
[Example 18]
A positive photosensitive resin composition was similarly prepared using N-3 produced in Synthesis Example 10 instead of N-1 used in Example 2.
[Example 19]
A positive photosensitive resin composition was similarly prepared using N-3 produced in Synthesis Example 10 instead of N-1 used in Example 3.
[Example 20]
A positive photosensitive resin composition was prepared in the same manner using N-3 produced in Synthesis Example 10 instead of N-1 used in Example 4.

[Example 21]
A positive photosensitive resin composition was similarly prepared using P-2 produced in Synthesis Example 6 instead of P-1 used in Example 1.
[Example 22]
A positive photosensitive resin composition was similarly prepared using P-2 produced in Synthesis Example 6 instead of P-1 used in Example 2.
[Example 23]
A positive photosensitive resin composition was similarly prepared using P-2 produced in Synthesis Example 6 instead of P-1 used in Example 3.
[Example 24]
A positive photosensitive resin composition was similarly prepared using P-2 produced in Synthesis Example 6 instead of P-1 used in Example 4.
[Example 25]
A positive photosensitive resin composition was similarly prepared using P-2 produced in Synthesis Example 6 instead of P-1 used in Example 5.
[Example 26]
A positive photosensitive resin composition was similarly prepared using P-2 produced in Synthesis Example 6 instead of P-1 used in Example 6.
[Example 27]
A positive photosensitive resin composition was similarly prepared using P-2 produced in Synthesis Example 6 instead of P-1 used in Example 7.
[Example 28]
A positive photosensitive resin composition was similarly prepared using P-2 produced in Synthesis Example 6 instead of P-1 used in Example 8.
[Example 29]
A positive photosensitive resin composition was similarly prepared using P-2 produced in Synthesis Example 6 instead of P-1 used in Example 9.
[Example 30]
A positive photosensitive resin composition was similarly prepared using P-2 produced in Synthesis Example 6 instead of P-1 used in Example 10.

[Example 31]
A positive photosensitive resin composition was similarly prepared using P-2 produced in Synthesis Example 6 instead of P-1 used in Example 11.
[Example 32]
A positive photosensitive resin composition was similarly prepared using P-2 produced in Synthesis Example 6 instead of P-1 used in Example 12.
[Example 33]
A positive photosensitive resin composition was similarly prepared using P-2 produced in Synthesis Example 6 instead of P-1 used in Example 13.
[Example 34]
A positive photosensitive resin composition was similarly prepared using P-2 produced in Synthesis Example 6 instead of P-1 used in Example 14.
[Example 35]
A positive photosensitive resin composition was similarly prepared using P-2 produced in Synthesis Example 6 instead of P-1 used in Example 15.
[Example 36]
A positive photosensitive resin composition was similarly prepared using P-2 produced in Synthesis Example 6 instead of P-1 used in Example 16.
[Example 37]
A positive photosensitive resin composition was prepared in the same manner using P-2 produced in Synthesis Example 6 instead of P-1 used in Example 17.
[Example 38]
A positive photosensitive resin composition was similarly prepared using P-2 produced in Synthesis Example 6 instead of P-1 used in Example 18.
[Example 39]
A positive photosensitive resin composition was similarly prepared using P-2 produced in Synthesis Example 6 instead of P-1 used in Example 19.
[Example 40]
A positive photosensitive resin composition was similarly prepared using P-2 produced in Synthesis Example 6 instead of P-1 used in Example 20.

[Example 41]
A positive photosensitive resin composition was similarly prepared using P-3 produced in Synthesis Example 7 instead of P-1 used in Example 1.
[Example 42]
A positive photosensitive resin composition was prepared in the same manner using P-3 produced in Synthesis Example 7 instead of P-1 used in Example 2.
[Example 43]
A positive photosensitive resin composition was similarly prepared using P-3 produced in Synthesis Example 7 instead of P-1 used in Example 3.
[Example 44]
A positive photosensitive resin composition was similarly prepared using P-3 produced in Synthesis Example 7 instead of P-1 used in Example 4.
[Example 45]
A positive photosensitive resin composition was similarly prepared using P-3 produced in Synthesis Example 7 instead of P-1 used in Example 5.
[Example 46]
A positive photosensitive resin composition was prepared in the same manner using P-3 produced in Synthesis Example 7 instead of P-1 used in Example 6.
[Example 47]
A positive photosensitive resin composition was similarly prepared using P-3 produced in Synthesis Example 7 instead of P-1 used in Example 7.
[Example 48]
A positive photosensitive resin composition was similarly prepared using P-3 produced in Synthesis Example 7 instead of P-1 used in Example 8.
[Example 49]
A positive photosensitive resin composition was similarly prepared using P-3 produced in Synthesis Example 7 instead of P-1 used in Example 9.
[Example 50]
A positive photosensitive resin composition was similarly prepared using P-3 produced in Synthesis Example 7 instead of P-1 used in Example 10.

[Example 51]
A positive photosensitive resin composition was similarly prepared using P-3 produced in Synthesis Example 7 instead of P-1 used in Example 11.
[Example 52]
A positive photosensitive resin composition was similarly prepared using P-3 produced in Synthesis Example 7 instead of P-1 used in Example 12.
[Example 53]
A positive photosensitive resin composition was prepared in the same manner using P-3 produced in Synthesis Example 7 instead of P-1 used in Example 13.
[Example 54]
A positive photosensitive resin composition was similarly prepared using P-3 produced in Synthesis Example 7 instead of P-1 used in Example 14.
[Example 55]
A positive photosensitive resin composition was prepared in the same manner using P-3 produced in Synthesis Example 7 instead of P-1 used in Example 15.
[Example 56]
A positive photosensitive resin composition was similarly prepared using P-3 produced in Synthesis Example 7 instead of P-1 used in Example 16.
[Example 57]
A positive photosensitive resin composition was similarly prepared using P-3 produced in Synthesis Example 7 instead of P-1 used in Example 17.
[Example 58]
A positive photosensitive resin composition was prepared in the same manner using P-3 produced in Synthesis Example 7 instead of P-1 used in Example 18.
[Example 59]
A positive photosensitive resin composition was similarly prepared using P-3 produced in Synthesis Example 7 instead of P-1 used in Example 19.
[Example 60]
A positive photosensitive resin composition was similarly prepared using P-3 produced in Synthesis Example 7 instead of P-1 used in Example 20.

[Comparative Example 1]
10 g of P-1 produced in Synthesis Example 5 was weighed and dissolved in 16.7 g of GBL together with 1.4 g of the quinonediazide compound Q-1 produced in Synthesis Example 4, and then filtered through a 1 μm filter. A photosensitive resin composition was prepared.
[Comparative Example 2]
10 g of P-1 produced in Synthesis Example 5 and 2 g of phenol resin EP4000B (trade name, m-cresol / p-cresol ratio = 60/40, manufactured by Asahi Organic Materials Co., Ltd.) were measured and produced in Synthesis Example 4. The quinonediazide compound Q-1 and 1.68 g were dissolved in 20 g of GBL, and then filtered through a 1 μm filter to prepare a positive photosensitive resin composition.
[Comparative Example 3]
10 g of P-1 produced in Synthesis Example 5 and 5 g of phenol resin EP4000B (trade name, m-cresol / p-cresol ratio = 60/40, manufactured by Asahi Organic Materials Co., Ltd.) were measured and produced in Synthesis Example 4. The quinonediazide compound Q-1 and 2.1 g together with GBL and 25 g were dissolved and then filtered through a 1 μm filter to prepare a positive photosensitive resin composition.
[Comparative Example 4]
10 g of P-1 produced in Synthesis Example 5 and 10 g of phenol resin EP4000B (trade name, m-cresol / p-cresol ratio = 60/40, manufactured by Asahi Organic Materials Co., Ltd.) were measured and produced in Synthesis Example 4. The quinonediazide compound Q-1 and 2.8 g together with GBL and 33.3 g were dissolved and then filtered through a 1 μm filter to prepare a positive photosensitive resin composition.
Type photosensitive resin composition was prepared.
[Comparative Example 5]
10 g of P-1 produced in Synthesis Example 5 and 20 g of phenol resin EP4000B (trade name, m-cresol / p-cresol ratio = 60/40, manufactured by Asahi Organic Materials Co., Ltd.) were measured and produced in Synthesis Example 4. The quinonediazide compound Q-1 and 4.2 g were dissolved in 50 g of GBL, and then filtered through a 1 μm filter to prepare a positive photosensitive resin composition.
[Comparative Example 6]
A positive photosensitive resin composition was similarly prepared using phenol resin MXP5560BF (trade name, phenol / m-cresol / p-cresol ratio = 50/30/20) instead of the phenol resin used in Comparative Example 2. did.
[Comparative Example 7]
Using the phenol resin MXP5560BF (trade name, phenol / m-cresol / p-cresol ratio = 50/30/20) instead of the phenol resin used in Comparative Example 3, a positive photosensitive resin composition was similarly prepared. did.
[Comparative Example 8]
Using the phenol resin MXP5560BF (trade name, phenol / m-cresol / p-cresol ratio = 50/30/20) instead of the phenol resin used in Comparative Example 4, a positive photosensitive resin composition was similarly prepared. did.
[Comparative Example 9]
Using the phenol resin MXP5560BF (trade name, phenol / m-cresol / p-cresol ratio = 50/30/20) instead of the phenol resin used in Comparative Example 5, a positive photosensitive resin composition was similarly prepared. did.
[Comparative Example 10]
A positive photosensitive resin composition was similarly prepared using N-4 produced in Synthesis Example 11 in place of the phenol resin used in Comparative Example 2.

[Comparative Example 11]
A positive photosensitive resin composition was similarly prepared using N-4 produced in Synthesis Example 11 instead of the phenol resin used in Comparative Example 3.
[Comparative Example 12]
A positive photosensitive resin composition was similarly prepared using N-4 produced in Synthesis Example 11 instead of the phenol resin used in Comparative Example 4.
[Comparative Example 13]
A positive photosensitive resin composition was similarly prepared using N-4 produced in Synthesis Example 11 instead of the phenol resin used in Comparative Example 5.
[Comparative Example 14]
A positive photosensitive resin composition was similarly prepared using P-2 produced in Synthesis Example 6 instead of P-1 used in Comparative Example 6.
[Comparative Example 15]
A positive photosensitive resin composition was similarly prepared using P-2 produced in Synthesis Example 6 instead of P-1 used in Comparative Example 7.
[Comparative Example 16]
A positive photosensitive resin composition was similarly prepared using P-2 produced in Synthesis Example 6 instead of P-1 used in Comparative Example 8.
[Comparative Example 17]
A positive photosensitive resin composition was prepared in the same manner using P-2 produced in Synthesis Example 6 instead of P-1 used in Comparative Example 9.
[Comparative Example 17]
A positive photosensitive resin composition was prepared in the same manner using P-2 produced in Synthesis Example 6 instead of P-1 used in Comparative Example 9.
[Examples 61 to 64]
A positive photosensitive resin composition was similarly prepared using the phenol resin N-5 produced in Synthesis Example 12 instead of N-1 used in Examples 1 to 4.
[Examples 65 to 68]
In place of N-1 used in Examples 1 to 4, a phenol resin N-6 (phenol component: bisphenol S, aldehyde component: formaldehyde, manufactured by Konishi Chemical Industry Co., Ltd.) was used in the same manner, and a positive photosensitive resin. A composition was prepared.
[Examples 69 to 72]
A positive photosensitive resin composition was similarly prepared using phenol resin MEH-7600-4H (trade name, manufactured by Gunei Chemical Co., Ltd.) instead of N-1 used in Examples 1 to 4.

The structure of the phenol resin described above is shown below.

The patterning characteristics of the prepared positive photosensitive resin compositions of Examples 1 to 60, Comparative Examples 1 to 17, and Examples 61 to 72 were evaluated, and the surface condition after development was evaluated. The results are shown in Table 1, Table 2 and Table 3.

[Examples 73 to 92, Comparative Examples 18 to 29]
Surface evaluation after dry etching treatment of cured films obtained from the positive photosensitive resin compositions prepared in the above Examples and Comparative Examples (Examples 73 to 82, Comparative Examples 18 to 23), die attach film adhesion Strength evaluation (Examples 83 to 92, Comparative Examples 24 to 29) was performed. The results are shown in Tables 4 and 5.

From the results shown in Table 1, Table 2 and Table 3, Examples 1 to 60 are excellent in sensitivity and development residual film ratio, and show that the surface state after development is good. Further, in Examples 21 to 40, by using a polymer having an ester structure introduced into the polymer skeleton, the remaining film ratio during development is improved as compared with Examples 1 to 20, and the surface condition after development is improved. Indicates that Further, in Examples 41 to 60, by using a polymer having an ester structure introduced in the side chain of the polymer, the remaining film ratio during development is improved as compared with Examples 21 to 40, and the surface condition after development is further improved. Indicates that it is good.
And from the result shown in Table 4 and Table 5, it consists of the positive photosensitive resin composition containing at least 1 sort (s) of resin selected from a polyimide precursor and a polybenzoxazole precursor, a quinonediazide compound, a phenol resin, and a solvent. The cured film obtained by applying the photosensitive resin layer to the substrate, exposing, developing, and curing it has a good surface state after the dry etching treatment and shows good die attach film adhesive strength.

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 (13)

(A) The following general formula (1):

(Wherein R ₁ and R ₂ each independently represents a divalent to octavalent organic group having 2 to 60 carbon atoms, and R ₃ , R ₄ , R ₅ and R ₆ are each independently hydrogen. An atom or a monovalent organic group having 1 to 20 carbon atoms, d and e are each independently an integer of 0 to 2 and are not simultaneously 0, and f and g are each independently An integer from 0 to 4, and n is a positive integer.)
A polymer whose main component is a structural unit represented by:
(B) a quinonediazide compound;
(C) a phenol resin,
The (c) phenolic resin has the following general formulas (2), (3), and (4), and general formula group (5):

(Wherein R ₇ and R ₈ each independently represents a monovalent organic group having 1 to 10 carbon atoms, h and j are each independently an integer of 1 to 3, i and k are Each independently represents an integer of 0 to 2, satisfying 1 ≦ (h + i) ≦ 4, 1 ≦ (j + k) ≦ 4, m1 is 0 or a positive integer, and m2 is a positive integer. )

(Wherein R ₉ and R ₁₀ each independently represents a monovalent organic group having 1 to 10 carbon atoms, l is 2 or 3, p is an integer of 1 to 3, o and q Are each independently an integer of 0 to 2, satisfying 2 ≦ (l + o) ≦ 4, 1 ≦ (p + q) ≦ 4, m3 is a positive integer, and m4 is 0 or a positive integer .)

(Wherein R ₁₁ and R ₁₂ each independently represents a monovalent organic group having 1 to 10 carbon atoms, r and u are each independently an integer of 1 to 3, and s and v are Each independently an integer from 0 to 2, satisfying 1 ≦ (r + s) ≦ 4, 1 ≦ (u + v) ≦ 4, m5 is 0 or a positive integer, and m6 is a positive integer, m11 is a positive integer, and P ₁ is a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group, a carboxyl group or an amino group.

{In the formula, each R ₁₃ independently represents a monovalent organic group having 1 to 10 carbon atoms, w is an integer of 1 to 3, x is an integer of 0 to 2, and 1 ≦ (w + x ) ≦ 4, m7 is a positive integer, and m8 is 0 or a positive integer, and Y is the following formula group (5 ′):

(P ₄ and P ₅ are each independently a hydrogen atom, a monovalent aliphatic group which may be substituted with fluorine having 1 to 20 carbon atoms, or substituted or unsubstituted 1 having 6 to 20 carbon atoms. Valent aromatic group.)
A divalent organic group selected from the group consisting of }
A positive photosensitive resin composition having a structure represented by at least one selected from the group consisting of: The phenol resin is represented by the following general formula (4 ′)

(Wherein R ₁₁ and R ₁₂ each independently represents a monovalent organic group having 1 to 10 carbon atoms, r, t and u are each independently an integer of 1 to 3; v is each independently an integer of 0 to 2, satisfies 1 ≦ (r + s) ≦ 4, 1 ≦ (u + v) ≦ 4, m5 is 0 or a positive integer, and m6 is a positive integer is there.)
The positive photosensitive resin composition of Claim 1 which has a structure represented by these. The phenol resin is a structure represented by at least one selected from the group consisting of the general formula group (5), and the Y is represented by the following general formula (5 ″):

(P ₄ and P ₅ are the same as defined in the formula group (5 ′).)
The positive photosensitive resin composition of Claim 1 which has a structure represented by these. The positive photosensitive resin composition according to any one of claims 1 to 3, wherein R ₁ or R ₂ of the general formula (1) or both of them has a structure having an ester bond. R ₁ or R _{2 in} the general formula (1) is represented by the following general formula (6):

(Wherein R ₁₈ , R ₁₉ and R ₂₀ each independently represents a divalent organic group having 2 to 60 carbon atoms, and at least one of R ₁₈ , R ₁₉ and R ₂₀ is alicyclic. Having a structure or an aliphatic structure, and m is 0 or 1.)
The positive photosensitive resin composition according to any one of claims 1 to 4, which has a structure represented by: R ₃ or R _{4 in} the general formula (1) is represented by the following general formula (7):

(In the formula, R ₂₁ represents a monovalent organic group having 1 to 19 carbon atoms.)
The positive photosensitive resin composition according to any one of claims 1 to 5, which has a structure represented by: (A) forming a photosensitive resin layer composed of the photosensitive resin composition according to any one of claims 1 to 6 on a substrate;
(B) a step of exposing the photosensitive resin layer;
(C) removing the exposed portion with a developer to obtain a relief pattern; and (D) heating the relief pattern.
A method for producing a cured relief pattern. A cured relief pattern produced by the method according to claim 7. 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 8. A display body device comprising a display body element and a cured film provided on top of the display body element, wherein the cured film is the cured relief pattern according to claim 8. A cured film containing at least one resin selected from the group consisting of polyimide and polybenzoxazole and a phenol resin,
The cured film has the following conditions:
Plasma type: Microwave Processing gas: O ₂
Treatment time: A cured film having an arithmetic average surface roughness of 0.5 to 5.0 nm as measured using an atomic force microscope (AFM) after a dry etching treatment of 60 seconds. The cured film according to claim 11, wherein the rate of change in weight loss when heat-treated at 240 ° C for 10 hours in an air atmosphere is 0.1 to 3.0%. The cured film according to claim 11 or 12, comprising 20 to 200 parts by mass of the phenol resin with respect to 100 parts by mass of at least one resin selected from the group consisting of the polyimide and polybenzoxazole.

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