JP2018055124A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition achieving a high film residual rate by development, high sensitivity, and a good profile of a cured relief pattern and less likely inducing corrosion of a metal after etching by a fluorine compound gas.SOLUTION: A positive photosensitive resin composition is provided, which comprises (a) a polymer having a structure represented by general formula (1) below as a main component, (b) a quinone diazide compound, and (c) a phenolic resin; and the composition contains 50 to 100 parts by mass of (c) component with respect to 100 parts by mass of (a) component.SELECTED DRAWING: None

Description

  The present invention relates to an insulating material for electronic parts, and a photosensitive resin composition used for forming relief patterns 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 characteristics, mechanical characteristics, 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 mixed with a photoacid generator such as a naphthoquinonediazide compound.

  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 composition described above 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 progressing, 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 called 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 of increasing the development residual film ratio, 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 the 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.

  In addition, a photosensitive resin composition (Patent Document 5) using 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. 4549001 JP-A-2005-250160 International Publication No. 2011/135887

  However, in the composition described in Patent Document 1, the trialkylsilyl ester easily hydrolyzes in the solution, so that a stable developability cannot be obtained.

  Moreover, in the material of patent document 2, since the addition amount of a phenol resin is 0.01-20 mass parts with respect to 100 mass parts of hydroxy polyamide resin, it is a problem that the image development residual film rate is inadequate. Met.

Furthermore, since the photosensitive resin composition described in Patent Document 3 adds 101 parts by mass or more of the phenol resin to 100 parts by mass of the hydroxypolyamide resin, the proportion of the phenol resin is large, and the heat resistance of the phenol resin is low. There was a problem that the pattern shape after curing deteriorated. Furthermore, since the phenol resin has low heat resistance in the cured film, degassing increases. The problem is that the degree of elongation of the cured film is also poor.
Regarding Patent Document 4, although there is a description about resolution after curing, there is no description about developability and sensitivity.

  In general, when a photosensitive resin composition is coated, exposed, developed, and cured on a metal and then etched using a fluorine-based compound, the opening portion is subjected to a reliability test such as a constant temperature and humidity condition. Corrosion may occur on the metal. When corrosion occurs in the semiconductor manufacturing process, there is a problem of reducing the reliability of the semiconductor package. These phenomena are not described in Patent Documents 1 to 5.

  Accordingly, an object of the present invention is to provide a photosensitive resin composition having a high development residual film ratio, high sensitivity, a good shape of a cured relief pattern, and metal corrosion hardly occurring after etching with a fluorine-based compound gas. Is to provide.

（式中、Ｒ₁は炭素原子数２〜６０の２価から８価の有機基を示し、Ｒ₂は炭素原子、水素原子、窒素原子、酸素原子及び硫黄原子から成る炭素原子数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原子数１から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（ａ）成分１００質量部に対して該（ｃ）成分を５０〜１００質量部含有する、ポジ型感光性樹脂組成物。
［２］ 該一般式（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］に記載のポジ型感光性樹脂組成物。
［３］ 該一般式（１）のＲ₁又はＲ₂が、下記一般式（２）：

（式中、Ｒ₈、Ｒ₉、及びＲ₁₀は、それぞれ独立に、炭素原子数１〜６０の２価の有機基を示し、Ｒ₈、Ｒ₉、及びＲ₁₀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］又は［２］に記載のポジ型感光性樹脂組成物。
［４］ 該一般式（１）のＲ₃若しくはＲ₄又はこれらの両者が、下記一般式（３）：

（式中、Ｒ₇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、上記［１］〜［３］のいずれかに記載のポジ型感光性樹脂組成物。
［５］ 該（ｃ）フェノール樹脂が、下記一般式（４）〜（６）：

（式中、Ｒ₁₁及びＲ₁₂はそれぞれ独立に炭素原子数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、但し１≦（ｈ＋ｉ）≦４、１≦（ｊ＋ｋ）≦４を満たし、そしてｍ１及びｍ２はそれぞれ独立に０又は正の整数であって同時に０にはならない。）

（式中、Ｒ₁₃及びＲ₁₄はそれぞれ独立に炭素原子数１〜１０の１価の有機基を示し、ｌ及びｐはそれぞれ独立に０〜２の整数であり、ｍ３は０又は正の整数であり、そしてｍ４は正の整数である。）

（式中、Ｒ₁₅は炭素原子数１〜１０の１価の有機基を示し、ｑは０〜２の整数であり、ｍ５は正の整数であり、そしてｍ６は０又は正の整数である。）
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ノボラック樹脂である、上記［１］〜［４］のいずれかに記載のポジ型感光性樹脂組成物。
［６］ （Ａ）上記［１］〜［５］のいずれかに記載の感光性樹脂組成物から成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、
を含む、硬化レリーフパターンの製造方法。
［７］ 上記［６］に記載の方法により製造された、硬化レリーフパターン。
［８］ 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［７］に記載の硬化レリーフパターンである、半導体装置。
［９］ 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［７］に記載の硬化レリーフパターンである、表示体装置。 As a result of earnestly examining and repeating experiments in view of the above-mentioned problems of the prior art, the present inventor has found that the above problems can be solved by mixing and using a hydroxypolyamide derivative and a phenol resin at a specific ratio, It came to make this invention. That is, the present invention is as follows.
[1] (a) The following general formula (1):

(In the formula, R ₁ represents a divalent to octavalent organic group having 2 to 60 carbon atoms, and R ₂ has 2 to 60 carbon atoms composed of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, and a sulfur atom. R ₃ , R ₄ , R ₅ , and R ₆ each independently represent a hydrogen 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 do not simultaneously become 0, f and g are each independently an integer of 0 to 4, and n is a positive integer.)
A polymer whose main component is a structure represented by:
(B) a quinonediazide compound;
(C) a phenol resin,
A positive photosensitive resin composition containing 50 to 100 parts by mass of the component (c) with respect to 100 parts by mass of the component (a).
[2] The positive photosensitive resin composition according to the above [1], wherein R ₁ or R ₂ of the general formula (1) or both of them have a structure having an ester bond.
[3] R ₁ or R _{2 in} the general formula (1) is represented by the following general formula (2):

(Wherein R ₈ , R ₉ and R ₁₀ each independently represents a divalent organic group having 1 to 60 carbon atoms, and at least one of R ₈ , R ₉ and R ₁₀ is It has an alicyclic structure or an aliphatic structure, and m is 0 or 1.)
The positive photosensitive resin composition according to the above [1] or [2], which has a structure represented by:
[4] R ₃ or R ₄ of the general formula (1) or both of them are represented by the following general formula (3):

(In the formula, R ₇ represents a monovalent organic group having 1 to 19 carbon atoms.)
The positive photosensitive resin composition in any one of said [1]-[3] which has a structure represented by these.
[5] The (c) phenol resin is represented by the following general formulas (4) to (6):

(Wherein R ₁₁ and R ₁₂ 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, and i and k are each independently (It is an integer of 0 to 2, where 1 ≦ (h + i) ≦ 4, 1 ≦ (j + k) ≦ 4 is satisfied, and m1 and m2 are each independently 0 or a positive integer and are not 0 simultaneously.)

Wherein R ₁₃ and R ₁₄ each independently represents a monovalent organic group having 1 to 10 carbon atoms, l and p are each independently an integer of 0 to 2, and m3 is 0 or a positive integer. And m4 is a positive integer.)

(Wherein R ₁₅ represents a monovalent organic group having 1 to 10 carbon atoms, q is an integer of 0 to 2, m5 is a positive integer, and m6 is 0 or a positive integer. .)
The positive photosensitive resin composition according to any one of the above [1] to [4], which is a novolak resin having a structure represented by at least one selected from the group consisting of:
[6] (A) A step of forming a photosensitive resin layer comprising the photosensitive resin composition according to any one of [1] to [5] 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.
[7] A cured relief pattern produced by the method according to [6] above.
[8] 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 [7].
[9] 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 [7]. apparatus.

  According to the present invention, it is possible to provide a photosensitive resin composition having a high development residual film ratio, high sensitivity, a good shape of a cured relief pattern, and hardly corroding metal after etching with a fluorine-based compound gas. it can.

It is a figure which shows the ¹³ C-NMR result of the hydroxy polyamide resin (P-2) obtained by the synthesis example 6. It is a figure which shows the < ¹ > H-NMR result of the phenol resin (N-1) obtained by the 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は炭素原子数２〜６０の２価から８価の有機基を示し、Ｒ₂は炭素原子、水素原子、窒素原子、酸素原子及び硫黄原子から成る炭素原子数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原子数１から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。 <Photosensitive resin composition>
In the present embodiment, the photosensitive resin composition has (a) general formula (1):

(In the formula, R ₁ represents a divalent to octavalent organic group having 2 to 60 carbon atoms, and R ₂ has 2 to 60 carbon atoms composed of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, and a sulfur atom. R ₃ , R ₄ , R ₅ , and R ₆ each independently represent a hydrogen 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 do not simultaneously become 0, f and g are each independently an integer of 0 to 4, and n is a positive integer.)
A polymer (hereinafter also referred to as polymer (a)), (b) a quinonediazide compound (hereinafter also referred to as quinonediazide compound (b)), and (c) a phenol resin (hereinafter referred to as “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.

  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 general formula (1), n is not limited as long as it is a positive integer, but from the viewpoint of developability, a range of 1 to 1000 is preferable, a range of 3 to 50 is more preferable, and a range of 3 to 30 is preferable. 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 In contrast, the meta position may be an amino group, the para position is a hydroxyl group, the meta position is a hydroxyl group, and the para position is an amino group. From the viewpoint of solubility in a solvent, the meta position is 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:

(In the formula, 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 alkaline 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.

  Examples of the method for producing the compound represented by the above structure include a method of reacting the above-described bisaminophenol with two molecules of nitrobenzoic acid and subsequently reducing the nitro group 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, an example of the organic group represented by R ₁ will be described later. It is preferably at least one organic group listed.

Specific examples of such a compound specifically 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:

(In the formula, 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 L) 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, 4,4 -Diaminodiphenylurea, 4,4'-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) ) 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] diphenylsulfone, 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.

  Moreover, 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.

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 the 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. Here, 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.

(In the formula, 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、Ｒ_５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。） Further, 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, the bond between the amide and the amide is strong due to the polarity of the amide, and the polymer is easily associated with the phenol resin. 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、Ａｒ_１及びＡｒ_２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 said ester structure, the structure represented by the following general formula (2), and the following structure:

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

（式中、Ｒ₈、Ｒ₉、及びＲ₁₀は、それぞれ独立に、炭素原子数１〜６０の２価の有機基を示し、Ｒ₈、Ｒ₉、及びＲ₁₀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 (2).

(Wherein R ₈ , R ₉ and R ₁₀ each independently represents a divalent organic group having 1 to 60 carbon atoms, and at least one of R ₈ , R ₉ and R ₁₀ is It has an alicyclic structure or an aliphatic structure, and m is 0 or 1.)

The structure represented by the general formula (2) includes, for example, (α) a hydroxyl group-containing compound having the structure of R _{8 in} the general formula (2), and (β) a polyvalent compound having the structures of R ₉ and R _10. It can be obtained by reacting at least one carboxylic acid compound selected from the group consisting of carboxylic acids and derivatives thereof.

Hereinafter, the hydroxyl group-containing compound having the (α) R ₈ structure will be described.

R ₈ is a residue derived from a divalent phenol compound or an alcohol compound. Examples of the hydroxyl group-containing compound having an R ₈ structure 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′-dihydroxydiphenylsulfone Bis (4-hydroxyphenyl) sulfide, diphenolic acid and the like.

  Moreover, the phenolic compound containing a functional group can also be used as a phenolic 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, , 5-hexadiene-3,4-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2, 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.

  As an alcohol compound, the alcohol compound containing a functional group can also be used similarly to the said 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 ₉ and R ₁₀ and derivatives thereof will be described.

The polyvalent carboxylic acid having the structure of R ₉ and R ₁₀ 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 (2). When it has the structure represented, it is advantageous also from a viewpoint of i-line permeability.

In the general formula (2), at least one of R ₈ , R ₉ and R ₁₀ 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 ₈ in the general formula (2) is aromatic, and R ₉ and R ₁₀ are both alicyclic structures or aliphatic structures (that is, R ₉ and R ₁₀ 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 ₈ preferably has 1 to 30 carbon atoms, and R ₉ and R ₁₀ each preferably have 1 to 15 carbon atoms. R ₈ , R ₉ and R ₁₀ contain 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は炭素原子数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、水素原子又は炭素原子数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 ₈ in the general formula (2) is more preferably selected from structures represented by the following general formula (7), and R ₉ and R More preferably, ₁₀ is selected from the structure represented by the following general formula (8).

(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 selected divalent group, 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. Well, 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 ratio of the ester group-containing structure represented by the general formula (2) in the polymer having the structural unit represented by the general formula (1) as a main component is the solubility in an alkali developer and the resulting resin film machine. It is preferable that it is 5-80 mol% at a point with a favorable physical property.

（式中、Ｒ₇は炭素原子数１〜１９の１価の有機基を示す。） R ₃ and / or R ₄ in the polymer whose main component is the structural unit represented by the general formula (1) preferably has a structure represented by the following general formula (3).

(In the formula, R ₇ represents a monovalent organic group having 1 to 19 carbon atoms.)

The structure of R ₇ 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 shrinkage during curing, R ₇ has 1 to 19 carbon atoms, more preferably 1 to 6, and R ₇ is more specifically a methyl group, an ethyl group, or a phenyl group. Is mentioned.

Of the number of R ₃ and R _{4 in} the polymer having the structural unit represented by the general formula (1) as a main component, the ratio of the number of groups represented by the general formula (3) to the alkali developer In terms of good solubility, the content is preferably 0.1 to 10 mol%.

The introduction of the group represented by the general formula (3) 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 as follows. 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, the bond between the amide and the amide is strong due to the polarity of the amide, and the polymer is easily associated with the phenol resin. Compatibility is difficult to increase. On the other hand, when the ester structure is introduced by the structure of the general formula (3), 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) having the structural unit represented by the general formula (1) as a main component 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 being less susceptible to metal corrosion 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) containing the structural unit represented by the general formula (1) as a main component 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). 1-50 mass parts is preferable and 5-30 mass parts 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).

(C) Phenol resin The photosensitive resin composition contains 50 to 100 parts by mass of (c) a phenol resin with respect to 100 parts by mass of the polymer (a). In the phenol resin (c), the unexposed part has a dissolution inhibiting effect on the quinonediazide compound (b), while the exposed part has a dissolution promoting action to generate contrast and form a pattern. In addition, when a photosensitive resin composition containing no phenol resin (c) or having a low content is coated, exposed, developed, and cured on a metal, and then etched using a fluorine compound, There is a problem that corrosion occurs on the metal and the reliability of the semiconductor package is lowered. On the other hand, the photosensitive resin composition which added phenol resin (c) 50 mass parts or more with respect to 100 mass parts of polymers which have as a main component the structural unit represented by (a) general formula (1). There is an effect of suppressing corrosion on the metal of the opening. The reason for this is not clear, but the inventor presumes the following reason. Corrosion on the metal is considered to be caused by the fluorine compound used for etching penetrating into the cured film during the etching process and then leaching onto the metal. In response to this phenomenon, the presence of a certain amount or more of phenolic resin in the composition prevents the penetration of fluorine-based compounds into the film, resulting in less fluorine-based compounds leaching onto the metal and corrosion on the metal. It is thought that it can be suppressed.

  In the present invention, as the phenol resin (c), either a novolak phenol resin or a resol phenol resin can be used from the viewpoint of solubility in a developer, and can be selected as desired. These phenol resins can be synthesized by using various phenol compounds alone or a mixture of plural kinds thereof.

  As a method for synthesizing a phenol resin, a method of polycondensing various phenol compounds alone or a mixture of a plurality of them with aldehydes such as formalin by a known method, or a phenol compound and a polymerization component are subjected to a polymerization reaction. The method of synthesize | combining by this and the method of synthesize | combining by these combination 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, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, methylenebisphenol Methylenebis p-cresol, bisphenol A, resorcin, catechol, 2-methylresorcin, 4-methylresorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, p-methoxyph Nord, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α-naphthol, β-naphthol, etc. These may be used alone or as a mixture of two or more.

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

  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-t-butylphenol, 2,6-bis (hydroxymethyl) -4-methoxyphenol, 2,6-bis (hydroxymethyl) -4-ethoxyphenol, 2,6-bis (hydroxymethyl) -4-propoxyphenol, 2,6-bis (hydroxymethyl) -4-n-butoxyphenol, 2,6 -Bis (hydroxymethyl) -4-t-butoxyphenol, bis (hydroxymethyl) biphenyl, etc. 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-tert-butylphenol, 2,6-bis (methoxymethyl) -4-methoxyphenol 2,6-bis (methoxymethyl) -4-ethoxyphenol, 2,6-bis (methoxymethyl) -4-propoxyphenol, 2,6-bis (methoxymethyl) -4-n-butoxyphenol, 2, 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 and the like.

（式中、Ｒ₁₁及びＲ₁₂はそれぞれ独立に炭素原子数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、但し１≦（ｈ＋ｉ）≦４、１≦（ｊ＋ｋ）≦４を満たし、そしてｍ１及びｍ２はそれぞれ独立に０又は正の整数であって同時に０にはならない。）

（式中、Ｒ₁₃及びＲ₁₄はそれぞれ独立に炭素原子数１〜１０の１価の有機基を示し、ｌ及びｐはそれぞれ独立に０〜２の整数であり、ｍ３は０又は正の整数であり、そしてｍ４は正の整数である。）

（式中、Ｒ₁₅は炭素原子数１〜１０の１価の有機基を示し、ｑは０〜２の整数であり、ｍ５は正の整数であり、そしてｍ６は０又は正の整数である。） In addition, the phenol resin (c) is selected from the group consisting of the following general formulas (4) to (6) from the viewpoints of surface uniformity after development and the shape, elongation, and degassing of the cured relief pattern. More preferred is a novolac resin having a structure represented by at least one.

(Wherein R ₁₁ and R ₁₂ 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, and i and k are each independently (It is an integer of 0 to 2, where 1 ≦ (h + i) ≦ 4, 1 ≦ (j + k) ≦ 4 is satisfied, and m1 and m2 are each independently 0 or a positive integer and are not 0 simultaneously.)

Wherein R ₁₃ and R ₁₄ each independently represents a monovalent organic group having 1 to 10 carbon atoms, l and p are each independently an integer of 0 to 2, and m3 is 0 or a positive integer. And m4 is a positive integer.)

(Wherein R ₁₅ represents a monovalent organic group having 1 to 10 carbon atoms, q is an integer of 0 to 2, m5 is a positive integer, and m6 is 0 or a positive integer. .)

  The weight average molecular weight of the phenol resin (c) is preferably 1,000 to 50,000, and 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.

  The blending amount of the phenol resin (c) with respect to 100 parts by mass of the polymer whose main component is the structural unit represented by (a) the general formula (1) is 50 to 100 parts by mass, preferably 75 to 100 parts by mass. More preferably, it is 90-100 mass parts.

  From the standpoint of obtaining the desired effect of reducing the film loss during development and patterning on the metal, and suppressing the corrosion of the metal after etching by the fluorine-based compound gas after curing, the above compounding amount is It is 50 parts by mass or more, and is 100 parts by mass or less from the viewpoint of the pattern shape after curing and the elongation after curing.

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.

  When the organic solvent is blended, the addition amount is preferably 100 to 100 parts by mass with respect to 100 parts by mass 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 which concerns on this invention can contain a crosslinking agent for the purpose of improving the chemical resistance of the film | membrane (photosensitive resin layer) after thermosetting as needed. 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). It is preferable that it is 1-100 mass parts with respect to 100 mass parts of total amount, and, More preferably, it is 3-50 mass parts. 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, tri Hexyl hydroxybenzenecarboxylate hexyl gallate and phloroglucinol carboxylate hexyl, octyl trihydroxybenzenecarboxylate octyl gallate and phloroglucinol carboxylate, dodecyl trihydroxybenzenecarboxylate dodecyl and fluorate Logucinol carboxylate dodecyl, trihydroxybenzenecarboxylate hexadecyl hexadecyl gallate and phloroglucinol carboxylate hex Sadecyl 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 (made by Honshu Chemical Industry Co., Ltd .: trade name), 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). 1-30 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- -Ol, cis-4-hepten-1-ol, cis-3-octen-1-ol, 4-ethyl-1-octin-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-decyne − , 7-diol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,2-cyclohexanediol, trans-p-menthane-3,8-diol, 2,4-dimethoxybenzyl alcohol, Examples include butyroin.

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, A hydroxyl group-containing compound having an unsaturated bond or a branched structure, such as 4-diol and 1,5-hexadiene-3,4-diol, is preferable, and monoalcohol is preferable to diol from the viewpoint of adhesion to the substrate, 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). -70 mass parts is preferable, 0.1-50 mass parts is more preferable, 1-40 mass parts is further more preferable, and 5-25 mass parts is especially preferable. 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 compounding quantity in the case of mix | blending dye is 0.1-10 with respect to 100 mass parts of total amounts of the polymer (a) which has a structural unit represented by General formula (1) as a main component, and a 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, myrtenol, 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.
The compounding quantity in the case of mix | blending a fragrance | flavor is 0.1-70 with respect to 100 mass parts of total amounts of the polymer (a) and phenol resin (c) which have a structural unit represented by General formula (1) as a main component. A mass part is preferable and 1-50 mass parts 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, organosiloxane 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 can be mentioned. 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 mono- or higher functional alkoxyl group and a silanol group, and serves as an adhesion aid for enhancing adhesion to a silicon wafer. From the viewpoint of solubility in a solvent, the number of carbon atoms of the organosilicon compound is preferably 4-30, and more preferably 4-18.

  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), and 3-mercaptopropyltriethoxysilane (manufactured by Asmax Corporation): Trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name LS1375, manufactured by Azumax Co., Ltd .: trade name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azumax Corporation: product) Name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane 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-mercaptobu Lutriethoxysilane, 4-mercaptobutyltripropoxysilane, N- (3-triethoxysilylpropyl) urea (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name LS3610, manufactured by Asmax Co., Ltd .: trade name SIU9055.0), N- ( 3-trimethoxysilylpropyl) urea (manufactured by Azmax Co., Ltd .: trade name SIU9058.0), N- (3-diethoxymethoxysilylpropyl) urea, N- (3-ethoxydimethoxysilylpropyl) urea, N- (3 -Tripropoxysilylpropyl) urea, N- (3-diethoxypropoxysilylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N- (3-dimethoxypropoxysilylpropyl) urea, N- (3 -Methoxydipropoxysilylpropyl) Rare, 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 SLA0 99.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SLA0599.1) aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SLA0599.2), 2- (trimethoxysilylethyl) Pyridine (manufactured by Azmax Co., Ltd .: trade name SIT8396.0), 2- (triethoxysilylethyl) pyridine, 2- (dimethoxysilylmethylethyl) pyridine, 2- (diethoxysilylmethylethyl) pyridine, (3-triethoxy (Silylpropyl) -t-butylcarbamate, (3-glycidoxypropyl) triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, Tetra-i Butoxysilane, tetra-t-butoxysilane, tetrakis (methoxyethoxysilane), tetrakis (methoxy-n-propoxysilane), tetrakis (ethoxyethoxysilane), tetrakis (methoxyethoxyethoxysilane), bis (trimethoxysilyl) ethane, Bis (trimethoxysilyl) hexane, bis (triethoxysilyl) methane, bis (triethoxysilyl) ethane, bis (triethoxysilyl) ethylene, bis (triethoxysilyl) octane, bis (triethoxysilyl) octadiene, bis [ 3- (triethoxysilyl) propyl] disulfide, bis [3- (triethoxysilyl) propyl] tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane, bis (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, isopropyl Methylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert Butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, Examples include, but are not limited to, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol, and the like. These may be used alone or in combination.

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

  The organosilicon compounds may be used alone or in combination of two or more. The compounding amount in the case of compounding the organosilicon compound 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). It is preferable that it is a mass part, 2-30 mass parts is more preferable, and 4-20 mass parts is further more preferable. 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.

(In the formula, 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, or a carbon atom. It is a group 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 is more preferred.
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). 1-30 mass parts is preferable, and 0.5-10 mass parts 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. The spin coating method using a spin coater is most preferable from the viewpoint of obtaining a coating film having a uniform film thickness.

(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. In these, the tetramethylammonium hydroxide aqueous solution is preferable, The density | concentration of this tetramethylammonium hydroxide becomes like this. Preferably, it is 0.5-10 mass%, More preferably, it is 1-5 mass%.

(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. .

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

<Weight average molecular weight (Mw)>
It was calculated by GPC in terms of standard polystyrene (an 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 6 μm as the cured resin film thickness when cured 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 evaluation film, the exposure amount using a stepper (Nikon Corporation NSR2005i8A) having an exposure wavelength of i-line (365 nm) through a test pattern reticle with a stepwise to 150mJ / cm ² ~800mJ / cm ² Changed and exposed.
・ Developed with a developer / developer (D-SPIN) at 23 ° C. using a 2.38% tetramethylammonium hydroxide aqueous solution AZ-300MIF (manufactured by AZ Electronic Materials) for 100 seconds, rinsed with pure water, and reliefd 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 shape of cured relief pattern>
The film on which the relief pattern was formed was heated in a vertical curing furnace VF200B (manufactured by Koyo Thermo System Co., Ltd.) in a nitrogen atmosphere at 320 ° C. for 30 minutes to obtain a cured relief pattern. At this time, a case where the 20 μm square relief pattern was maintained without being buried was defined as “good”, and a shape whose shape was broken and the pattern was buried was designated as “defective”.

<Metal corrosion evaluation>
A metal corrosion evaluation sample was prepared by the following method. Rotate the photosensitive resin compositions obtained in Examples and Comparative Examples on a 6-inch silicon wafer substrate with an aluminum vapor deposition layer and a silicon nitride film layer so that the film thickness after curing is about 6 μm. It was applied and prebaked on a hot plate at 125 ° C. for 180 seconds to form a coating film. The initial film thickness of each composition was adjusted to 6 μm as the cured resin film thickness when cured 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.). This coating film was exposed at an exposure amount of 800 mJ / cm ² using a stepper (NSR2005i8A manufactured by Nikon Corporation) having an exposure wavelength of i-line (365 nm) through a reticle with a test pattern. Developed with a developing machine (D-SPIN) at 23 ° C. using a 2.38% tetramethylammonium hydroxide aqueous solution AZ-300MIF (manufactured by AZ Electronic Materials) for 100 seconds, rinsed with pure water, and formed a relief pattern. Formed. The film on which the relief pattern was formed was heated in a vertical curing furnace VF200B (manufactured by Koyo Thermo System Co., Ltd.) in a nitrogen atmosphere at 320 ° C. for 30 minutes to obtain a cured relief pattern.

The cured film RIE apparatus was etched in the silicon nitride film 20 minutes by CF4 / O2 = 47.5 / 2.5 in gas (ANELVA manufactured DEM-451), followed by 1 minute of the surface cleaning with O ₂ gas By performing, the sample which aluminum exposed to the opening part of the cured film was obtained.

  This sample was allowed to stand for 7 days under conditions of an air temperature of 23 ° C. and a relative humidity of 50%.

  The opening of the 100 μm square relief pattern of the above sample was observed with an optical microscope at an observation magnification of 500 times, and compared with the sample before standing for 7 days under conditions of an air temperature of 23 ° C. and a relative humidity of 50%. In the case where the aluminum was discolored, it was judged as “bad”, and in the case where no discoloration occurred, “good”.

[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) was dissolved 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 dropping, 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. 9 g (0.366 mol) dissolved in 1 L of acetonitrile, 256.7 g (1.808 mol) of disodium hydrogen phosphate and 217.1 g (1.809 mol) of sodium dihydrogen phosphate dissolved 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 (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter also referred to as “TEMPO”) 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 to 50 ° C. for 18 hours to be reacted. 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 (trade name: Tris, manufactured by Honshu Chemical Industry Co., Ltd.) 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 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. The precipitate was washed with water and 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 structure:

  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, and is a single composition. confirmed.

[Synthesis Example 6]
<Synthesis of (a) hydroxy polyamide 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 ( chlorocarbonyl) tricyclo [5,2,1,0 ^2,6] decane mixture stirred solution 47.0 g (0.175 mol) and room temperature (20-25 ° C. longitudinal 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 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. In the reaction system, it was kept at -15 to 0 ° C., and it took 1 hour to drop into the reaction vessel.

  The ice bath was removed after completion | finish of dripping, it maintained at 0-10 degreeC, and it stirred for 1 hour, and also 4.74 g (0.06 mol) of pyridine was added. Thereafter, the reaction solution was returned to room temperature, 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, and 50 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樹脂（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 is dropped into 12 L of ion-exchanged water under high-speed stirring, and the polymer is dispersed and precipitated, recovered, appropriately washed with water, dehydrated and then vacuum-dried.

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

  The weight average molecular weight (Mw) by GPC of the hydroxy polyamide resin thus synthesized was a single sharp curve of 12,700 in terms of polystyrene, and it was confirmed that it was a single composition.

FIG. 1 shows the ¹³ C-NMR result of the obtained 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]
<Synthesis of (a) hydroxy polyamide resin (P-3)>
In a 1 L separable flask equipped with a Teflon (registered trademark) vertical stirrer, 59 g (0.1 mol) of P-2 produced in Synthesis Example 6 and triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0. 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, appropriately washed with water, dehydrated and then 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, and is a single composition. confirmed.

[Synthesis Example 8]
<Synthesis of phenol resin (N-1)>
First, a 1.0 L separable flask equipped with a Dean-Stark apparatus 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 ｍ／ｎ ＝ 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 a 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 m / n = 30/70)
A phenol resin (N-1) having the structure: 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).

（モル比率 ｍ／ｎ ＝ ６０／ ４０）
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１０，６００であった。 [Synthesis Example 9]
<Synthesis of phenolic resin (N-2)>
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 m / n = 60/40)
A phenol resin (N-2) having the structure: The weight average molecular weight by GPC of the synthesized resin was 10,600 in terms of polystyrene.

<Preparation of positive photosensitive resin composition>
[Example 1]
10 g of P-1 produced in Synthesis Example 5 and 5 g of phenol resin (trade name EP4000B, 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 2.25 g were dissolved in 25 g of GBL, and then 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 7.5 g of phenol resin (trade name EP4000B, m-cresol / p-cresol ratio = 60/40, manufactured by Asahi Organic Materials Co., Ltd.) were measured, and Synthesis Example 4 The quinonediazide compounds Q-1 and 2.625 g produced in 1 above were dissolved in 29.2 g of GBL, and then 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 phenol resin (trade name EP4000B, 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 3.0 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.

[Example 4]
A positive photosensitive resin composition was similarly prepared using N-1 produced in Synthesis Example 8 instead of the phenol resin used in Example 1.
[Example 5]
A positive photosensitive resin composition was similarly prepared using N-1 produced in Synthesis Example 8 instead of the phenol resin used in Example 2.
[Example 6]
A positive photosensitive resin composition was similarly prepared using N-1 produced in Synthesis Example 8 instead of the phenol resin used in Example 3.
[Example 7]
In place of the phenol resin used in Example 1, a phenol resin (trade name: AEG018, phenol component: bisphenol A, aldehyde component: formaldehyde, manufactured by Gunei Chemical Co., Ltd.) was used in the same manner, and a positive photosensitive resin composition. Was prepared.
[Example 8]
In place of the phenol resin used in Example 2, a phenol resin (trade name: AEG018, phenol component: bisphenol A, aldehyde component: formaldehyde, manufactured by Gunei Chemical Co., Ltd.) was used in the same manner, and a positive photosensitive resin composition. Was prepared.
[Example 9]
In place of the phenol resin used in Example 3, a phenol resin (trade name AEG018, phenol component: bisphenol A, aldehyde component: formaldehyde, manufactured by Gunei Chemical Co., Ltd.) was used in the same manner, and a positive photosensitive resin composition. Was prepared.
[Example 10]
Instead of the phenol resin used in Example 1, phenol resin (trade name AEG024, phenol component: m-cresol / p-cresol ratio = 60/40, aldehyde component: formaldehyde / salicylaldehyde ratio = 70/30, Gunei Chemical Co., Ltd. In the same manner, a positive photosensitive resin composition was prepared.

[Example 11]
Instead of the phenol resin used in Example 2, phenol resin (trade name AEG024, phenol component: m-cresol / p-cresol ratio = 60/40, aldehyde component: formaldehyde / salicylaldehyde ratio = 70/30, Gunei Chemical In the same manner, a positive photosensitive resin composition was prepared.
[Example 12]
Instead of the phenol resin used in Example 3, phenol resin (trade name AEG024, phenol component: m-cresol / p-cresol ratio = 60/40, aldehyde component: formaldehyde / salicylaldehyde ratio = 70/30, Gunei Chemical In the same manner, a positive photosensitive resin composition was prepared.
[Example 13]
A positive photosensitive resin composition was similarly prepared using N-2 produced in Synthesis Example 9 instead of the phenol resin used in Example 1.
[Example 14]
A positive photosensitive resin composition was similarly prepared using N-2 produced in Synthesis Example 9 instead of the phenol resin used in Example 2.
[Example 15]
A positive photosensitive resin composition was similarly prepared using N-2 produced in Synthesis Example 9 instead of the phenol resin used in Example 3.
[Example 16]
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 17]
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 18]
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 19]
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 20]
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 21]
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 22]
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 23]
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 24]
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 25]
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 26]
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 27]
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 28]
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 29]
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 30]
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 31]
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 32]
A positive photosensitive resin composition was similarly prepared using P-3 produced in Synthesis Example 7 instead of P-1 used in Example 2.
[Example 33]
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 34]
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 35]
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 36]
A positive photosensitive resin composition was similarly prepared using P-3 produced in Synthesis Example 7 instead of P-1 used in Example 6.
[Example 37]
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 38]
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 39]
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 40]
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 41]
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 42]
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 43]
A positive photosensitive resin composition was similarly prepared using P-3 produced in Synthesis Example 7 instead of P-1 used in Example 13.
[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 14.
[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 15.

[Comparative Example 1]
10 g of P-1 produced in Synthesis Example 5 and 2 g of phenol resin (trade name EP4000B, 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 1.8 g together with GBL and 20 g were dissolved and then filtered through a 1 μm filter to prepare a positive photosensitive resin composition.

[Comparative Example 2]
10 g of P-1 produced in Synthesis Example 5 and 4.9 g of phenol resin (trade name EP4000B, m-cresol / p-cresol ratio = 60/40, manufactured by Asahi Organic Materials Co., Ltd.) were weighed, and Synthesis Example 4 Along with the quinonediazide compound Q-1 and 2.235 g produced in 1 above, GBL was dissolved in 24.8 g, followed by filtration with 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 10.1 g of phenol resin (trade name EP4000B, m-cresol / p-cresol ratio = 60/40, manufactured by Asahi Organic Materials Co., Ltd.) were weighed, and Synthesis Example 4 The quinonediazide compound Q-1 produced in 1) was dissolved in 33.5 g of GBL together with 3.015 g, 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 15.0 g of phenol resin (trade name EP4000B, m-cresol / p-cresol ratio = 60/40, manufactured by Asahi Organic Materials Co., Ltd.) were weighed, and Synthesis Example 4 The quinonediazide compound Q-1 produced in 1) was dissolved in GBL and 41.7 g together with 3.75 g, and then filtered through a 1 μm filter to prepare a positive photosensitive resin composition.

[Comparative Example 5]
A positive photosensitive resin composition was similarly prepared using N-1 produced in Synthesis Example 8 instead of the phenol resin used in Comparative Example 1.

[Comparative Example 6]
A positive photosensitive resin composition was similarly prepared using N-1 produced in Synthesis Example 8 instead of the phenol resin used in Comparative Example 2.
[Comparative Example 7]
A positive photosensitive resin composition was similarly prepared using N-1 produced in Synthesis Example 8 instead of the phenol resin used in Comparative Example 3.
[Comparative Example 8]
A positive photosensitive resin composition was similarly prepared using N-1 produced in Synthesis Example 8 instead of the phenol resin used in Comparative Example 4.
[Comparative Example 9]
In place of the phenol resin used in Comparative Example 1, a phenol resin (trade name AEG018, phenol component: bisphenol A, aldehyde component: formaldehyde, manufactured by Gunei Chemical Co., Ltd.) was used in the same manner, and a positive photosensitive resin composition. Was prepared.
[Comparative Example 10]
In place of the phenol resin used in Comparative Example 2, a phenol resin (trade name: AEG018, phenol component: bisphenol A, aldehyde component: formaldehyde, manufactured by Gunei Chemical Co., Ltd.) was used in the same manner, and a positive photosensitive resin composition. Was prepared.

[Comparative Example 11]
A positive photosensitive resin composition is similarly used in place of the phenol resin used in Comparative Example 3, using a phenol resin (trade name: AEG018, phenol component: bisphenol A, aldehyde component: formaldehyde, manufactured by Gunei Chemical Co., Ltd.) Was prepared.
[Comparative Example 12]
In place of the phenol resin used in Comparative Example 4, a phenol resin (trade name AEG018, phenol component: bisphenol A, aldehyde component: formaldehyde, manufactured by Gunei Chemical Co., Ltd.) was used in the same manner, and a positive photosensitive resin composition. Was prepared.
[Comparative Example 13]
Instead of the phenol resin used in Comparative Example 1, phenol resin (trade name: AEG024, phenol component: m-cresol / p-cresol ratio = 60/40, aldehyde component: formaldehyde / salicylaldehyde ratio = 70/30, Gunei Chemical In the same manner, a positive photosensitive resin composition was prepared.
[Comparative Example 14]
Instead of the phenol resin used in Comparative Example 2, phenol resin (trade name AEG024, phenol component: m-cresol / p-cresol ratio = 60/40, aldehyde component: formaldehyde / salicylaldehyde ratio = 70/30, Gunei Chemical In the same manner, a positive photosensitive resin composition was prepared.
[Comparative Example 15]
Instead of the phenol resin used in Comparative Example 3, phenol resin (trade name AEG024, phenol component: m-cresol / p-cresol ratio = 60/40, aldehyde component: formaldehyde / salicylaldehyde ratio = 70/30, Gunei Chemical In the same manner, a positive photosensitive resin composition was prepared.
[Comparative Example 16]
Instead of the phenol resin used in Comparative Example 4, phenol resin (trade name: AEG024, phenol component: m-cresol / p-cresol ratio = 60/40, aldehyde component: formaldehyde / salicylaldehyde ratio = 70/30, Gunei Chemical In the same manner, a positive photosensitive resin composition was prepared.
[Comparative Example 17]
A positive photosensitive resin composition was similarly prepared using N-2 produced in Synthesis Example 9 instead of the phenol resin used in Comparative Example 1.
[Comparative Example 18]
A positive photosensitive resin composition was similarly prepared using N-2 produced in Synthesis Example 9 instead of the phenol resin used in Comparative Example 2.
[Comparative Example 19]
A positive photosensitive resin composition was similarly prepared using N-2 produced in Synthesis Example 9 instead of the phenol resin used in Comparative Example 3.
[Comparative Example 20]
A positive photosensitive resin composition was similarly prepared using N-2 produced in Synthesis Example 9 instead of the phenol resin used in Comparative Example 4.

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

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

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

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

The structure of each phenol resin mentioned above is shown below.

  Evaluation of the patterning characteristics of the positive photosensitive resin compositions of Examples 1 to 45 and Comparative Examples 1 to 60 prepared, shape evaluation of the cured relief pattern, and metal corrosion evaluation were performed, and the results are shown in Table 1 and Table 2. Show.

  From the results shown in Table 1 and Table 2, Examples 1 to 45 are excellent in sensitivity and development residual film ratio, can form a good pattern after curing, and give a resin film that suppresses metal corrosion. Show. Moreover, in Examples 16-30, it shows that the residual film rate at the time of image development is improving compared with Examples 1-15 by using the polymer which introduce | transduced ester structure into the polymer frame | skeleton. Furthermore, in Examples 31-45, it is shown that the remaining film ratio at the time of development is improved as compared with Examples 16-30 by using a polymer having an ester structure introduced in the side chain of the polymer.

  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 (9)

(A) The following general formula (1):

(In the formula, R ₁ represents a divalent to octavalent organic group having 2 to 60 carbon atoms, and R ₂ has 2 to 60 carbon atoms composed of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, and a sulfur atom. R ₃ , R ₄ , R ₅ , and R ₆ each independently represent a hydrogen 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 do not simultaneously become 0, f and g are each independently an integer of 0 to 4, and n is a positive integer.)
A polymer whose main component is a structure represented by:
(B) a quinonediazide compound;
(C) a phenol resin,
A positive photosensitive resin composition containing 50 to 100 parts by mass of the component (c) with respect to 100 parts by mass of the component (a). _2. The positive photosensitive resin composition according to claim 1, wherein R ₁ or R ₂ of the general formula (1) or both of them have a structure having an ester bond. R ₁ or R _{2 in} the general formula (1) is represented by the following general formula (2):

(Wherein R ₈ , R ₉ and R ₁₀ each independently represents a divalent organic group having 1 to 60 carbon atoms, and at least one of R ₈ , R ₉ and R ₁₀ is It has an alicyclic structure or an aliphatic structure, and m is 0 or 1.)
The positive photosensitive resin composition of Claim 1 or 2 which has a structure represented by these. R ₃ or R _{4 in} the general formula (1) or both of them are represented by the following general formula (3):

(In the formula, R ₇ represents a monovalent organic group having 1 to 19 carbon atoms.)
The positive photosensitive resin composition of any one of Claims 1-3 which has a structure represented by these. The (c) phenol resin is represented by the following general formulas (4) to (6):

(Wherein R ₁₁ and R ₁₂ 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, and i and k are each independently (It is an integer of 0 to 2, where 1 ≦ (h + i) ≦ 4, 1 ≦ (j + k) ≦ 4 is satisfied, and m1 and m2 are each independently 0 or a positive integer and are not 0 simultaneously.)

Wherein R ₁₃ and R ₁₄ each independently represents a monovalent organic group having 1 to 10 carbon atoms, l and p are each independently an integer of 0 to 2, and m3 is 0 or a positive integer. And m4 is a positive integer.)

(Wherein R ₁₅ represents a monovalent organic group having 1 to 10 carbon atoms, q is an integer of 0 to 2, m5 is a positive integer, and m6 is 0 or a positive integer. .)
The positive photosensitive resin composition according to claim 1, which is a novolak resin having a structure represented by at least one selected from the group consisting of: (A) The process of forming the photosensitive resin layer which consists of the photosensitive resin composition of any one of Claims 1-5 on a board | 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 6.   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 7.   A display body device comprising a display body element and a cured film provided on the display body element, wherein the cured film is the cured relief pattern according to claim 7.

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