JP6073626B2 - Photosensitive resin composition - Google Patents

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.

  Among them, 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 (Patent Document 1). .

  In this photosensitive resin composition, the unexposed naphthoquinonediazide compound (that is, photosensitive diazoquinone compound) and polybenzoxazole (PBO) precursor have a low dissolution rate in an alkaline aqueous solution, whereas the exposed photosensitive diazoquinone. The compound has a high dissolution rate in an alkaline aqueous solution by chemically changing to an indenecarboxylic acid compound. 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.

  However, the positive photosensitive resin composition containing the photosensitive diazoquinone compound tends to be less sensitive than a general negative photosensitive resin composition. Therefore, a more sensitive composition is required.

  Thus, as a photosensitive resin composition for improving sensitivity and resolution, for example, Patent Document 2 discloses a method of adding an organic acid such as m-toluic acid or m-anisic acid to a PBO precursor.

JP-A-63-96162 International Publication No. 08/020573 Pamphlet

  However, although the sensitivity and resolution of the photosensitive resin composition of Patent Document 2 are improved, there is room for improvement in the residual film ratio after curing and the pattern cross-sectional shape at the time of curing.

  Accordingly, an object of the present invention is to provide a positive photosensitive resin composition having good lithography performance such as high sensitivity and high resolution, a high residual film ratio after curing, and a good pattern cross-sectional shape after curing. That is.

  In light of the above-described problems of the prior art, the present inventors have conducted extensive studies and repeated experiments. As a result, the present invention solves the above problems by using an alkali-soluble resin in combination with a salicylic acid oligomer having a specific structure. The inventors have found that a photosensitive resin composition can be obtained, and have reached the present invention.

（式中、Ｒ_１及びＲ_２は、それぞれ独立に、水素原子又は炭素数１〜１０の１価の有機基を示し；かつ、ｎの平均値は０以上５．０以下であるが、ｎの平均値が０の場合、Ｒ_１及びＲ_２は同時に水素原子になることはない）
で表されるサリチル酸オリゴマー又はその混合物０．１〜１０質量部
を含む、ポジ型感光性樹脂組成物。
［２］
前記ｎの平均値が、０．２以上４．０以下である、［１］に記載のポジ型感光性樹脂組成物。
［３］
前記サリチル酸オリゴマー又はその混合物中の、ｎの平均値が０．２以上であり、かつＲ_１及びＲ_２が、全て水素原子である、［１］又は［２］に記載のポジ型感光性樹脂組成物。
［４］
前記（Ａ）アルカリ可溶性樹脂が、（Ａ−１）フェノール性水酸基を有するポリイミド、（Ａ−２）ポリベンゾオキサゾール前駆体並びにアミド結合のオルト位にエステル基及び／又はカルボキシル基を有するポリアミド及び（Ａ−３）フェノール樹脂からなる群から選ばれる少なくとも１種を含む、［１］〜［３］のいずれか１項に記載のポジ型感光性樹脂組成物。
［５］
前記（Ａ）アルカリ可溶性樹脂が、ポリベンゾオキサゾール前駆体１００質量部に対してフェノール樹脂を２１質量部以上１００質量部以下の割合で含む、［１］〜［４］のいずれか１項に記載のポジ型感光性樹脂組成物。
［６］
前記（Ａ−３）フェノール樹脂が、下記一般式（ａ）又は（ｂ）：

（式中、Ｒ_３、Ｒ_４、Ｒ_５及びＲ_６は、それぞれ独立に、炭素数１から１０の一価の有機基であり；ａ及びｃは、１又は２であり；ｂ、ｄ、ｅ及びｆは、それぞれ０から２の整数であり；ｍ_１、ｍ_２及びｍ_３は、それぞれ独立に０又は正の整数であり；ｍ_４は、正の整数である；ただし、ｍ_１とｍ_２は、同時に０になることはない。）
で表されるノボラック樹脂である、［４］又は［５］に記載のポジ型感光性樹脂組成物。
［７］
（ａ）［１］〜［６］のいずれか１項に記載の感光性樹脂組成物から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、
（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。
［８］
［７］に記載の方法により製造された硬化レリーフパターン。
［９］
半導体素子と、該半導体素子の上部に設けられた［８］に記載の硬化レリーフパターンとを備える半導体装置。
［１０］
表示体素子と、該表示体素子の上部に設けられた［８］に記載の硬化レリーフパターンとを備える表示体装置。 That is, the present invention is as follows.
[1]
(A) 100 parts by mass of an alkali-soluble resin;
(B) 1-50 parts by mass of a photoacid generator; and (C) the following general formula (1):

(Wherein R ₁ and R ₂ each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms; and the average value of n is 0 or more and 5.0 or less, n When the average value of is 0, R ₁ and R ₂ are not simultaneously hydrogen atoms)
A positive photosensitive resin composition comprising 0.1 to 10 parts by mass of a salicylic acid oligomer represented by the formula:
[2]
The positive photosensitive resin composition according to [1], wherein the average value of n is 0.2 or more and 4.0 or less.
[3]
The positive photosensitive resin according to [1] or [2], wherein an average value of n in the salicylic acid oligomer or a mixture thereof is 0.2 or more, and R ₁ and R ₂ are all hydrogen atoms. Composition.
[4]
The (A) alkali-soluble resin comprises (A-1) a polyimide having a phenolic hydroxyl group, (A-2) a polybenzoxazole precursor, a polyamide having an ester group and / or a carboxyl group at the ortho position of the amide bond, and ( A-3) The positive photosensitive resin composition according to any one of [1] to [3], comprising at least one selected from the group consisting of phenol resins.
[5]
The (A) alkali-soluble resin according to any one of [1] to [4], wherein the phenol resin contains a phenol resin at a ratio of 21 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the polybenzoxazole precursor. A positive photosensitive resin composition.
[6]
The (A-3) phenol resin is represented by the following general formula (a) or (b):

(Wherein R ₃ , R ₄ , R ₅ and R ₆ are each independently a monovalent organic group having 1 to 10 carbon atoms; a and c are 1 or 2; b, d, e and f are each an integer from 0 to 2; m ₁ , m ₂ and m ₃ are each independently 0 or a positive integer; m ₄ is a positive integer; provided that m ₁ and m ₂ is never 0 at the same time.)
The positive photosensitive resin composition according to [4] or [5], which is a novolak resin represented by:
[7]
(A) forming a photosensitive resin layer on a substrate from the photosensitive resin composition according to any one of [1] to [6];
(B) a step of exposing the photosensitive resin layer;
(C) removing the exposed portion with a developer to obtain a relief pattern;
(D) heating the relief pattern;
A method for producing a cured relief pattern.
[8]
A cured relief pattern produced by the method according to [7].
[9]
A semiconductor device comprising a semiconductor element and the cured relief pattern according to [8] provided on an upper part of the semiconductor element.
[10]
A display device comprising a display element and the cured relief pattern according to [8] provided on the display element.

  According to the present invention, it is possible to provide a positive photosensitive resin composition having good lithography performance such as high sensitivity and high resolution, having a high residual film ratio after curing, and having a good pattern cross-sectional shape after curing. it can.

  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、Ｒ_１及びＲ_２は、それぞれ独立に、水素原子又は炭素数１〜１０の１価の有機基を示し；かつ、ｎの平均値は０以上５．０以下であるが、ｎの平均値が０の場合、Ｒ_１及びＲ_２は同時に水素原子になることはない。）。 <Photosensitive resin composition>
In the present embodiment, the photosensitive resin composition comprises (B) a photoacid generator (hereinafter photoacid) with respect to 100 parts by mass of (A) alkali-soluble resin (hereinafter also referred to as alkali-soluble resin (A)). 1 to 50 parts by mass of a generator (B) and (C) a salicylic acid oligomer having a structure represented by the following general formula (1) or a mixture thereof (hereinafter also referred to as salicylic acid oligomer (C)) 0.1 Contains 10 parts by weight:

(Wherein R ₁ and R ₂ each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms; and the average value of n is 0 or more and 5.0 or less, n When the average value of is 0, R ₁ and R ₂ are not simultaneously hydrogen atoms.)

  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.

(A) Alkali-soluble resin The alkali-soluble resin (A) used in the present invention is a resin soluble in an alkaline aqueous solution having a phenolic hydroxyl group and / or carboxyl group, or a phenolic hydroxyl group and / or carboxyl by heat or light. A resin soluble in an alkaline aqueous solution capable of generating a group is shown.

  (A) Among the alkali-soluble resins, (A-1) a polyimide having a phenolic hydroxyl group; (A-2) a polyamide having an ester group and / or a carboxyl group at the ortho position of the PBO precursor and amide bond (A-3) phenol resin and derivatives thereof; and (A-4) polyhydroxystyrene and derivatives thereof.

（式中、Ｘ_１及びＹ_１は、各々独立に、少なくとも２個の炭素原子を有する４価の有機基を表し；Ｙ_１は１以上のベンゼン環を含み、Ｙ_１に結合しているＯＨ基は、該ベンゼン環に結合し；そしてｍ_５は、１〜１０００の整数である。）。 (A-1) Polyimide having a phenolic hydroxyl group As the polyimide having a phenolic hydroxyl group, a resin having a structural unit represented by the following general formula (5) is preferably used:

(Wherein X ₁ and Y ₁ each independently represents a tetravalent organic group having at least two carbon atoms; Y ₁ contains one or more benzene rings and is bonded to Y _1. group is bound to the benzene ring; and _{m 5} is an integer of 1 to 1000.)..

（式中、Ｘ_１、Ｙ_１及びＸ_２は、各々独立に、少なくとも２個の炭素原子を有する４価の有機基を表し；Ｙ_２は、少なくとも２個の炭素原子を有する２価又は３価の有機基を表し；ｎ_２は、０又は１であり；ｍ_５は、１〜１０００の整数であり；ｍ_６は、１〜５００の整数であり、かつ０．５≦ｍ_５／（ｍ_５＋ｍ_６）≦１．０を満たし、そしてポリマーの構造はランダム構造でもブロック構造でも良い。）。 The polyimide having a phenolic hydroxyl group may be composed only of the unit structure represented by the general formula (5). However, in order to control the alkali solubility of the resin, the polyimide is represented by the following general formula (6). The unit structure may be:

Wherein X ₁ , Y ₁ and X ₂ each independently represents a tetravalent organic group having at least 2 carbon atoms; Y ₂ is divalent or 3 having at least 2 carbon atoms. N ₂ is 0 or 1; m ₅ is an integer from 1 to 1000; m ₆ is an integer from 1 to 500 and 0.5 ≦ m ₅ / ( m ₅ + m ₆ ) ≦ 1.0, and the polymer structure may be random or block.)

By the unit containing X ₁ and Y ₁ in the general formulas (5) and (6), (A-1) a polyimide having a phenolic hydroxyl group is formed.

  When synthesizing a polyimide having a phenolic hydroxyl group (A-1) having a structure represented by each of the general formula (5) and the general formula (6), for example, tetracarboxylic dianhydride and a phenolic hydroxyl group. It can be obtained by polycondensation of a diamine compound containing

  The tetracarboxylic dianhydride is an aromatic tetracarboxylic dianhydride having 8 to 36 carbon atoms or an alicyclic having 6 to 34 carbon atoms in terms of solubility in a solvent and solubility in an alkaline aqueous solution. The formula tetracarboxylic dianhydride is preferred.

  Specifically, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-cyclohexene-1,2-dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3,4- Benzenetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4 , 4′-biphenyltetracarboxylic dianhydride, 3,3 ″, 4,4 ″ -ter-phenyl tetracarboxylic dianhydride, 3,3 ′ ″, 4,4 ′ ″- Quaterphenyl (quater-phenyl) tetracarboxylic dianhydride, 3,3 ″ ″, 4,4 ″ ″-quinque-phenyl tetracarboxylic dianhydride, 2,2 ′, 3 3'-biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylidene-4,4'-diphthalic dianhydride, 2,2-propylidene-4,4 '-Diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4 , 4′-diphthalic dianhydride, 1,5-pentamethylene-4,4′-diphthalic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, thio-4,4′- Diphthalic dianhydride, sulfonyl-4,4′-diphthalic dianhydride, 1,3-bis (3,4-dicarboxyphenyl) benzene dianhydride, 1,3-bis (3,4-dicarboxy) Phenoxy) benzene dianhydride, 1,4-bis ( , 4-Dicarboxyphenoxy) benzene dianhydride, 1,3-bis [2- (3,4-dicarboxyphenyl) -2-propyl] benzene dianhydride, 1,4-bis [2- (3 4-Dicarboxyphenyl) -2-propyl] benzene dianhydride, bis [3- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, bis [4- (3,4-dicarboxyphenoxy) phenyl Methane dianhydride, 2,2-bis [3- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane Dianhydride, bis (3,4-dicarboxyphenoxy) dimethylsilane dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane Anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, ethylene Tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane 1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3 ′, 4,4′-bicyclohexyltetracarbo Acid dianhydride, carbonyl-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1 , 2-Ethylene-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride 2,2-propylidene-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, thio -4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo [2,2,2 ] Oct-7 Ene-2,3,5,6-tetracarboxylic dianhydride, rel- [1S, 5R, 6R] -3-oxabicyclo [3,2,1] octane-2,4-dione-6-spiro- 3 ′-(tetrahydrofuran-2 ′, 5′-dione), 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride , Ethylene glycol-bis (3,4-dicarboxylic anhydride phenyl) ether, and the like.

  Among them, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-cyclohexene-1,2 dicarboxylic acid anhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis ( 3,4-dicarboxyphenyl) sulfone dianhydride, 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic anhydride) is preferred, and among these, 5- (2,5-di Oxotetrahydro-3-furyl) -3-methyl-cyclohexene-1,2 dicarboxylic acid anhydride, bis (3,4-dicarboxyphenyl) ether dianhydride is transparent to i-line of mercury lamp, to alkaline aqueous solution It is particularly preferable in terms of solubility and photosensitivity.

  As the diamine compound containing a phenolic hydroxyl group, those selected from the above-mentioned bisaminophenol compounds are preferable, and among them, 2,2-bis (3-amino-4-hydroxyphenyl) propane is a resin composition. More preferable in terms of light sensitivity.

Examples of the diamine containing an organic group of Y ₂ in the general formula (6) include non-phenolic diamine (when n ₂ = 0) and 2,4-diaminophenol (when n ₂ = 1).

（式（ｄ）、（ｅ）中、Ｘ_６は、単結合及び下記式（ｆ）：

の構造からなる群より選ばれる少なくとも１種の構造を表し：そしてｍ_９は、１〜１０００の整数である。）。 Accordingly, (A-1) a polyimide containing a phenolic hydroxyl group represented by the general formula (5) and the general formula (6), respectively, is transparent in the i-line region and dissolved in an alkaline developer in the exposed portion. From the viewpoint of properties, a structure represented by the following general formula (d) or (e) is preferable:

(In the formulas (d) and (e), X ₆ represents a single bond and the following formula (f):

And at least one structure selected from the group consisting of the following structures: and m ₉ is an integer of 1-1000. ).

  (A-1) The dehydration condensation reaction when synthesizing a polyimide having a phenolic hydroxyl group is carried out according to, for example, the method described in International Publication No. 01/034679 pamphlet, and the tetracarboxylic dianhydride and the phenolic diamine. In the presence of an acid catalyst or a base catalyst, by heating to 30 ° C to 220 ° C, preferably 170 ° C to 200 ° C.

  As the acid catalyst, it is possible to use an inorganic acid such as sulfuric acid or an organic acid such as p-toluenesulfonic acid that is usually used in the production of polyimide. Base catalysts include pyridine, triethylamine, dimethylaminopyridine, 1,8-diazabicyclo (5,4,0) undecene-7, 1,3,5,7-tetraazatricyclo (3,3,1,1, 3,7) Decane, triethylenediamine or the like may be used. Further, a mixed system of γ-valerolactone and pyridine may be used.

  Furthermore, without adding a polycondensation catalyst or the like, the temperature of the reaction solution is maintained at a temperature higher than the temperature at which the imidization reaction occurs, and water produced by the dehydration reaction is reacted with water using an azeotropic solvent such as toluene. It can also be produced by a method in which the imidation dehydration condensation reaction is completed.

  In the dehydration condensation reaction, it is preferable to use a polar organic solvent for dissolving a polymer soluble in an alkaline aqueous solution in addition to toluene which is a solvent for azeotropically distilling water as a reaction solvent. As this polar solvent, γ-butyrolactone, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, tetramethylurea, sulfolane and the like are used.

  In addition, when using 2 or more component tetracarboxylic dianhydride or 2 or more component phenolic diamine or non-phenolic diamine, you may form a block copolycondensate using a sequential reaction. In addition, when preparing raw materials of three or more components, the raw materials may be simultaneously charged into the reaction system to obtain a random copolycondensate.

  (A-1) The terminal of the polyimide having a phenolic hydroxyl group may be modified with, for example, the following compound. Examples of methods for modifying the terminal include maleic anhydride, succinic anhydride, cinnamic anhydride, 4-ethynylphthalic anhydride, phenylethynylphthalic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride , Cyclohexane-1,2-dicarboxylic anhydride, 4-methylcyclohexane-1,2-dicarboxylic anhydride, 4-aminostyrene, 4-ethynylaniline, 3-ethynylaniline, etc. are added in an appropriate amount during the synthesis of the polyimide. The method of doing is mentioned. Moreover, you may leave dicarboxylic acid as a terminal.

  (A-1) The terminal group of the polyimide having a phenolic hydroxyl group is preferably at least one terminal group selected from the group consisting of terminal groups represented by the following general formula (g) from the viewpoint of sensitivity. .

（式中、Ｌ_６は、−ＣＨ_２−、−Ｏ−又は−Ｓ−を表し、そしてＬ_７は、水素原子、炭素原子数１〜６のアルキル基又は炭素原子数２〜６のアルケニル基を表す。）

(In the formula, L ₆ represents —CH ₂ —, —O— or —S—, and L ₇ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. Represents.)

（式中、Ｘ_３は、炭素原子数２〜６０の２価から８価の有機基を示し；Ｙ_３は、炭素原子数２〜６０の２価から８価の有機基を示し；Ｒ_７、Ｒ_８、Ｒ_９及びＲ_１０は、それぞれ独立に水素原子又は炭素原子数１〜２０の１価の有機基を示し；ｇ及びｈ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；ｉ及びｊは、それぞれ独立に０〜４の整数であり；そしてｍ_７は、１〜１０００の整数である。）。 (A-2) PBO precursor and polyamide having an ester group and / or carboxyl group at the ortho position of the amide bond (A-2) PBO precursor and polyamide having an ester group and / or a carboxyl group at the ortho position of the amide bond Includes a PBO precursor; a polyimide precursor derived from a tetracarboxylic acid and a diamine and having a carboxyl group at the ortho position of the amide bond; and a polyamic acid ester in which a part of the carboxyl group is sealed. A structure represented by the general formula (7) is preferably used:

(Wherein X ₃ represents a divalent to octavalent organic group having 2 to 60 carbon atoms; Y ₃ represents a divalent to octavalent organic group having 2 to 60 carbon atoms; R ₇ , R ₈ , R ₉ and R ₁₀ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms; g and h are each independently an integer of 0 to 2 and simultaneously 0 I and j are each independently an integer from 0 to 4; and m ₇ is an integer from 1 to 1000.)

（式中、Ｘ_３は、炭素原子数２〜６０の２価から８価の有機基を示し；Ｙ_３は、炭素原子数２〜６０の２価から８価の有機基を示し；Ｒ_７、Ｒ_８、Ｒ_９及びＲ_１０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；ｇ及びｈ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；ｉ及びｊは、それぞれ独立に０〜４の整数であり；Ｘ_４及びＹ_４は、各々独立に、少なくとも２個の炭素原子を有する２価の有機基を表し；ｍ_７は、１〜１０００の整数であり；ｍ_８は、１〜５００の整数であり、かつ０．５≦ｍ_７／（ｍ_７＋ｍ_８）≦１．０あり；そして、ポリマーの構造は、ランダム構造でもブロック構造でも交互構造でもよい。）。 Further, (A-2) the PBO precursor and the polyamide having an ester group and / or a carboxyl group at the ortho position of the amide bond may be composed only of the structure represented by the general formula (7). In order to control alkali solubility, the structure represented by the following general formula (8) may be used:

(Wherein X ₃ represents a divalent to octavalent organic group having 2 to 60 carbon atoms; Y ₃ represents a divalent to octavalent organic group having 2 to 60 carbon atoms; R ₇ , R ₈ , R ₉ and R ₁₀ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms; g and h are each independently an integer of 0 to 2 and simultaneously 0 I and j are each independently an integer of 0 to 4; X ₄ and Y ₄ each independently represent a divalent organic group having at least 2 carbon atoms; ₇ is an integer from 1 to 1000; m ₈ is an integer from 1 to 500 and 0.5 ≦ m ₇ / (m ₇ + m ₈ ) ≦ 1.0; and the polymer structure is Random structure, block structure or alternating structure may be used.)

Y ₃ is preferably a tetravalent organic group having 2 to 30 carbon atoms from the viewpoint of improving the solubility in an alkali developer and the heat resistance of the resulting resin film. X ₃ is preferably a divalent organic group having 2 to 30 carbon atoms from the viewpoint of improving the solubility in an alkali developer and the heat resistance of the resulting resin film. m ₇ is an integer of 1 to 1000, more preferably an integer of 2 to 200, from the viewpoint of improving the solubility in an alkali developer and the mechanical properties of the resulting resin film. An integer is more preferable, and an integer of 3 to 60 is most preferable.

The m ₈ diamide units in the general formula (8) have a structure obtained by polycondensation of a diamine having a Y ₄ (NH ₂ ) ₂ structure and a dicarboxylic acid having a X ₄ (COOH) ₂ structure.
Y ₄ is preferably a divalent organic group having 2 to 30 carbon atoms from the viewpoint of improving the solubility in an alkali developer and the heat resistance of the resulting resin film. X ₄ is preferably a divalent organic group having 2 to 30 carbon atoms from the viewpoint of improving the solubility in an alkaline developer and the heat resistance of the resulting resin film. m ₈ is an integer of 1 to 500, and more preferably an integer of 1 to 10 from the viewpoint of improving the solubility in an alkali developer and the mechanical properties of the resulting resin film.

In the structure represented by the general formula (8), the higher the proportion of the units containing Y ₃ and X ₃ (for example, dihydroxydiamide units), the more the solubility of the (A) alkali-soluble resin in the alkaline aqueous solution is improved. The value of m ₇ / (m ₇ + m ₈ ) is 0.5 or more, more preferably 0.7 or more, and most preferably 0.8 or more.

  Among the structures represented by the general formulas (7) and (8), a structure containing two hydroxyl groups in the unit structure is preferable. Therefore, this case will be described.

A polymer containing two hydroxyl groups in a unit structure is a polycondensation of a dicarboxylic acid having a X ₃ (COOH) ₂ structure and a bisaminophenol having a Y ₃ (NH ₂ ) ₂ (OH) ₂ structure. Can be obtained.

  The two amino groups and hydroxy groups of the bisaminophenol are each in the ortho position. When the bisaminophenol is heated to about 250 to 400 ° C., the bisaminophenol is cyclized to be changed to polybenzoxazole which is a heat resistant resin.

Examples of the bisaminophenol having a structure of Y ₃ (NH ₂ ) ₂ (OH) ₂ include 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, and 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-bis (4-a Mino-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- Examples include diamino-4,6-dihydroxybenzene. These bisaminophenols can be used alone or in admixture of two or more.

Of these bisaminophenols having the structure of Y ₃ (NH ₂ ) ₂ (OH) ₂ , those particularly preferred from the viewpoint of heat resistance are bisaminophenols in which Y ₃ is selected from the following structures:

（式中、Ｙ_５は、少なくとも２個の炭素原子を有する４価の有機基を表す。）。 Further, as a compound having a structure of Y ₃ (NH ₂ ) ₂ (OH) ₂ , a compound represented by the following general formula (10), which is a diamine having a PBO precursor structure in the molecule, can also be used:

(Wherein Y ₅ represents a tetravalent organic group having at least two carbon atoms).

Y ₅ preferably has the same structure as the structure of Y ₃ contained in the compounds exemplified as preferred for Y ₃ (NH ₂ ) ₂ (OH) ₂ described above.

More preferred examples of the diamine represented by the general formula (10) 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、Ｘ_５は、炭素数２〜６０の２価の有機基である。） As another method for obtaining a diamine having a PBO precursor structure in the molecule, two molecules of nitroaminophenol are reacted with dicarboxylic acid dichloride having the structure of X ₅ (COCl) ₂ , followed by nitro group conversion. There is also a method for obtaining a diamine represented by the following general formula by reduction to an amino group:

(In the formula, X ₅ is a divalent organic group having 2 to 60 carbon atoms.)

Specific examples of such diamine compounds include the following structures:

Further, as a polymer containing two hydroxyl groups, a dicarboxylic acid having a structure of X ₃ (COOH) ₂ and a diamine having a structure of Y ₃ (NH ₂ ) ₂ (OH) ₂ (COOR ₆ ) ₂ are combined with each other. A condensed polymer can also be used.

（式中、Ｘ_６は、炭素数４〜６０の４価の有機基を示し；そしてＲ_６は、炭素数１〜２０の１価の炭化水素基を示す。）。 As the diamine having a Y ₃ (NH ₂ ) ₂ (OH) ₂ (COOR ₆ ) ₂ structure, for example, a compound having two polyimide precursor structures in the molecule represented by the following general formula (14) (hereinafter, "Bisaminophenol having a PI precursor structure in the molecule"):

(In the formula, X ₆ 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).

（Ｒ_６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 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, a monoamine or the like, and a hydroxyl group at a position ortho to each other An example is a method in which two molecules of aniline having a nitro group are condensed and then the nitro group is reduced.

Y ₄ in the general formula (8) is a divalent organic group having two carbon atoms, and is derived from a diamine represented by Y ₄ (NH ₂ ) ₂ . Examples of such diamines include aromatic diamines, aliphatic diamines, and silicon diamines.

  Among these, examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and 4,4′-diamino. Diphenyl 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-a Nophenyl) 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-amino) Phenoxyphenyl) sulfide, 1,4- (4-aminophenoxyphenyl) benzene, 1,3- (4-aminophenoxyphenyl) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4′-di -(3-aminophenoxy) diphenylsulfone, 4,4'-diaminobenzanilide and the like, and the hydrogen atom of the aromatic nucleus of these aromatic diamines are chlorine atom, fluorine atom, bromine atom, methyl group, methoxy group, cyano group A compound substituted by at least one group or atom selected from the group consisting of a group and a phenyl group It is below.

  Examples of the aliphatic diamine include ethylenediamine, 1,3-propanediamine, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8. And compounds such as -diaminooctane, 1,9-diaminononane, 1,10-diaminodecane.

In order to enhance the adhesion between the photosensitive resin composition and a base material of the present invention, as part or all of the diamine having a structure of Y 4 _{(NH 2) 2,} can be selected silicon diamine. Examples of silicon diamines include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (4-aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetramethyldi Examples include siloxane, 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, and bis (γ-aminopropyl) tetraphenyldisiloxane.

（式中、Ａ_１は、−ＣＨ_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−及び単結合からなる群より選ばれる少なくとも１つの２価の基を示し；Ｌ_１は、それぞれ独立にハロゲン原子、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＝０〜８である。）；

（式中、ｎ_１０は、１〜１２の整数である。）；及び

（式中、Ｌ_２、Ｌ_３及びＬ_４は、それぞれ独立に水素原子又はメチル基を示し；そしてＬ_５は、水素原子、メチル基又は水酸基を示す。）。 X ₃ and X ₄ each have a structure represented by the following general formulas (16) to (18):

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. L ₁ represents a group selected from the group consisting of a halogen atom, a hydrocarbon group, an amide group, a urea group, an imide group and a urethane group; and k = 0 ~ 8));

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

(Wherein L ₂ , L ₃ and L ₄ each independently represents 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 of a dicarboxylic acid having a tricyclodecane skeleton includes bis (carboxy) tricyclo [5,2,1,02,6] decane. Examples of production of the compound include synthesis examples described in International Publication No. 2009/081950 pamphlet.

（式中、Ａ_２は、−ＣＨ_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−、及び−ＣＯＯ−からなる群より選ばれる少なくとも１つの２価の基を表す。）。 Furthermore, as a dicarboxylic acid having X ₃ (COOH) ₂ and X ₄ (COOH) ₂ structures, a dicarboxylic acid obtained by ring-opening a tetracarboxylic dianhydride with a monoalcohol, a monoamine, or the like 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:

Wherein A ₂ is a group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, and —COO—. Represents at least one divalent group selected from the above.

（式中、Ｙ_６は、Ｙ_３（ＯＨ）_２（ＮＨ−）_２で表される２価の有機基を表し；かつ、Ｙ_３は前記一般式（７）におけるものと同義である。）。 Further, trimellitic acid chloride is reacted with bisaminophenol to produce tetracarboxylic dianhydride, and the dicarboxylic acid obtained by ring opening in the same manner as the above tetracarboxylic dianhydride is used. It can also be used. Examples of the tetracarboxylic dianhydride obtained here include compounds represented by the following general formula (20):

(In the formula, Y ₆ represents a divalent organic group represented by Y ₃ (OH) ₂ (NH—) ₂ ; and Y ₃ has the same meaning as in General Formula (7)). .

  As a method for producing a precursor having a repeating unit represented by the above general formula (7) and general formula (8), dicarboxylic acid and thionyl chloride are used to obtain dicarboxylic acid chloride, Examples thereof include a method in which bisaminophenol (diamine) is allowed to act and 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.

  The precursor having a repeating unit represented by the general formula (7) and the general formula (8) (for example, PBO precursor) is sealed with an organic group (hereinafter also referred to as “sealing group”). It is also preferable to stop use. For example, 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, a compound having an amino group or a hydroxyl group is used as a sealing group. Is preferred. Examples of the compound include aniline, ethynylaniline, norborneneamine, butylamine, propargylamine, ethanol, propargyl alcohol, benzyl alcohol, hydroxyethyl methacrylate and hydroxyethyl acrylate.

  Conversely, when the sum of the bisaminophenol component and the diamine component is used as an excess number of moles compared to the dicarboxylic acid component, the compound having a blocking group may be an acid anhydride, carboxylic acid, acid chloride, or 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, cyclohexene dicarboxylic acid anhydride, methacryloyloxyethyl methacrylate, phenyl isocyanate, mesyl chloride, tosyl chloride and the like.

（式中、Ｌ_６は、−ＣＨ_２−、−Ｏ−又は−Ｓ−を表し；かつ、Ｌ_７は、水素原子、炭素原子数１〜６のアルキル基又は炭素原子数２〜６のアルケニル基を表す。）
で表される基が挙げられる。 Among these, preferred end groups include the following general formula (21):

(In the formula, L ₆ represents —CH ₂ —, —O— or —S—; and L ₇ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl having 2 to 6 carbon atoms. Represents a group.)
The group represented by these is mentioned.

  (A-1) Polyimide having a phenolic hydroxyl group, (A-2) Gel permeation chromatography of a polyamide having an ester group and / or a carboxyl group at the ortho position of the PBO precursor and amide bond (hereinafter referred to as “GPC”) The polystyrene-reduced weight average molecular weight according to (also referred to as “polystyrene”) is preferably 3,000 to 70,000, and more preferably 6,000 to 50,000. The weight average molecular weight is preferably 3,000 or more from the viewpoint of physical properties of the cured relief pattern. Moreover, from a viewpoint of resolution, 70,000 or less is preferable. 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 organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko.

  (A) Both alkali-soluble resins are unit structures represented by the general formula (5) and the general formula (6), and unit structures represented by the general formula (7) and the general formula (8). You may have.

  The structures of the both are described above in the formation of the structure represented by the general formula (7) or (8), for example, the polyimide skeleton having a phenolic hydroxyl group represented by the general formula (5) or (6). It can be obtained by copolymerizing with a polymerization component. The copolymerization ratio at the time of copolymerization is arbitrarily selected, but the ratio of [structure represented by general formula (7) or (8)]: [structure represented by general formula (5) or (6)] , For example, the ratio of hydroxypolyamide: polyimide having a phenolic hydroxyl group is preferably in the range of 10:90 to 100: 0 from the viewpoint of photosensitivity.

(A-3) Phenol resin and its derivative (A) The structure in the case where the alkali-soluble resin is a phenol resin and its derivative is not particularly limited, but a novolak resin is preferably used from the viewpoint of stability. It is done.

  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. And a method of synthesizing by a combination thereof.

  Here, specific examples of the polymerization component include a compound having two methylol groups in the molecule, a compound having two alkoxymethyl groups in the molecule, and a compound having two haloalkyl groups in the molecule. .

  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, 2- t-butylphenol, 3-t-butylphenol, 4-t-butylphenol, methylenebisphenol, methylenebisp-cresol, bisphenol A, resorcin, catechol, 2-methylresorcin, 4-methylresorcin, 5-methylresorcin, 4-t- Butyl catechol, o-ku Rophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α-naphthol, β-naphthol, thymol, isothymol and the like can be mentioned, and these can be used alone or as a mixture.

  Examples of aldehydes include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropionaldehyde, β-phenylpropionaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde. Chloroacetaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, terephthalaldehyde, etc. Can be mentioned.

  Examples of ketones include acetone, methyl ethyl ketone, diethyl ketone, and diphenyl ketone. These can be used alone or in combination of two or more.

  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.

  Moreover, the phenol resin is from the group consisting of the following general formulas (a) to (c) from the viewpoint of uniformity of the surface after development, the shape of the cured relief pattern, the degree of elongation, and degassing during heating of the cured relief pattern. More preferred is a novolak resin having at least one selected structure.

（式中、Ｒ_３及びＲ_４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；ａ及びｃは、１又は２であり；ｂ及びｄは、それぞれ独立に０〜２の整数であり；ｍ_１、ｍ_２は、それぞれ独立に０又は正の整数であるが、ｍ_１とｍ_２が同時に０になることはない。）

(Wherein R ₃ and R ₄ each independently represents a monovalent organic group having 1 to 10 carbon atoms; a and c are 1 or 2; b and d are each independently 0 to 0; M _{1 and} m ₂ are each independently 0 or a positive integer, but m ₁ and m ₂ are not 0 at the same time.)

（式中、Ｒ_５及びＲ_６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；ｅ及びｆは、それぞれ独立に０〜２の整数であり；ｍ_３は、０又は正の整数であり；そしてｍ_４は正の整数である。）

(Wherein, _{R 5} and _{R 6} are each independently a monovalent organic group having 1 to 10 carbon atoms; e and f are each independently an integer of 0 to 2; _{m 3} is 0 Or a positive integer; and m ₄ is a positive integer.)

（式中、Ｒ_１３は、炭素原子数１〜１０の１価の有機基を示し；ｋは、０〜２の整数であり；ｍ_１０は、正の整数であり；そしてｍ_１１は、０又は正の整数である。）

(Wherein R ₁₃ represents a monovalent organic group having 1 to 10 carbon atoms; k is an integer of 0 to 2; m ₁₀ is a positive integer; and m ₁₁ is 0. Or a positive integer.)

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

  (A) As said alkali-soluble resin, said resin can be used individually or in mixture of 2 or more types. Among them, in particular, (A-2) PBO precursor represented by the general formula (7) or (8), polyamide having an ester group and / or a carboxyl group at the ortho position of the amide bond, and (A-3) phenol It is preferable to use a mixture with a resin.

  (A-3) A phenol resin and (A-2) PBO precursor represented by the general formula (7) or (8) and a polyamide having an ester group and / or a carboxyl group at the ortho position of the amide bond are mixed. The mixing ratio when (A-3) increases the ratio of (A-3) the phenolic resin, the effect of suppressing the film loss during development, and the patterning on the metal, the metal after etching with the fluorine-based compound gas after curing The effect of inhibiting corrosion is obtained. On the other hand, the smaller the ratio of (A-3) phenolic resin, the better the pattern shape after curing and the elongation after curing, so the ratios when mixing are general formulas (7), (8) The phenol resin is 21 to 100 parts by mass, preferably 75 to 100 parts by mass, and more preferably 90 to 100 parts by mass with respect to 100 parts by mass of the PBO precursor represented by any of the above.

(A-4) Polyhydroxystyrene and derivatives thereof (A) Specific examples of the case where the alkali-soluble resin is polyhydroxystyrene and derivatives thereof include, for example, poly-o-hydroxystyrene, poly-m-hydroxystyrene, poly -P-hydroxystyrene, poly- [alpha] -methyl-o-hydroxystyrene, poly- [alpha] -methyl-m-hydroxystyrene, poly- [alpha] -methyl-p-hydroxystyrene, or a partially acetylated product, silylated product, or the like thereof. It is done. These polyhydroxystyrenes or derivatives thereof have a weight average molecular weight of 3,000 to 100,000, particularly preferably 4,000 to 20,000.

(B) Photoacid generator (B) As the photoacid generator, a compound having a naphthoquinonediazide structure, an onium salt, a halogen-containing compound and the like can be used. From the viewpoint of solvent solubility and storage stability, naphtho A compound having a quinonediazide structure (hereinafter also referred to as “naphthoquinonediazide compound” or “NQD compound”) is preferred.

  Examples of the onium salt include iodonium salts, sulfonium salts, phosphonium salts, ammonium salts, diazonium salts, and the like, and onium salts selected from the group consisting of diaryliodonium salts, triarylsulfonium salts, and trialkylsulfonium salts are preferable.

  Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and the like, and trichloromethyltriazine is preferable.

  The NQD compound is preferably a compound having a 1,2-naphthoquinonediazide structure. 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.

（式中、Ｑは、水素原子又は以下の構造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：

）。 Examples of preferred NQD compounds include, for example, those represented by the following structure:

(Wherein Q is a hydrogen atom or a naphthoquinone diazide sulfonate group represented by either of the following structures, 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.

  1-50 mass parts is preferable and, as for the compounding quantity with respect to 100 mass parts of alkali-soluble resin (A) of a photo-acid generator (B), 5-30 mass parts is more preferable. When the blending amount of the photoacid generator (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 of the cured film is good and the exposure is performed. There is little development residue (scum) of the part.

（式中、Ｒ_１及びＲ_２は、それぞれ独立に、水素原子又は炭素数１〜１０の１価の有機基を示し；かつ、ｎの平均値は０以上５．０以下であるが、ｎの平均値が０の場合、Ｒ_１及びＲ_２は同時に水素原子になることはない。）。 (C) Salicylic acid oligomer (C) The salicylic acid oligomer or mixture thereof used in the present invention has a structure represented by the following general formula (1):

(Wherein R ₁ and R ₂ each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms; and the average value of n is 0 or more and 5.0 or less, n When the average value of is 0, R ₁ and R ₂ are not simultaneously hydrogen atoms.)

  Conventionally, in order to improve the sensitivity and resolution of a positive photosensitive resin composition, as described in WO08 / 020573, an organic acid such as m-toluic acid or m-anisic acid is used as a PBO precursor. In this method, although sensitivity and resolution are improved, there is room for improvement in the residual film ratio after curing and the pattern cross-sectional shape at the time of curing.

  However, when the salicylic acid oligomer represented by the general formula (1) or a mixture thereof according to the present invention is used, the present inventors have a large effect of promoting dissolution of the exposed area, and the remaining film ratio after heat curing of the relief pattern And the pattern cross-sectional shape was found to be good.

  Here, the average value of n in the general formula (1) is a value obtained by a measurement method described later.

R ₁ and R ₂ in the general formula (1) are both preferably a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, and more preferably both are hydrogen atoms, in that the dissolution promoting effect is good. Preferably there is.

  The average value of n is preferably 0.2 or more and 4.8 or less, and more preferably 0.8 or more and 4.0 or less, from the viewpoint of good dissolution promoting effect and residual film ratio upon curing. 1.0 or more and 3.0 or less is more preferable.

When the average value of n is zero, that is, when the salicylic acid oligomer includes substantially only the substance of n = 0 in the general formula (1), R ₁ and R ₂ are each independently a hydrogen atom or a carbon atom number of 1 It is a monovalent organic group of 10 to 10 and is not limited unless R ₁ and R ₂ simultaneously become hydrogen atoms. Among them, from the viewpoint of the dissolution accelerating effect, R ₁ is an alkyl group having 1 to 3 carbon hydrogen atom or a carbon, preferably when R ₂ is an alkyl group of 1 to 5 carbon atoms, R ₁ is a hydrogen atom And R ₂ is particularly preferably a methyl group.

  Although it does not necessarily limit as a manufacturing method of the salicylic acid oligomer represented by General formula (1) in this invention, or its mixture, The method of condensing salicylic acid and aldehydes, such as formaldehyde, is mentioned.

  Examples of aldehydes include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropionaldehyde, β-phenylpropionaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, chloro Examples include acetaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, terephthalaldehyde and the like. . Examples of ketones include acetone, methyl ethyl ketone, diethyl ketone, and diphenyl ketone. These can be used alone or in combination of two or more.

  (C) The salicylic acid oligomer can be used as a mixture after the reaction or after purification alone.

  The compounding quantity with respect to alkali-soluble resin of the said (C) salicylic acid oligomer or its mixture is 0.1-10 mass parts with respect to 100 mass parts of alkali-soluble resin (A), and 1.0-9.0 mass parts is 1.0-9.0 mass parts. preferable. (C) If the compounding quantity of a salicylic acid oligomer or its mixture is 0.1 mass part or more, the development residue of an exposure part will decrease and a sensitivity will be favorable. Moreover, if the said compounding quantity is 10 mass parts or less, there will be little film loss at the time of hardening, and the tensile elongation rate of the film | membrane after hardening will be favorable.

<Other ingredients>
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 of 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 amount added is preferably 10 to 2,000 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A). 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, It is preferable that a compounding quantity is 1-100 mass parts with respect to 100 mass parts of alkali-soluble resin (A), More preferably. 3 to 50 parts by mass. When the blending amount is 1 part by mass or more, crosslinking proceeds well and the patterning property becomes good. When the blending amount is 100 parts by mass or less, the mechanical properties after curing are kept good.

  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 Particularly preferred.

  These hydroxyl group-containing compounds may be used alone or in combination of two or more.

  0.01-70 mass parts is preferable with respect to 100 mass parts of alkali-soluble resin (A), 0.1-50 mass parts is more preferable, and the compounding quantity in the case of mix | blending said alcohol is 1-40 mass parts. Is more preferable, and 5 to 25 parts by mass is particularly 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. As for the compounding quantity in the case of mix | blending dye, 0.1-10 mass parts is preferable with respect to 100 mass parts of alkali-soluble resin (A). If the blending amount is 0.1 parts by mass or more, the visualization effect is obtained well, and if it is 10 parts by mass or less, the heat resistance of the film after thermosetting is good.

  Examples of the perfume include terpene compounds, and monoterpene compounds and sesquiterpene compounds are preferable from the viewpoint of solubility in solvents.

  Specifically, linalool, isophytol, dihydrolinalol, linalool acetate, linalool oxide, geranyl linalool, lavandulol, tetrahydrolabandulol, lavandulol acetate, nerol, nerol acetate, geraniol, citral, geranyl acetate, geranylacetone , Geraniic acid, citral dimethyl acetal, citronellol, citronellal, hydroxycitronellal, dimethyl octanal, citronellyl acid, citronellyl acetate, tageton, artemisia ketone, pregol, isopulegol, menthol, menthol acetate, isomenthol, neomenthol, mentanol , Menthanetriol, menthanetetraol, carbomenthol, menthoxyacetic acid, perillyl alcohol, perilaldehyde Carbeol, piperitol, terpene-4-ol, terpineol, terpineol, dihydroterpineol, sobreol, thymol, borneol, bornyl acetate, isoborneol, isobornyl acetate, cineol, pinol, pinocarbeveol, mirutenol, mirutenal, berbenol, pinocamphe 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.

  0.1-70 mass parts is preferable with respect to 100 mass parts of alkali-soluble resin (A), and, as for the compounding quantity in the case of mix | blending a fragrance | flavor, 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.

  0-10 mass parts is preferable with respect to 100 mass parts of alkali-soluble resin (A), and, as for the compounding quantity of surfactant, 0.01-1 mass part 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 organosilicon compound include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name KBM803, manufactured by Chisso Corporation: trade name of Silaace S810), 3-mercaptopropyltriethoxysilane (AZMAX Corporation). Manufactured by trade name: SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name: LS1375, manufactured by Azumax Co., Ltd .: tradename: SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azumax Corporation) : Trade name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydi Toxisilane, 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-methyl Captobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N- (3-triethoxysilylpropyl) urea (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name LS3610, manufactured by Asmax Co., Ltd .: trade name SIU9055.0), N -(3-trimethoxysilylpropyl) urea (manufactured by Azmax Co., Ltd .: trade name SIU9058.0), N- (3-diethoxymethoxysilylpropyl) urea, N- (3-ethoxydimethoxysilylpropyl) urea, N- (3-Tripropoxysilylpropyl) urea, N- (3-diethoxypropoxysilylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N- (3-dimethoxypropoxysilylpropyl) urea, N- (3-methoxydipropoxysilyl group (Lopyl) urea, N- (3-trimethoxysilylethyl) urea, N- (3-ethoxydimethoxysilylethyl) urea, N- (3-tripropoxysilylethyl) urea, N- (3-tripropoxysilylethyl) Urea, N- (3-ethoxydipropoxysilylethyl) urea, N- (3-dimethoxypropoxysilylethyl) urea, N- (3-methoxydipropoxysilylethyl) urea, N- (3-trimethoxysilylbutyl) Urea, N- (3-triethoxysilylbutyl) urea, N- (3-tripropoxysilylbutyl) urea, 3- (m-aminophenoxy) propyltrimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SLA0598.0) , M-aminophenyltrimethoxysilane (manufactured by AZMAX Co., Ltd .: commodity SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.1) aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.2), 2- (trimethoxysilylethyl) Pyridine (manufactured by Azmax Co., Ltd .: trade name SIT8396.0), 2- (triethoxysilylethyl) pyridine, 2- (dimethoxysilylmethylethyl) pyridine, 2- (diethoxysilylmethylethyl) pyridine, (3-triethoxy (Silylpropyl) -t-butylcarbamate, (3-glycidoxypropyl) triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, Tra-i-butoxysilane, tetra-t-butoxysilane, tetrakis (methoxyethoxysilane), tetrakis (methoxy-n-propoxysilane), tetrakis (ethoxyethoxysilane), tetrakis (methoxyethoxyethoxysilane), bis (trimethoxy Silyl) 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 Orchid, bis (pentadionate) titanium-O, O'-bis (oxyethyl) -aminopropyltriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilane Diol, n-butyldiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenyl Silanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenyl Examples thereof include, but are not limited to, silanol, isopropyl diphenyl silanol, n-butyl diphenyl silanol, isobutyl diphenyl silanol, tert-butyl diphenyl silanol, and triphenyl silanol. These may be used alone or in combination.

As the organosilicon compound, among the aforementioned 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 preferred:

  The organosilicon compounds may be used alone or in combination of two or more. When the organosilicon compound is blended, the blending amount is preferably 1 to 40 parts by weight, more preferably 2 to 30 parts by weight, and 4 to 20 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (A). Further preferred. 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、Ｚ_７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；Ｚ_８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; Z ₈ is a hydrogen atom, a hydroxyl group, and the number of carbon atoms. A group selected from the group consisting of 1 to 5 monovalent hydrocarbon groups and aminoalkyl groups.).

  Among the heterocyclic structure compounds, from the viewpoint of sensitivity on a copper substrate, from 5-mercapto-1-phenyltetrazole, 1,2,3-benzotriazole, benzothiazole, benzoxazole, benzimidazole and 2-mercaptobenzoxazole. 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.

  0.1-30 mass parts is preferable with respect to 100 mass parts of alkali-soluble resin (A), and, as for the compounding quantity in the case of mix | blending a heterocyclic structure compound, 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) 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 photosensitive resin layer on 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 development, the photosensitive resin layer can be eluted and removed 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 of a quaternary ammonium salt such as quaternary ammonium salt or the like, 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. 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 can be given.

  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) of polymer>
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: Shodex 805M / 806M series manufactured by Showa Denko KK Mobile phase: N-methylpyrrolidone 40 ° C
Flow rate: 1.0 ml / min

<Degree of polymerization of salicylic acid oligomer (average value of n)>
After confirming that the raw material salicylic acid did not remain by GPC, it was calculated by NMR. The calculation is based on the ratio of the integral value E ₁ of aromatic ring protons observed at 6.5 to 8.0 ppm to the integral value E ₂ of aliphatic chain protons observed at 3.5 to 4.5 ppm ( From E ₁ / E ₂ ), the following formula was used.
_{n = (3- (E 1 /} E 2)) / ((E 1 / E 2) -1)

The NMR and GPC measurement conditions used are as follows:
<1H NMR measurement conditions>
Measuring device: JNM-GSX400 type manufactured by JEOL Ltd. Measuring temperature: 23 ° C.
Measurement solvent: deuterated tetrahydrofuran solvent (THF-d ₈ )
Measurement concentration: 8 mg / 0.7 mg (sample / deuterated solvent)
<GPC measurement conditions>
Pump: JASCO PU-980
Detector: JASCO RI-930
Column: Shodex 805/804/803 series manufactured by Showa Denko KK Mobile phase: Tetrahydrofuran, 40 ° C
Flow rate: 1.0 ml / min

<Evaluation of patterning characteristics>
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.
・ Developing 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 relief A pattern was formed.

[Sensitivity (mJ / cm ² )]
In the coating film produced on the said conditions, the minimum exposure amount which the 100 micrometer square relief pattern of an exposure part can melt | dissolve completely was evaluated as a sensitivity.

<Evaluation of residual film rate after curing 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.
The post-curing residual film ratio (%) was defined as (film thickness of cured relief pattern after curing) × 100 / (film thickness of relief pattern after development).

<Evaluation of cross-sectional shape after curing>
As the pattern cross-sectional shape evaluation after curing, the pattern cross-sectional shape of the cured relief pattern having a line and space of 50 μm: 50 μm was observed with a scanning electron microscope (SEM), and a tangent line was drawn at half the height of the cured film thickness. When the inner angle with respect to the surface of the base material (silicon wafer in the above case) exceeds 50 °, it was judged as “good”, and when it was 50 ° or less, it was judged as “bad”.

[Synthesis Example 1]
<(A) Synthesis of diamine compound for raw material of alkali-soluble resin>
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, filtration was performed to remove the palladium compound as a catalyst, and the mixture was concentrated by a rotary evaporator to obtain a diamine having the following structure. The obtained solid was used for the reaction as it was.

[Synthesis Example 2]
<(A) preparation of bis (carboxy) tricyclo [5,2,1,0 ^2,6] decane for raw material of the alkali-soluble resin>
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 for (A) the starting alkali-soluble resin>
Obtained in Synthesis Example 2 Bis (carboxy) tricyclo [5,2,1,0 ^2,6] decane 62.5 g (278 mmol), thionyl chloride 97 mL (1.33 mol), pyridine 0.4mL of (5.0 mmol) 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 concentrated by removing excess thionyl chloride by azeotroping with toluene under reduced pressure, and oily bis (chlorocarbonyl) tricyclo [5,2,1,0 ^{2, 6} ] 73.3 g (100% yield) of decane was obtained.

[Synthesis Example 4]
<(B) Synthesis of quinonediazide compound (Q-1) as a photoacid generator>
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).

[Synthesis Example 5]
<(A) Synthesis of hydroxypolyamide resin (P-1) as alkali-soluble resin>
Under a dry nitrogen stream, 13.6 g (0.0225 mol) of the diamine obtained in Synthesis Example 1 and 4-ethynylaniline (trade name: P-APAC, manufactured by Fuji Photo Film Co., Ltd.) 0 as a terminal blocking agent .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.

  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]
<(A) Synthesis of hydroxypolyamide resin (P-2) as alkali-soluble resin>
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 44.4 g (0.17 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”) 67.8 g (0.185 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, 22.5 g (0.14 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 10.8 g (0.14 mol) of pyridine were added, and 50 The reaction solution was immersed in a hot water bath at 0 ° C. for 24 hours.

  Ethanol was added to the reaction solution to precipitate a polymer, and then recovered and dissolved in 646 g of GBL. Subsequently, ion exchange was performed with 62.1 g of a cation exchange resin (manufactured by Organo, Amberlyst A21) and 59.6 g of an anion exchange resin (manufactured by Organo, Amberlyst 15). This solution was dropped into 12 L of ion-exchanged water under high-speed stirring, and the polymer was dispersed and precipitated, collected, appropriately washed with water and dehydrated, and then vacuum-dried to obtain a hydroxypolyamide resin (P-2) powder.

  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.

[Synthesis Example 7]
<(A) Synthesis of phenol resin (N-1) as alkali-soluble resin>
First, the separable flask with a Dean-Stark apparatus having a capacity of 1.0 L was purged with nitrogen, and then, in the separable flask, 73.7 g (0.667 mol) of resorcin, 4,4′-bis (methoxymethyl) biphenyl (BMMB) 36.4 g (0.15 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.

  Next, in a separate container, 49.9 g (0.300 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 was dropped into 8 L of water under high-speed stirring to disperse and precipitate the resin, and this was recovered, washed with water and dehydrated appropriately, and then vacuum dried to obtain a resin (N-1). The weight average molecular weight by GPC of the synthesized resin was 9,900 in terms of polystyrene.

[Synthesis Example 8]
<(A) Synthesis of phenol resin (N-2) as alkali-soluble resin>
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 was dropped into 8 L of water under high-speed stirring to disperse and precipitate the resin, which was recovered, appropriately washed with water and dehydrated, and then vacuum dried to obtain a phenol resin (N-2).

[Synthesis Example 9]
<Synthesis of (C) salicylic acid oligomer (S-1)>
First, a separable flask having a capacity of 1.0 L with a Dean-Stark apparatus was purged with nitrogen, and then 100 g (0.72 mol) of 2-hydroxybenzoic acid and 14.49 g (0.48 mol) of formaldehyde in the separable flask. P-Toluenesulfonic acid (2.40 g, 0.015 mol) was 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. After completion of the reaction, the reaction vessel was cooled in the atmosphere, and 500 g of PGME was separately added thereto and stirred. The reaction diluted solution was dropped into 4000 g of water under high-speed stirring to disperse and precipitate the compound, which was recovered, appropriately washed with water, dehydrated and then vacuum-dried, and a salicylic acid oligomer having an average value of n of 0.8 ( S-1) was obtained.

[Synthesis Example 10]
<Synthesis of (C) salicylic acid oligomer (S-2)>
First, a 1.0 L separable flask equipped with a Dean-Stark apparatus was purged with nitrogen, and then in the separable flask, 100 g (0.72 mol) of 2-hydroxybenzoic acid and 16.31 g (0.54 mol) of formaldehyde were added. P-Toluenesulfonic acid (2.40 g, 0.015 mol) was 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. After completion of the reaction, the reaction vessel was cooled in the atmosphere, and 500 g of PGME was separately added thereto and stirred. The reaction diluted solution was dropped into 4000 g of water under high-speed stirring to disperse and precipitate the compound, which was recovered, appropriately washed with water, dehydrated and then vacuum dried, and a salicylic acid oligomer having an average value of n of 1.5 ( S-2) was obtained.

[Synthesis Example 11]
<Synthesis of (C) salicylic acid oligomer (S-3)>
First, a 1.0 L separable flask equipped with a Dean-Stark apparatus was purged with nitrogen, and then, in the separable flask, 100 g (0.72 mol) of 2-hydroxybenzoic acid and 17.39 g (0.58 mol) of formaldehyde. P-Toluenesulfonic acid (2.40 g, 0.015 mol) was 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. After completion of the reaction, the reaction vessel was cooled in the atmosphere, and 500 g of PGME was separately added thereto and stirred. The reaction dilution is dropped into 4000 g of water under high-speed stirring to disperse and precipitate the compound, which is recovered, appropriately washed with water and dehydrated, and then vacuum-dried, and a salicylic acid oligomer having an average value of n of 2.8 ( S-3) was obtained.

[Synthesis Example 12]
<Synthesis of (C) salicylic acid oligomer (S-4)>
First, the separable flask with a Dean-Stark apparatus having a capacity of 1.0 L was purged with nitrogen, and then 100 g (0.72 mol) of 2-hydroxybenzoic acid and 18.12 g (0.60 mol) of formaldehyde in the separable flask. P-Toluenesulfonic acid (2.40 g, 0.015 mol) was 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. After completion of the reaction, the reaction vessel was cooled in the atmosphere, and 500 g of PGME was separately added thereto and stirred. The reaction diluted solution was dropped into 4000 g of water under high-speed stirring to disperse and precipitate the compound, which was recovered, washed with water, dehydrated, and vacuum-dried, and a salicylic acid oligomer having an average value of n of 4.0 ( S-4) was obtained.

[Synthesis Example 13]
<Synthesis of (C) salicylic acid oligomer (S-5)>
First, a 1.0 L separable flask equipped with a Dean-Stark apparatus was purged with nitrogen, and then, in the separable flask, 100 g (0.72 mol) of 2-hydroxybenzoic acid and 18.64 g (0.62 mol) of formaldehyde P-Toluenesulfonic acid (2.40 g, 0.015 mol) was 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. After completion of the reaction, the reaction vessel was cooled in the atmosphere, and 500 g of PGME was separately added thereto and stirred. The reaction dilution is dropped into 4000 g of water under high-speed stirring to disperse and precipitate the compound, which is recovered, washed with water, dehydrated, and vacuum-dried. The salicylic acid oligomer (average value of n is 4.8) S-5) was obtained.

[Synthesis Example 14]
<Synthesis of (C) salicylic acid oligomer (S-6)>
First, the separable flask with a Dean-Stark apparatus having a capacity of 1.0 L was purged with nitrogen, and then 100 g (0.72 mol) of 2-hydroxybenzoic acid and 19.57 g (0.65 mol) of formaldehyde in the separable flask. P-Toluenesulfonic acid (2.40 g, 0.015 mol) was 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. After completion of the reaction, the reaction vessel was cooled in the atmosphere, and 500 g of PGME was separately added thereto and stirred. The reaction diluted solution was dropped into 4000 g of water under high-speed stirring to disperse and precipitate the compound, which was recovered, appropriately washed with water and dehydrated, and then vacuum-dried to obtain a salicylic acid oligomer having an average value of n of 7.2 ( S-6) was obtained.

[Synthesis Example 15]
<Synthesis of (C) salicylic acid oligomer (S-7)>
First, the separable flask with a Dean-Stark apparatus having a capacity of 1.0 L was purged with nitrogen, and then 100 g (0.72 mol) of 2-hydroxybenzoic acid and 23.92 g (0.54 mol) of acetaldehyde in the separable flask. P-Toluenesulfonic acid (2.40 g, 0.015 mol) was 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. After completion of the reaction, the reaction vessel was cooled in the atmosphere, and 500 g of PGME was separately added thereto and stirred. The reaction diluted solution was dropped into 4000 g of water under high-speed stirring to disperse and precipitate the compound, which was recovered, appropriately washed with water, dehydrated and then vacuum-dried, and a salicylic acid oligomer having an average value of n of 1.2 ( S-7) was obtained.

[Synthesis Example 16]
<Synthesis of (C) salicylic acid oligomer (S-8)>
First, a 1.0 L separable flask equipped with a Dean-Stark apparatus was purged with nitrogen, and then, in the separable flask, 100 g (0.72 mol) of 2-hydroxybenzoic acid and 25.51 g (0.58 mol) of acetaldehyde. P-Toluenesulfonic acid (2.40 g, 0.015 mol) was 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. After completion of the reaction, the reaction vessel was cooled in the atmosphere, and 500 g of PGME was separately added thereto and stirred. The reaction dilution is dropped into 4000 g of water under high-speed stirring to disperse and precipitate the compound, which is recovered, appropriately washed with water, dehydrated and then vacuum-dried, and a salicylic acid oligomer having an average value of n of 2.1 ( S-8) was obtained.

[Synthesis Example 17]
<Synthesis of (C) salicylic acid oligomer (S-9)>
The salicylic acid oligomer (S-2) with an average value of n of 1.5 synthesized in Synthesis Example 10 was dissolved in THF and separated by a silica column, and then dropped into water with high-speed stirring to precipitate the compound. Was appropriately washed with water and dehydrated, followed by vacuum drying to obtain a salicylic acid oligomer (S-9) having an average value of n of 1.0.

[Synthesis Example 18]
<Synthesis of (C) salicylic acid oligomer (S-10)>
The salicylic acid oligomer (S-2) with an average value of n of 1.5 synthesized in Synthesis Example 10 was dissolved in THF and separated by a silica column, and then dropped into water with high-speed stirring to precipitate the compound. Was appropriately washed with water and dehydrated, followed by vacuum drying to obtain a salicylic acid oligomer (S-10) having an average value of n of 2.0.

[Synthesis Example 19]
<Synthesis of (C) salicylic acid oligomer (S-11)>
The salicylic acid oligomer (S-2) with an average value of n of 1.5 synthesized in Synthesis Example 10 was dissolved in THF and separated by a silica column, and then dropped into water with high-speed stirring to precipitate the compound. Was appropriately washed with water and dehydrated, followed by vacuum drying to obtain a salicylic acid oligomer (S-11) having an average value of n of 0.

[Synthesis Example 20]
<Synthesis of (C) salicylic acid oligomer (S-12)>
The salicylic acid oligomer (S-7) having an average value of n of 1.2 synthesized in Synthesis Example 15 was dissolved in THF, separated by a silica column, and then added dropwise to water with high-speed stirring to precipitate the compound. Was collected, washed with water and dehydrated appropriately, followed by vacuum drying to obtain a salicylic acid oligomer (S-12) having an average value of n of 0.

[Examples 1 to 13, Comparative Examples 1 to 5]
The photosensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 5 described in Table 1 are listed in Table 1 with respect to 100 parts by mass of (A) alkali-soluble resin (P-1, P-2). The indicated amount of (B) naphthoquinonediazide compound (Q-1) and (C) salicylic acid oligomer (S-1 to S-12) are appropriately dissolved in 170 to 220 parts by mass of GBL, and then filtered through a 0.2 μm filter. Prepared. In addition, R2 in Formula (1) was a hydrogen atom in all examples.

  The sensitivity and the cured residual film rate of the prepared positive photosensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 5 were evaluated. The results are shown in Table 2 below.

[Examples 14 to 17, Comparative Examples 6 and 7]
The photosensitive resin compositions of Examples 14 to 17 and Comparative Examples 6 and 7 described in Table 3 are (A) alkali-soluble resin (N-1, N-2, phenol resin (trade name: EP4000B m-cresol / p-cresol ratio = 60/40, manufactured by Asahi Organic Materials Co., Ltd.), polyhydroxystyrene (trade name: Marcalinker Maruzen Petrochemical Co., Ltd.) 100 parts by mass (B) in the amount shown in Table 3 The naphthoquinonediazide compound (Q-1) and (C) salicylic acid oligomer (S-1) were appropriately dissolved in 170 to 220 parts by mass of GBL and then filtered through a 0.2 μm filter.

  The sensitivity of the prepared positive photosensitive resin compositions of Examples 14 to 17 and Comparative Examples 6 and 7 and the cured residual film ratio were evaluated. The results are shown in Table 4 below.

[Examples 18 to 20, Comparative Examples 8 and 9]
The photosensitive resin compositions of Examples 18 to 20 and Comparative Examples 8 and 9 described in Table 5 are (A) 100 parts by mass of an alkali-soluble resin (P-1, P-2, N-1, N-2). The amount of (B) naphthoquinonediazide compound (Q-1) and (C) salicylic acid oligomer (S-1) shown in Table 5 were appropriately dissolved in 170 to 220 parts by mass of GBL, and then 0.2 μm filter. And filtered.

  The sensitivity, the cured residual film rate, and the post-curing pattern cross-sectional shape of the prepared positive type photosensitive resin compositions of Examples 18 to 20 and Comparative Examples 8 and 9 were evaluated. The results are shown in Table 6 below.

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

Claims (7)

(A) 100 parts by mass of an alkali-soluble resin;
(B) 1-50 parts by mass of a photoacid generator; and (C) the following general formula (1):

(Wherein R ₁ and R ₂ each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms; and the average value of n is 0 or more and 5.0 or less, n When the average value of is 0, R ₁ and R ₂ are not simultaneously hydrogen atoms)
A positive photosensitive resin composition comprising 0.1 to 10 parts by mass of a salicylic acid oligomer represented by the formula:   2. The positive photosensitive resin composition according to claim 1, wherein the average value of n is 0.2 or more and 4.0 or less. The positive photosensitive resin composition according to claim 1 or 2, wherein an average value of n in the salicylic acid oligomer or a mixture thereof is 0.2 or more, and R ₁ and R ₂ are all hydrogen atoms. . The (A) alkali-soluble resin is (A-1) a polyimide having a phenolic hydroxyl group, (A-2) a polybenzoxazole precursor , (A-2 ′) an ester group and / or a carboxyl at the ortho position of the amide bond. polyamide having a group, and (a-3) containing at least one selected from the group consisting of phenolic resins, the positive photosensitive resin composition according to any one of claims 1 to 3.   The positive electrode according to any one of claims 1 to 4, wherein the (A) alkali-soluble resin contains a phenol resin in a proportion of 21 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the polybenzoxazole precursor. Type photosensitive resin composition. The (A-3) phenol resin is represented by the following general formula (a) or (b):

(Wherein R ₃ , R ₄ , R ₅ , and R ₆ are each independently a monovalent organic group having 1 to 10 carbon atoms; a and c are 1 or 2; b, d , E and f are each an integer from 0 to 2; m ₁ , m ₂ and m ₃ are each independently 0 or a positive integer; and m ₄ is a positive integer; m ₁ and m ₂ are not 0 at the same time.)
The positive photosensitive resin composition of Claim 4 or 5 which is novolak resin represented by these. (A) forming a photosensitive resin layer on a substrate from the photosensitive resin composition according to any one of claims 1 to 6;
(B) a step of exposing the photosensitive resin layer;
(C) removing the exposed portion of the photosensitive resin layer with a developer to obtain a relief pattern;
(D) heating the relief pattern;
A method for producing a cured relief pattern.