JP2020064325A - Photosensitive resin composition - Google Patents

Abstract

To provide a photosensitive resin composition that can be uniformly applied on the whole surface of a substrate by a spin coating method even in a smaller discharge mass and gives excellent in-plane uniformity of the obtained coating film and a constant film thickness in an edge portion of the substrate.SOLUTION: A photosensitive resin composition for spin coating is provided, which comprises (A) an alkali-soluble resin, (B) a photoacid generator, and (C) a solvent having a vapor pressure of 10 Pa to 250 Pa at 25°C and a density of 0.7 g/cmto 1.02 g/cmat 25°C. The photosensitive resin composition for spin coating has a density of 0.75 g/cmto 1.1 g/cmat 25°C; and the photosensitive resin composition for spin coating has a viscosity of 0.5 Pa s to 2 Pa s at 25°C.SELECTED DRAWING: None

Description

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

  As materials for the surface protective film and the interlayer insulating film of a semiconductor device, an alkaline aqueous solution-soluble hydroxypolyamide that becomes a heat resistant resin after curing, such as polybenzoxazole (hereinafter, also referred to as “PBO”) precursor and photosensitive diazoquinone. A photoacid generator such as a compound is mixed with a solvent such as γ-butyl lactone (hereinafter referred to as “GBL”) to prepare a varnish of the PBO precursor composition, and the PBO precursor composition is mixed with the positive photosensitive resin. The method used as a composition is disclosed in Patent Document 1, for example.

  In the process of manufacturing a semiconductor device, generally, a varnish of the precursor composition is applied to a substrate such as a silicon wafer by a spin coating method, patterned by active light rays, developed, and subjected to thermal polybenzoxazole treatment, etc. By applying the above, it is possible to easily form a surface protective film, an interlayer insulating film, or the like, which will be a part of the semiconductor device.

  In a dynamic random access memory or a NAND flash memory, which is a kind of semiconductor memory, low cost production has been strongly demanded in recent years. Therefore, even in the step of forming the surface protection film of the semiconductor memory, it is strongly required to form a uniform surface protection film at low cost.

  As one of the methods, a method of reducing the amount of the photosensitive resin composition used when applying the photosensitive resin composition onto a substrate is disclosed (Patent Document 2).

  In addition, a photosensitive resin composition that is excellent in film thickness uniformity when forming a thin film or in coverage of a substrate edge portion is exemplified (Patent Document 3).

JP-A-63-096162 JP, 2004-153262, A JP, 2007-86215, A

  However, the method described in Patent Document 2 has a problem that it is difficult to control the film thickness and bubbles easily enter because the rotation speed is extremely high.

  Further, although the photosensitive resin composition described in Patent Document 3 improves the film thickness uniformity at the time of thin film formation or the coverage of the substrate edge portion, there is room for improvement in the discharge mass.

  Therefore, an object of the present invention is that even with a smaller discharge mass, it can be uniformly applied to the entire surface by a spin coating method, and the in-plane uniformity of the coating film is excellent, and the film of the edge portion of the substrate is excellent. It is to provide a photosensitive resin composition having a constant thickness.

In view of the above-mentioned problems of the prior art, the present inventors have made diligent studies, and as a result, a photosensitive resin composition containing an alkali-soluble resin, a photoacid generator, and a specific solvent, wherein the resin The inventors have found that a photosensitive resin composition that solves the above problems can be obtained by adjusting the density and viscosity of the composition at 25 ° C. within a specific range, and have completed the present invention.
That is, the present invention is as follows.

[1] (A) Alkali-soluble resin;
The solvent and (C) vapor at 25 ° C. pressure is 10Pa～250Pa, and density at 25 ° C. is ^{0.7g / cm 3 ~1.02g / cm 3} ; (B) a photoacid generator;
A spin-coating a photosensitive resin composition comprising, density at 25 ° C. of the spin-coating a photosensitive resin composition ^is a ^{0.75g / cm 3 ~1.1g / cm 3} , and the spin-coating The photosensitive resin composition for spin coating, wherein the viscosity of the photosensitive resin composition for spin coating at 25 ° C. is 0.5 Pa · s to 2 Pa · s.

[2] The (C) Density of solvent ^{is 0.8g / cm 3 ~0.95g / cm 3} , a spinning photosensitive resin composition according to [1].

  [3] The photosensitive resin composition for spin coating contains 30% by mass to 100% by mass of the solvent (C) based on the total mass of all the solvents contained in the photosensitive resin composition for spin coating. The photosensitive resin composition for spin coating according to [1] or [2].

  [4] The solvent for spin coating according to any one of [1] to [3], wherein the solvent (C) is at least one selected from the group consisting of ketones, ethers, alcohols and glycols. Resin composition.

｛式中、Ｒ_１及びＲ_２は、それぞれ独立に、炭素原子数１〜９のアルキル基であり、そしてＲ_１とＲ_２の炭素原子数の和が、７〜１０である。｝

｛式中、Ｒ_３及びＲ_４は、それぞれ独立に、炭素原子数１〜１１のアルキル基であり、そしてＲ_３とＲ_４の炭素原子数の和が、９〜１２である。｝

｛式中、Ｒ_５は、炭素原子数５〜１０のアルキル基である。｝

｛式中、Ｒ_６及びＲ_７は、それぞれ独立に、水素原子、炭素原子数１〜５のアルキル基、又は下記一般式（５）：

（式中、Ｒ_９は、炭素原子数１〜５のアルキル基を表す）
で表される基Ｘを表すが、Ｒ_６及びＲ_７の両方が基Ｘになることはなく、Ｒ_８は、水素原子又は炭素数１若しくは２のアルキル基を表し、そしてｎ５は、１≦ｎ５≦３を満たす数である。｝
で表される化合物から成る群から選択される少なくとも１つである、［１］〜［４］のいずれか一項に記載のスピンコート用感光性樹脂組成物。 [5] The solvent (C) has the following general formulas (1) to (4):

{In the formula, R ₁ and R ₂ are each independently an alkyl group having 1 to 9 carbon atoms, and the sum of the carbon atoms of R ₁ and R ₂ is 7 to 10. }

{In the formula, R ₃ and R ₄ are each independently an alkyl group having 1 to 11 carbon atoms, and the sum of the number of carbon atoms of R ₃ and R ₄ is 9 to 12. }

{In the formula, R ₅ is an alkyl group having 5 to 10 carbon atoms. }

{In the formula, R ₆ and R ₇ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or the following general formula (5):

(In the formula, R ₉ represents an alkyl group having 1 to 5 carbon atoms)
Represents a group X represented by, but R ₆ and R ₇ do not become the group X, R ₈ represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and n5 is 1 ≦ It is a number that satisfies n5 ≦ 3. }
The photosensitive resin composition for spin coating according to any one of [1] to [4], which is at least one selected from the group consisting of compounds represented by:

  [6] The solvent (C) is 2-octanone, 2-nonanone, diisobutyl ketone, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether. The photosensitive resin composition for spin coating according to any one of [1] to [5], which is at least one selected from the group consisting of ether, dipropylene glycol dimethyl ether, and dipropylene glycol methylpropyl ether. .

  [7] The (A) alkali-soluble resin is at least one selected from the group consisting of alkali-soluble polyimides, polyimide precursors, polybenzoxazole precursors, and phenolic resins. [1] to [6] The photosensitive resin composition for spin coating according to claim 1.

｛式中、Ｘ_１及びＹ_１は、各々独立に、２〜６０個の炭素原子を有する２〜８価の有機基を表し、Ｒ_１０及びＲ_１１は、各々独立に、水素原子又は炭素原子数１〜１０のアルキル基を表し、ｍ１は、１〜１０００の整数であり、ｎ１〜ｎ４は、それぞれ独立に、０〜４の整数であり、ｎ１及びｎ３は、０≦（ｎ１＋ｎ３）≦６を満たし、ｎ２及びｎ４は、０≦（ｎ２＋ｎ４）≦６を満たし、そしてｎ１〜ｎ４の全てが０になることはない。｝
で表される樹脂及び／又はフェノール樹脂を含む、［１］〜［７］のいずれか一項に記載のスピンコート用感光性樹脂組成物。 [8] The alkali-soluble resin (A) has the following general formula (6):

{In the formula, X ₁ and Y ₁ each independently represent a divalent to octavalent organic group having 2 to 60 carbon atoms, and R ₁₀ and R ₁₁ are each independently a hydrogen atom or a carbon atom. Represents an alkyl group of the numbers 1 to 10, m1 is an integer of 1 to 1000, n1 to n4 are each independently an integer of 0 to 4, and n1 and n3 are 0 ≦ (n1 + n3) ≦ 6. And n2 and n4 satisfy 0 ≦ (n2 + n4) ≦ 6, and all of n1 to n4 are not 0. }
The photosensitive resin composition for spin coating according to any one of [1] to [7], which contains a resin represented by and / or a phenol resin.

  [9] The spin according to [8], wherein the (A) alkali-soluble resin contains 50 parts by mass to 150 parts by mass of a phenol resin with respect to 100 parts by mass of the resin represented by the general formula (6). Photosensitive resin composition for coat.

  [10] The photosensitive resin composition for spin coating according to any one of [1] to [9], wherein the photoacid generator (B) is a quinonediazide compound.

[11] The following:
(A) The photosensitive resin composition for spin coating according to any one of [1] to [10] is spin-coated on a substrate to form a photosensitive resin layer or a photosensitive film on the substrate. Process,
(B) a step of exposing the photosensitive resin layer or the photosensitive film,
A cured relief pattern including (c) a step of removing an exposed part or an unexposed part of the photosensitive resin layer or the photosensitive film with a developer to obtain a relief pattern, and (d) a step of heating the relief pattern. Manufacturing method.

  [12] A cured relief pattern obtained by the method described in [11].

  [13] A semiconductor device comprising a semiconductor element and a cured film provided on the semiconductor element, wherein the cured film is the cured relief pattern according to [12].

  [14] A display device including a display element and a cured film provided on the display element, wherein the cured film is the cured relief pattern according to [12]. apparatus.

  According to the present invention, a photosensitive resin composition having excellent wettability and spreadability at the time of producing a coating film by a spin coating method with a smaller discharge mass and excellent in-plane uniformity of the coating film, and the photosensitive resin composition are provided. Can be provided.

  Hereinafter, exemplary embodiments for carrying out the present invention (hereinafter, abbreviated as “embodiments”) will be described in detail. The present invention is not limited to the embodiments described below, and various modifications can be made within the scope of the invention.

<Photosensitive resin composition>
Each component constituting the photosensitive resin composition of the present invention will be specifically described below.

(A) Alkali-Soluble Resin (A) The alkali-soluble resin used in the present composition is a resin having an acidic functional group such as a phenolic hydroxyl group and a carboxyl group and soluble in an alkaline aqueous solution.

  Specifically, the (A) alkali-soluble resin is (i) a PBO precursor hydroxypolyamide, (ii) a tetracarboxylic acid and a diamine-derived polyamide having a carboxyl group at the ortho position of an amide bond, and (iii) ) Aqueous alkali-soluble polyimide having a phenolic hydroxyl group in the side chain, (iv) phenol resin and its derivative, (v) polyhydroxystyrene and its derivative, (vi) acrylic resin and its derivative, and these resins in the molecule It is a resin having a structure copolymerized with. Further, these resins may be used alone or in combination.

｛式中、Ｘ_１及びＹ_１は、各々独立に、２〜６０個の炭素原子を有する２〜８価の有機基を表し、Ｒ_１０及びＲ_１１は、各々独立に、水素原子又は炭素原子数１〜１０のアルキル基を表し、ｍ１は、１〜１０００の整数であり、ｎ１〜ｎ４は、それぞれ独立に、０〜４の整数であり、ｎ１及びｎ３は、０≦（ｎ１＋ｎ３）≦６を満たし、ｎ２及びｎ４は、０≦（ｎ２＋ｎ４）≦６を満たし、そしてｎ１〜ｎ４の全てが０になることはない。｝
で表される樹脂を主成分とする（ｉ）ＰＢＯ前駆体であるヒドロキシポリアミドが望ましい。
これは、ポリマーが処理後に環構造を有することで、耐熱性及び耐溶剤性が飛躍的に向上し、強靭な膜が得られるためである。 As the alkali-soluble resin (A), a polymer having an imide ring, an oxazole ring, or the like after being heated or treated with a suitable catalyst, represented by the following general formula (6):

{In the formula, X ₁ and Y ₁ each independently represent a divalent to octavalent organic group having 2 to 60 carbon atoms, and R ₁₀ and R ₁₁ are each independently a hydrogen atom or a carbon atom. Represents an alkyl group of the numbers 1 to 10, m1 is an integer of 1 to 1000, n1 to n4 are each independently an integer of 0 to 4, and n1 and n3 are 0 ≦ (n1 + n3) ≦ 6. And n2 and n4 satisfy 0 ≦ (n2 + n4) ≦ 6, and all of n1 to n4 are not 0. }
A hydroxypolyamide, which is (i) a PBO precursor whose main component is a resin represented by
This is because when the polymer has a ring structure after the treatment, heat resistance and solvent resistance are dramatically improved, and a tough film is obtained.

  The resin structure in the alkali-soluble resin represented by the general formula (6) may be one type or two or more types. When two or more kinds of structural units are present, the arrangement of the structural units may be block or random, and the repeating number m1 is the total number of repeating units of the two or more kinds of structural units.

The polyhydroxyamide (i) PBO precursor is described in detail below.
The repeating unit represented by the general formula (6) includes, for example, a dicarboxylic acid having a structure of Y ₁ (OH) _n2 (COOR ₁₁ ) _n4 (COOH) ₂ and X ₁ (NH ₂ ) ₂ (OH) _n1 ( It can be obtained by polycondensing a diamine having a COOR ₁₀ ) _n3 structure, for example, bisaminophenol.
Since the two groups of amino group and hydroxy group of the bisaminophenol are in the ortho positions with respect to each other, the polyhydroxyamide is ring-closed by being heated to about 280 ° C to 400 ° C to form PBO which is a heat resistant resin. Change. m ₁ is preferably in the range of ₁ to 1000, more preferably in the range of 1 to 300, further preferably in the range of 3 to 50, and most preferably in the range of 3 to 30.

Examples of the diamine having the X ₁ (NH ₂ ) ₂ (OH) _n1 (COOR ₁₀ ) _n3 structure include bisaminophenol compounds, and specifically, 3,3′-dihydroxybenzidine and 3,3 ′. -Diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3 , 3'-dihydroxydiphenyl sulfone, 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-amino-3-hydroxyphenyl) propane, 4,4′-diamino-3,3′-dihydroxybenzophenone, 3,3′- Diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5- Examples thereof include dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, and 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenol compounds may be used alone or in combination.

Among the diamines having the X ₁ (NH ₂ ) ₂ (OH) _n1 (COOR ₁₀ ) _n3 structure, particularly preferable one is the case where X ₁ is an organic group selected from the following structures.

（式中、Ｘ₂は、少なくとも２個の炭素原子を有する４価の有機基である。）
上記Ｘ_２は、前述したＸ_１で示される有機基として好ましいものから成る群から選択される少なくとも１つの有機基であることが好ましい。 Further, as a diamine having an X ₁ (NH ₂ ) ₂ (OH) _n1 (COOR ₁₀ ) _n3 structure, two sets of diamines having an amide bond and a phenolic hydroxyl group at the ortho positions in the molecule (hereinafter, referred to as “intramolecular”). It is also possible to use a diamine having a PBO precursor structure. For example, there may be mentioned a diamine represented by the following general formula, which is obtained by reacting the above-mentioned bisaminophenol with 2 molecules of nitrobenzoic acid and subsequently reducing the same.

(In the formula, X ₂ is a tetravalent organic group having at least 2 carbon atoms.)
It is preferable that X ₂ is at least one organic group selected from the group consisting of preferable organic groups represented by X ₁ .

｛式中、Ｙ_２は、少なくとも２個の炭素原子を有する２価の有機基である。｝
上記Ｙ_２は、後述するＹ_１で示される有機基として好ましいものから成る群から選択される少なくとも１つの有機基であることが好ましい。 As another method for obtaining a diamine having a PBO precursor structure in the molecule, a dicarboxylic acid dichloride having a structure of Y ₂ (COCl) ₂ is reacted with two molecules of nitroaminophenol to reduce the dicarboxylic acid dichloride, and the diamine is represented by the following structure. There is also a method to obtain the diamine.

{In the formula, Y ₂ is a divalent organic group having at least 2 carbon atoms. }
It is preferable that Y ₂ is at least one organic group selected from the group consisting of preferable organic groups represented by Y ₁ described later.

｛式中、Ｙ_３は、少なくとも４個の炭素原子を有する４価の有機基であり、そしてＲ_１２は、炭素原子数１〜１０の炭化水素基を表す。｝ Further, as a bisaminophenol having an X ₁ (NH ₂ ) ₂ (OH) _n1 (COOR ₁₀ ) _n3 structure, a diamine having two sets of polyimide precursor structures in a molecule (hereinafter, referred to as “PI precursor structure in a molecule”). It is also possible to use "bisaminophenol" having a. As a method for obtaining such a bisaminophenol compound, for example, a dicarboxylic acid obtained by ring-opening a tetracarboxylic dianhydride with a monoalcohol, a monoamine, or the like, and an aniline having a hydroxy group and a nitro group at the ortho positions with respect to each other are used. There is also a method in which two molecules are condensed and then the nitro group is reduced to obtain bisaminophenol represented by the following general formula.

{In the formula, Y ₃ is a tetravalent organic group having at least 4 carbon atoms, and R ₁₂ represents a hydrocarbon group having 1 to 10 carbon atoms. }

For the resin represented by the general formula (6), as the diamine, a diamine having no phenolic hydroxyl group is used in addition to the diamine having the X ₁ (NH ₂ ) ₂ (OH) _n1 (COOR ₁₀ ) _n3 structure. You can also Examples of such diamines include aromatic diamines, aliphatic diamines, and silicon diamines.

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

  As the aliphatic diamine, for example, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1 , Linear aliphatic diamines such as 12-dodecanediamine; 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, Branched-chain aliphatic diamines such as 2,4,4-trimethyl-1,6-hexanediamine, 2-methyl-1,8-octanediamine, 5-methyl-1,9-nonanediamine; cyclohexanediamine, methylcyclohexanediamine , Isophoronediamine, bis (4-aminocyclohexyl) methane, norbornanedimethylamine, trisic Examples thereof include alicyclic diamines such as rodecan dimethylamine.

  Examples of the silicon diamine include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (4-aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetramethyldisiloxane. Examples thereof include siloxane, 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane and bis (γ-aminopropyl) tetraphenyldisiloxane.

｛式中、Ａ₁は、−ＣＨ₂−、−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＣＯ−、−ＮＨＣＯ−及び−Ｃ（ＣＦ_３）₂−から成る群から選択される少なくとも１つの２価の基又は単結合であり、ｍ₂は、１〜３０の整数であり、Ｌ₁は、それぞれ独立に、炭素数１〜４のアルキル基、不飽和基、及びハロゲン原子から成る群から選択される少なくとも１つの基であり、ｊは、それぞれ独立に、０〜４の整数であり、ｋは、０又は１の整数であり、そしてｌは、０〜２の整数である。｝ As the dicarboxylic acid having a Y ₁ (OH) _n2 (COOR ₁₁ ) _n4 (COOH) ₂ structure, an aromatic group, an alicyclic group, or an aliphatic group in which Y ₁ is selected from the structures represented by the following formulas The dicarboxylic acid which is

{In the formula, A ₁ is at least selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO— and —C (CF ₃ ) ₂ —. It is one divalent group or a single bond, m ₂ is an integer of 1 to 30, and L ₁ is independently an alkyl group having 1 to 4 carbon atoms, an unsaturated group, and a halogen atom. Is at least one group selected from the group, j is each independently an integer from 0 to 4, k is an integer from 0 or 1, and 1 is an integer from 0 to 2. }

  Examples of the aromatic dicarboxylic acid include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 4,4′-dicarboxyl Biphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, 5-tert-butylisophthale Acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid and the like can be mentioned.

  Examples of the alicyclic dicarboxylic acid include 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid and the like.

  Examples of the aliphatic dicarboxylic acid include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid and 2,2-dimethylsuccinic acid. Citric acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3- Dimethyl glutaric acid, 3-ethyl-3-methyl glutaric acid, adipic acid, octafluoroadipic acid, 3-methyl adipic acid, pimelic acid, 2,2,6,6-tetramethyl pimelic acid, suberic acid, dodecafluoro Suberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dode Acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanoic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid. Examples thereof include acids, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, and diglycolic acid.

Further, a derivative of 5-aminoisophthalic acid can be used as a part or all of the dicarboxylic acid having the Y ₁ (OH) _n2 (COOR ₁₁ ) _n4 (COOH) ₂ structure.
Specific compounds to be reacted with 5-aminoisophthalic acid to obtain the derivative include 5-norbornene-2,3-dicarboxylic acid anhydride and exo-3,6-epoxy-1,2,3,3. 6-tetrahydrophthalic anhydride, 3-ethynyl-1,2-phthalic anhydride, 4-ethynyl-1,2-phthalic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, 1 -Cyclohexene-1,2-dicarboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, allylsuccinic anhydride , Isocyanatoethyl methacrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate , 3-cyclohexene-1-carboxylic acid chloride, 2-furancarboxylic acid chloride, crotonic acid chloride, cinnamic acid chloride, methacrylic acid chloride, acrylic acid chloride, propioric acid chloride, tetrolic acid chloride, thiophene-2-acetyl chloride, p-styrenesulfonyl chloride, glycidyl methacrylate, allyl glycidyl ether, chloroformic acid methyl ester, chloroformic acid ethyl ester, chloroformic acid n-propyl ester, chloroformic acid isopropyl ester, chloroformic acid isobutyl ester, chloroformic acid 2- Ethoxy ester, chloroformic acid-sec-butyl ester, chloroformic acid benzyl ester, chloroformic acid 2-ethylhexyl ester, chloroformic acid allyl ester, chloroformic acid phenyl ester, chloroformic acid 2,2,2-Trichloroethyl ester, chloroformic acid-2-butoxyethyl ester, chloroformic acid-p-nitrobenzyl ester, chloroformic acid-p-methoxybenzyl ester, chloroformic acid isobornylbenzyl ester, chloro Formic acid-p-biphenylisopropylbenzyl ester, 2-t-butyloxycarbonyl-oximino-2-phenylacetonitrile, S-t-butyloxycarbonyl-4,6-dimethyl-thiopyrimidine, di-t-butyl-dicarbonate, N-ethoxycarbonylphthalimide, ethyldithiocarbonyl chloride, formic acid chloride, benzoyl chloride, p-toluenesulfonic acid chloride, methanesulfonic acid chloride, acetyl chloride, trityl chloride, trimethylchlorosilane, hexamethyldisilaza , N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (dimethylamino) trimethylsilane, trimethylsilyldiphenylurea, bis (trimethylsilyl) urea, phenyl isocyanate , N-butyl isocyanate, n-octadecyl isocyanate, o-tolyl isocyanate, 1,2-phthalic anhydride, and cis-1,2-cyclohexanedicarboxylic anhydride, and glutaric anhydride.

｛式中、Ｂは、−ＣＨ₂−、−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＣＯ−、−ＮＨＣＯ−、及び−Ｃ（ＣＦ_３）₂−、−ＣＯＯ−から成る群から選択される少なくとも１つの２価の基を表す。｝ Furthermore, as the dicarboxylic acid having a Y ₁ (OH) _n2 (COOR ₁₁ ) _n4 (COOH) ₂ structure, a dicarboxylic acid obtained by ring-opening tetracarboxylic dianhydride with a monoalcohol, a monoamine, or the like can 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 above tetracarboxylic acid dianhydride include compounds represented by the following chemical formulas.

{Wherein, B _{is, -CH 2 -, - O -} , - S -, - SO 2 -, - CO -, - NHCO-, and _{-C (CF 3) 2 -,} - from the group consisting of COO- Represents at least one divalent group selected. }

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

｛式中、Ｘ_３は、前述のＸ_１（ＯＨ）₂（ＮＨ−）₂で表される２価の有機基を表す。｝ Further, by reacting bisaminophenol with trimellitic acid chloride to produce tetracarboxylic acid dianhydride, and ring-opening in the same manner as the above tetracarboxylic acid dianhydride to be used as a dicarboxylic acid. You can also Examples of the tetracarboxylic dianhydride thus obtained include the chemical formulas shown below.

{In the formula, X ₃ represents a divalent organic group represented by X ₁ (OH) ₂ (NH-) ₂ described above. }

  As a method of polycondensation of the dicarboxylic acid and the bisaminophenol compound or diamine for synthesizing the polyhydroxyamide, dicarboxylic acid and thionyl chloride are used to form a dicarboxylic acid chloride, and then bisaminophenol or diamine is allowed to act on the polycarboxylic acid. And a method of polycondensing dicarboxylic acid and bisaminophenol or diamine with dicyclohexylcarbodiimide. In the method using dicyclohexylcarbodiimide, hydroxybenztriazole can be simultaneously acted on.

  In the polyhydroxyamide having the repeating unit represented by the general formula (6), it is also preferable to use the terminal group after being capped with an organic group (hereinafter referred to as “capping group”).

  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, norbornene amine, butyl amine, propargyl amine, ethanol, propargyl alcohol, benzyl alcohol, hydroxyethyl methacrylate and hydroxyethyl acrylate.

  On the contrary, 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 sealing group is an acid anhydride, a carboxylic acid, an acid chloride, or It is preferable to use a compound having an isocyanate group or the like. Examples of the compound include benzoyl chloride, norbornene dicarboxylic acid anhydride, norbornene carboxylic acid, ethynyl phthalic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic acid anhydride, methylcyclohexanedicarboxylic acid anhydride. Compounds, cyclohexenedicarboxylic acid anhydride, methacryloyloxyethyl methacrylate, phenyl isocyanate, mesyl chloride, and tosylic acid chloride.

｛式中、Ｌ_２は、−ＣＨ₂−、−Ｏ−又は−Ｓ−を表し、そしてＬ_３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, a preferable terminal group has the following structure:

{In the formula, L ₂ represents —CH ₂ —, —O— or —S—, and L ₃ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms. Represents }
And a group represented by.

  (Ii) Polyamides derived from tetracarboxylic acid dianhydride and diamine and having a carboxyl group at the ortho position of the amide bond include the above-mentioned tetracarboxylic acid dianhydride and the above-mentioned diamine having no phenolic hydroxyl group. -Obtained by condensation reaction in a polar organic solvent such as butyrolactone, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, tetramethylurea, or sulfolane, if necessary, using a catalyst such as pyridine or triethylamine. .

  The average weight molecular weight of the polyamide is preferably in the range of 8000 to 70,000. As a method of adjusting the molecular weight, a method of controlling by changing the molar ratio of the charges of tetracarboxylic acid and diamine can be used. A method in which a carboxylic acid terminal is obtained by charging more tetracarboxylic acid than diamine is preferable in terms of storage stability at room temperature. It is also possible to charge more diamine than tetracarboxylic acid and then to seal the end group with a compound having an acid anhydride, a carboxylic acid, an acid chloride, an isocyanate group or the like.

  The polyamide resin containing a solvent obtained in the above reaction can be used as a resin composition as it is, or, without using the polycondensate solution produced as it is, a polycondensate through a purification step. May be used after being isolated and redissolved in an appropriate solvent again. As a specific purification step, first, a polycondensate is precipitated by adding a poor solvent such as methanol, ethanol, isopropanol, or water to the polycondensate solution obtained by the above production method. Next, it is dissolved again in a good solvent such as γ-butyrolactone or N-methylpyrrolidone, and the solution is passed through a column filled with an ion exchange resin to remove ionic impurities. Finally, the solution is dropped into pure water, the precipitate is filtered off, and vacuum drying is performed. As a result, low molecular weight components, ionic impurities, etc. can be removed.

(Iii) An alkali aqueous solution-soluble polyimide having a phenolic hydroxyl group in the side chain is prepared by combining the tetracarboxylic acid anhydride and the diamine having the X ₁ (NH ₂ ) ₂ (OH) _n1 (COOR ₁₀ ) _n3 structure with γ -In a polar organic solvent such as butyrolactone, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, tetramethylurea, and sulfolane, if necessary, a condensation reaction is performed using a catalyst such as pyridine or triethylamine to give a polyimide precursor. It is obtained by dehydrating and ring-closing the polyimide precursor by subsequently heating in the presence of a catalyst such as pyridine and acetic anhydride or in the absence of a catalyst.
The average weight molecular weight of the polyimide resin is preferably in the range of 5,000 to 70,000. As a method of adjusting the molecular weight, a method of controlling by changing the charged molar ratio of tetracarboxylic acid and diamine can be used. A method in which the tetracarboxylic acid is charged in a larger amount than the diamine so that the carboxylic acid is terminated is preferable in terms of storage stability at room temperature. It is also possible to charge more diamine than the acid anhydride and seal the end group with a compound having an acid anhydride, a carboxylic acid, an acid chloride, an isocyanate group or the like.
The solvent-containing polyamide resin obtained by the above reaction may be used as a resin composition as it is, or may be subjected to the purification step as described above.

As the (A) alkali-soluble resin, (iv) phenol resin and its derivative are also preferably used.
When a phenol resin is used as the alkali-soluble resin (A), the unexposed portion has a dissolution-inhibiting effect, while the exposed portion has a dissolution-promoting effect, because the (B) photo-acid generator has a high affinity. A high-sensitivity, high-resolution photosensitive resin composition is obtained by generating high contrast.
When the photosensitive resin composition is spin-coated on a metal, exposed, developed, and cured, and then subjected to an etching treatment using a fluorine-based compound gas, the fluorine-based compound gas used for the etching is a phenol resin during the etching treatment. Since it hardly penetrates into the cured film, the corrosion due to the fluorine compound is less likely to occur on the metal.
Further, since the phenol resin has a high affinity for the organic solvent and a high solubility, the in-plane uniformity is excellent and the film thickness of the edge portion of the substrate tends to be uniform when spin-coated.

  The above-mentioned effects are derived not only when the phenol resin alone is used as the alkali-soluble resin, but also from the phenol resin, the above-mentioned (i) PBO precursor polyhydroxyamide, (ii) tetracarboxylic acid and diamine, It also appears when a polyamide having a carboxyl group at the ortho position of the amide bond and (iii) a polyimide soluble in an alkaline aqueous solution having a phenolic hydroxyl group in the side chain are mixed.

  When 100 parts by mass of the polymer of (i) to (iii) above is mixed with 10 parts by mass to 300 parts by mass, preferably 50 parts by mass to 150 parts by mass of a phenol resin, high sensitivity to an electron beam is obtained. Therefore, the amount is preferably 300 parts by mass or less from the viewpoint of heat resistance.

  As a method for synthesizing a phenol resin, a method of polycondensing one of various phenol compounds or an arbitrary mixture thereof with an aldehyde such as formalin by a known method, or a phenol compound, a methylol group, an alkoxymethyl group and Examples thereof include a method of synthesizing a compound having two haloalkyl groups in the molecule by a polymerization reaction under an acid catalyst, or a method of synthesizing a combination thereof.

  As the phenols, for example, phenol, orthocresol, metacresol, paracresol, 2,3-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,4- Dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, 2-t-butylphenol, 3-t-butylphenol, 4-t-butylphenol, 2-methylresorcinol , 4-methylresorcinol, 5-methylresorcinol, 4-t-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-isopropylphenol, 2- Met Shi-5-methylphenol, 2-t-butyl-5-methylphenol, thymol, and the like Isochimoru. These can be used alone or in combination of two or more.

  Examples of aldehydes include formaldehyde, formalin, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropionaldehyde, β-phenylpropionaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p- Examples thereof include hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde and terephthalaldehyde. To be

  Examples of ketones include acetone, methyl ethyl ketone, diethyl ketone, diphenyl ketone, and the like. 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-t-butylphenol, 2,6-bis (methoxymethyl) -4-methoxyphenol 2,6-bis (methoxymethyl) -4-ethoxyphenol, 2,6-bis (methoxymethyl) -4-propoxyphenol, 2,6-bis (methoxymethyl) -4-n-butoxyphenol, 2, 6-bis (methoxymethyl) -4-t-butoxyphenol, bis (methoxymethyl) biphenyl and the like can be mentioned. From the viewpoint of reaction activity, the alkoxymethyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 2 carbon atoms, and most preferably 1.

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

  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. In the present specification, the weight average molecular weight is a value obtained by gel permeation chromatography (GPC) in terms of standard polystyrene.

  (V) The polyhydroxystyrene resin and its derivative will be described in detail. Specific examples of the polyhydroxystyrene resin and its derivative include, for example, poly-o-hydroxystyrene, poly-m-hydroxystyrene, poly-p-hydroxystyrene, poly-α-methyl-o-hydroxystyrene, poly-α. -Methyl-m-hydroxystyrene, poly-α-methyl-p-hydroxystyrene, or their partially acetylated products, silylated products and the like. The mass average molecular weight of these polyhydroxystyrene resins or their derivatives is usually in the range of 3,000 to 100,000, particularly preferably 4,000 to 20,000.

  (Iv) As the acrylic resin and its derivative, for example, acrylic acid, methacrylic acid, maleic acid, and their derivatives, which are monomers having an alkali-soluble group, are added in the presence of an anionic polymerization initiator or a cationic polymerization initiator. An acrylic resin obtained by polymerization can be used. In addition, a monomer having an alkali-soluble group and an alkali-insoluble acrylic acid ester, methacrylic acid ester, maleic acid ester, styrene, vinyl alcohol, vinyl acetate, vinyl ester, or a derivative thereof, etc. in a range having alkali water solubility May be copolymerized. The weight average molecular weight of the acrylic resin or its derivative is usually 3,000 to 100,000, and particularly preferably 4,000 to 20,000.

(B) Photo-acid generator As the photo-acid generator (B) contained in the photosensitive resin composition of the present invention, it is possible to apply the photosensitive resin composition in a positive type or a negative type to desired applications. The compound which does can be utilized. When the photosensitive resin composition is used as a positive type, as the photoacid generator (B), for example, a quinonediazide compound, an onium salt, a halogen-containing compound and the like can be used, but the solubility and storage stability in a solvent are stable. From the viewpoint of sex, a quinonediazide compound is preferable.

  Examples of the onium salts include iodonium salts, sulfonium salts, phosphonium salts, ammonium salts, diazonium salts, and the like, and onium salts selected from the group consisting of diaryl iodonium salts, triarylsulfonium salts, and trialkylsulfonium salts. Is preferred.

  Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds, and trichloromethyltriazine is preferable from the viewpoint of high sensitivity.

  The quinonediazide compound is preferably a naphthoquinonediazide compound (hereinafter also referred to as “NQD compound”), and among them, a compound having a 1,2-naphthoquinonediazide structure is preferable. The naphthoquinonediazide structure is a 1,2-naphthoquinonediazide-4-sulfonic acid ester of a polyhydroxy compound having a specific structure described in detail below, and a 1,2-naphthoquinonediazide-5-sulfonic acid ester of the polyhydroxy compound. Is at least one NQD compound selected from the group consisting of:

  The NQD compound is obtained by a conventional method by converting a naphthoquinonediazide sulfonic acid compound into a sulfonyl chloride with chlorosulfonic acid or thionyl chloride, and subjecting the obtained naphthoquinone diazide sulfonyl chloride to a condensation reaction with 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, triethylamine or the like. 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、又は下記式群のいずれかで表されるナフトキノンジアジドスルホン酸エステル基であるが、全てのＱが水素原子であることはない。｝

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

{In the formula, Q is a hydrogen atom or a naphthoquinonediazide sulfonic acid ester group represented by any of the following formula groups, but not all Q is a hydrogen atom. }

  Further, as the NQD compound, a naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule can be used, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound can be used. It can also be used as a mixture with a quinonediazide sulfonyl ester compound.

  When used as a positive photosensitive resin composition, the compounding amount of (B) the photo-acid generator with respect to the total of (A) the alkali-soluble resin is 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the total alkali-soluble resin. Is preferred and 5 parts by mass to 30 parts by mass is more preferred. (B) When the compounding amount of the photo-acid generator is 1 part by mass or more, the patterning property of the resin is good, while when it is 50 parts by mass or less, the tensile elongation of the cured film is good. In addition, the development residue (scum) in the exposed area is small, which is preferable.

  The photosensitive resin composition of the present invention is used as a negative photosensitive resin composition by combining the photoacid generator (B) of the following a) to ke) and the crosslinking agent (D) described below. Available. In that case, the following compounds are mentioned as (B) photo-acid generator.

A) Trichloromethyl-s-triazines Tris (2,4,6-trichloromethyl) -s-triazine, 2-phenyl-bis (4,6-trichloromethyl) -s-triazine, 2- (3-chlorophenyl) -Bis (4,6-trichloromethyl) -s-triazine, 2- (2-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -bis (4. 6-trichloromethyl) -s-triazine, 2- (3-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxyphenyl) -bis (4,6-trichloromethyl) ) -S-Triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methylthiophenyl) Bis (4,6-trichloromethyl-s-triazine, 2- (2-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -bis (4,6 -Trichloromethyl) -s-triazine, 2- (3-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxynaphthyl) -bis (4,6-trichloromethyl) -S-triazine, 2- (3,4,5-trimethoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methylthio-β-styryl) -bis (4 , 6-Trichloromethyl) -s-triazine, 2- (3-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methylthio-β Styryl) - bis (4,6-trichloromethyl) -s-triazine.

A) Diaryliodoniums Diphenyliodonium tetrafluoroborate, diphenyliodonium tetrafluorophosphate, diphenyliodonium tetrafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, 4-methoxyphenyl Phenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, 4- Met Xyphenylphenyl iodonium-p-toluene sulfonate, bis (4-ter-butylphenyl) iodonium tetrafluoroborate, bis (4-ter-butylphenyl) iodonium hexafluoroarsenate, bis (4-ter-butylphenyl) iodonium Trifluoromethanesulfonate, bis (4-ter-butylphenyl) iodonium trifluoroacetate, bis (4-ter-butylphenyl) iodonium-p-toluenesulfonate and the like.

C) Triarylsulfonium salts Triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfo Nato, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenylsulfonium trinate Fluoroacetate, 4- Methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoroarsenate, 4-phenylthiophenyldiphenyltrifluoromethane Sulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate, 4-phenylthiophenyldiphenyl-p-toluenesulfonate and the like.

  Among these compounds, trichloromethyl-S-triazines include 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -S-triazine and 2- (4-chlorophenyl) -bis (4. 6-trichloromethyl) -S-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -S-triazine, 2- (4-methoxy-β-styryl) -bis (4,6 -Trichloromethyl) -S-triazine, 2- (4-methoxynaphthyl) -bis (4,6-trichloromethyl) -S-triazine and the like, and diaryliodonium salts include diphenyliodonium trifluoroacetate and diphenyliodonium trifluoromethane. Sulfonate, 4-methoxyphenylphenyliodonium trifluoromethane For example, trifonate, 4-methoxyphenylphenyliodonium trifluoroacetate, and triarylsulfonium salts include triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, and 4-methoxyphenyldiphenyl. Suitable examples include sulfonium trifluoroacetate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate, and the like.

D) Diazoketone compound Examples of the diazoketone compound include 1,3-diketo-2-diazo compounds, diazobenzoquinone compounds, diazonaphthoquinone compounds, and the like, and specific examples include 1,2-naphthoquinonediazide-4 of phenols. -Sulfonic acid ester compounds may be mentioned.

E) Sulfone compound Examples of the sulfone compound include β-ketosulfone compounds, β-sulfonylsulfone compounds and α-diazo compounds of these compounds, and specific examples include 4-trisphenacylsulfone and mesitylphenacyl. Examples thereof include sulfone and bis (phenacylsulfonyl) methane.

F) Sulfonic acid compounds Examples of sulfonic acid compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, imino sulfonates and the like. Preferred specific examples include benzoin tosylate, pyrogallol tristrifluoromethanesulfonate, o-nitrobenzyl trifluoromethanesulfonate, o-nitrobenzyl p-toluenesulfonate and the like.

G) Sulfonimide compound Specific examples of the sulfonimide compound include, for example, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N Examples thereof include-(trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide and N- (trifluoromethylsulfonyloxy) naphthylimide.

Oxime ester compound 2- [2- (4-methylphenylsulfonyloxyimino)]-2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (trade name "Ciba Specialty Chemicals" Irgacure PAG121 "), [2- (propylsulfonyloxyimino) -2,3-dihydrothiophen-3-ylidene] -2- (2-methylphenyl) acetonitrile (trade name" Irgacure PAG103 ", Ciba Specialty Chemicals, Inc.), [ 2- (n-octanesulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (Ciba Specialty Chemicals, Inc., trade name “Irgacure PAG108”), α- (n- Octanesulfonyl Oki Imino) -4-methoxybenzyl cyanide (Ciba Specialty Chemicals tradename "CGI725"), and the like.

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

  Above all, from the viewpoint of sensitivity, the above-mentioned oxime ester compound group is particularly preferable.

  When (B) the photo-acid generator is combined with (D) a cross-linking agent described below to form a negative photosensitive resin composition, the compounding amount of the (B) photo-acid generator is 100% by weight of all alkali-soluble resin. It is 0.1 to 100 parts by mass with respect to parts. When the blending amount is 0.1 parts by mass or more, the effect of improving the sensitivity can be sufficiently obtained, and when the blending amount is 100 parts by mass or less, the mechanical properties after curing are good. The blending amount is preferably 1 to 40 parts by mass.

(C) a 10Pa~250Pa vapor pressure at 25 ° C., and in the embodiment of the density solvent present invention is 0.7g ^/ cm ³ ~1.02g ^/ cm 3 at 25 ℃, (A) an alkali-soluble When a resin and (B) a photo-acid generator are dissolved in a solvent to form a varnish and used as a photosensitive resin composition for spin coating, (C) the vapor pressure at 25 ° C. is 10 Pa to 250 Pa and the density is 0. 0.7 to 1.02 g / cm ³ of solvent is used.

If the density is a photosensitive resin composition containing a solvent of ^{0.7g / cm 3 ~1.02g / cm 3} , are widely used in the photosensitive resin composition γ--butyrolactone (density 1.13 g / cm The density of the photosensitive resin composition is smaller than that of the photosensitive resin composition composed of ³ ). In a photosensitive resin composition having a high density and a photosensitive resin composition having a low density, when a varnish of the same mass is discharged onto the substrate to be spin-coated, the volume of the varnish becomes larger in the photosensitive resin composition having a lower density. The present inventors have found that a wider area can be coated.
That is, when a silicon wafer or the like having a fixed area on the substrate is applied, if a photosensitive resin composition having a low density is used, the mass of the varnish required for coating the entire surface is reduced.

  Furthermore, by using a solvent having a vapor pressure of 10 Pa to 250 Pa at 25 ° C., the uniformity of the coating film is dramatically improved. When a solvent having a vapor pressure of 10 Pa or more is used, the solvent component is sufficiently volatilized during prebaking, so the solvent is removed from the film after prebaking, and the effect of uneven temperature on the hot plate used during prebaking or exhaust unevenness is small. The film thickness uniformity of the coating film after prebaking becomes good. When a solvent having a vapor pressure of 10 Pa or higher is used, the film thickness of the edge portion of the substrate becomes uniform after coating. On the other hand, when a solvent having a vapor pressure of 250 Pa or less is used, the solvent components are less likely to volatilize excessively during spin coating, so that the uniformity of the film thickness is improved.

(C) a pressure at 25 ° C. is 10Pa～250Pa, and as the solvent density at 25 ° C. is ^{0.7g / cm 3 ~1.02g / cm 3} , specifically, (A) an alkali-soluble resin From the viewpoint of solubility or density with respect to, a ketone type, an ether type, an alcohol type, and a glycol type are preferable.

｛式中、Ｒ_１及びＲ_２は、それぞれ独立に、炭素原子数１〜９のアルキル基であり、そしてＲ_１とＲ_２の炭素原子数の和が、７〜１０である。｝ The ketone solvent preferably has a structure represented by the following general formula (1).

{In the formula, R ₁ and R ₂ are each independently an alkyl group having 1 to 9 carbon atoms, and the sum of the carbon atoms of R ₁ and R ₂ is 7 to 10. }

  Specific examples of the ketone solvent include diisobutyl ketone, 5-methyl-3-heptanone, 2-methyl-3-heptanone, 6-methyl-2-heptanone, 2-methyl-4-heptanone and 3-methyl-. 4-heptanone, 2-octanone, 3-octanone, 4-octanone, 5-methyl-2-octanone, 2-nonanone, 3-nonanone, 4-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4- Examples thereof include decanone, 5-decanone, propiophenone, 1-phenylacetone, 3,3-dimethylpentane-4,4-dione and cyclooctanone.

  Among these, diisobutyl ketone, 2-octanone, 2-nonanone, and 2-decanone have excellent in-plane uniformity of the coating film, and the density of the photosensitive resin composition is lowered, so that the coating film is prepared by the spin coating method. Is preferable, and 2-octanone or 2-nonanone is most preferable.

｛式中、Ｒ_３及びＲ_４は、それぞれ独立に、炭素原子数１〜１１のアルキル基であり、そしてＲ_３とＲ_４の炭素原子数の和が、９〜１２である。｝ The ether solvent preferably has a structure represented by the following general formula (2).

{In the formula, R ₃ and R ₄ are each independently an alkyl group having 1 to 11 carbon atoms, and the sum of the number of carbon atoms of R ₃ and R ₄ is 9 to 12. }

  Specific examples of the ether solvent include amyl ether, isoamyl ether, 1-ethoxyheptane, 1-propoxyheptane, 1-butoxyheptane, 1-propoxyheptane, 1-methoxyoctane, 1-ethoxyoctane, 1-propoxy. Octane, 1-butoxyoctane, 1-methoxynonane, 1-ethoxynonane, 1-propoxynonane, benzyl methyl ether, benzyl dimethyl ether and the like can be mentioned.

  Among these, amyl ether, isoamyl ether, 1-methoxyoctane, 1-butoxyoctane is preferable from the viewpoint that the density of the photosensitive resin composition is lowered and the discharge mass at the time of coating film production by the spin coating method can be reduced. Most preferred is ether.

｛式中、Ｒ_５は、炭素原子数５〜１０のアルキル基である。｝ The alcohol-based solvent preferably has a structure represented by the following general formula (3).

{In the formula, R ₅ is an alkyl group having 5 to 10 carbon atoms. }

  Specific examples of the alcohol solvent include 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 1-octanol, 2-octanol, 3-octanol. , 4-octanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, 2-methyl-1-hexanol, 3-methyl-1-hexanol, 4- Methyl-1-hexanol, 5-methyl-1-hexanol, 2-methyl-2-hexanol, 3-methyl-2-hexanol, 4-methyl-2-hexanol, 5-methyl-2-hexanol, 2-ethyl- 1-hexanol, cyclohexanol, cycloheptanol, cyclooctanol and the like can be mentioned. .

  Among these, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, and 2-ethyl-1-hexanol have excellent in-plane uniformity of the coating film, and the density of the photosensitive resin composition decreases. From the viewpoint that the discharge mass at the time of coating film production by the spin coating method can be reduced, 1-heptanol and 2-ethyl-1-hexanol are most preferable.

｛式中、Ｒ_６及びＲ_７は、それぞれ独立に、水素原子、炭素原子数１〜５のアルキル基、又は下記一般式（５）：

（式中、Ｒ_９は、炭素原子数１〜５のアルキル基を表す）
で表される基Ｘを表すが、Ｒ_６及びＲ_７の両方が基Ｘになることはなく、Ｒ_８は、水素原子又は炭素数１若しくは２のアルキル基を表し、そしてｎ５は、１≦ｎ５≦３を満たす数である。｝ As the glycol solvent, the structure represented by the general formula (4) is preferable.

{In the formula, R ₆ and R ₇ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or the following general formula (5):

(In the formula, R ₉ represents an alkyl group having 1 to 5 carbon atoms)
Represents a group X represented by, but R ₆ and R ₇ do not become the group X, R ₈ represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and n5 is 1 ≦ It is a number that satisfies n5 ≦ 3. }

  Specific examples of the glycol solvent include propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoethyl ether. Examples include propyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether acetate, dipropylene glycol dimethyl ether, and dipropylene glycol methyl propyl ether. Among them, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol dimethyl ether, and dipropylene glycol methylpropyl ether are coated. The in-plane uniformity of the film is excellent, the density of the photosensitive resin composition is lowered, and the discharge mass at the time of coating film production by the spin coating method can be reduced, which is preferable, and dipropylene glycol dimethyl ether and dipropylene glycol methyl are used. Propyl ether is most preferred.

In the embodiment, in addition to the (C) solvent, density at 25 ° C. of spin coating the photosensitive resin composition does not exceed the scope of ^{0.75g / cm 3 ~1.1g / cm 3} , and 25 ° C. Within the range where the viscosity in does not exceed 0.5 Pa · s to 2 Pa · s, for example, one or more of the following solvents can be mixed and used.
Examples of such a solvent include N-methyl-2-pyrrolidone, γ-butyrolactone (GBL), N, N-dimethylacetamide (hereinafter, also referred to as “DMAc”), dimethylimidazolinone, tetramethylurea, and dimethyl. Sulfoxide, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, propylene glycol Glycol monomethyl ether acetate.

  Of these solvents, non-amide solvents are preferable because they have little influence on the photosensitizer and the like. Specifically, examples of more preferable solvents include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. From the viewpoint of high solubility in the (A) alkali-soluble resin and prevention of precipitation of the (B) photoacid generator over time, γ-butyrolactone is most preferable when used in combination with the (C) solvent.

In the embodiment, the photosensitive resin composition for spin coating, (C) a 10Pa~250Pa vapor pressure at 25 ° C., and a density at 25 ° C. is at 0.7g ^/ cm ³ ~1.02g ^/ cm 3 It is preferable to use a mixed solvent in which the mass ratio of a solvent to γ-butyl lactone is 95: 5 to 30:70, because the film thickness uniformity of the prebaked film of the photosensitive resin composition for spin coating is improved. Further, the mixed solvent (C) in which the mass ratio of the solvent and γ-butyl lactone is 90:10 to 40:60 is compatible with both the film thickness uniformity of the prebake film and the reduction of the discharge mass at the time of producing the spin coat film. To more preferable.

Density for spin coating the photosensitive resin composition ^{is 0.75g / cm 3 ~1.1g / cm 3} . By setting the density within this range, the ejection mass at the time of producing the spin coat film can be dramatically reduced. More preferably, the range of 0.95g / ^{cm 3} ~1.09g / ^cm 3 is preferred from the viewpoint of the uniformity of the discharge mass reduction and coating film.

  The viscosity of the photosensitive resin composition for spin coating at 25 ° C. is 0.5 Pa · s to 2 Pa · s. By setting the viscosity within this range, the film thickness required for a normal semiconductor protective film (3 μm to 20 μm in the final cured film) can be produced by a spin coating method at an appropriate rotation speed (500 rpm to 5000 rpm). It will be possible. Further, when the viscosity of the photosensitive resin composition for spin coating at 25 ° C. is in the range of 0.6 Pa · s to 1.5 Pa · s, the film thickness can be easily adjusted by the number of rotations at the time of coating. , And more preferable. Regarding the unit of viscosity, it should be understood that 1 [P] is equal to 0.1 [Pa · s] (1P = 0.1 Pa · s).

(D) Crosslinking Agent In the embodiment, when the photosensitive resin composition for spin coating is used in a positive type, it is used in order to increase the chemical resistance of the film (photosensitive resin layer) after thermosetting. When used in a mold, the cross-linking agent (D) can be preferably used for the purpose of enhancing the chemical resistance of the film after thermosetting and for the purpose of pattern formation.

  (D) The crosslinking agent comprises 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 compound selected from the group 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. It is preferable from the viewpoint of chemical resistance after heat curing.

｛式中、Ｒ_１３は、水酸基であり、ｍ_３は、０〜３の整数であり、Ｒ_１４は、炭素数１〜３０の有機基であり、ｍ_４は、０〜３の整数であり、Ｒ_１５は、水素原子又は炭素数１〜８のアルキル基であり、ｍ_５は、１〜６の整数であり、そしてｍ３及びｍ５は、２≦（ｍ３＋ｍ５）≦６を満たす。｝ As the aromatic compound having a methylol group and / or an alkoxymethyl group, those having a structure represented by the following general formula (7) are preferable.

{In the formula, R ₁₃ is a hydroxyl group, m ₃ is an integer of 0 to 3, R ₁₄ is an organic group having 1 to 30 carbon atoms, and m ₄ is an integer of 0 to 3. , R ₁₅ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, m ₅ is an integer of 1 to 6, and m3 and m5 satisfy 2 ≦ (m3 + m5) ≦ 6. }

More specific examples of the aromatic compound having a methylol group and / or an alkoxymethyl group include the following compounds.

  As the compound in which the N-position is substituted with a methylol group and / or an alkoxymethyl group, more specifically, a melamine resin, a benzoguanamine resin, a glycoluril resin, a hydroxyethylene urea resin, a urea resin, a glycol urea resin, an alkoxymethylated melamine Resins, alkoxymethylated benzoguanamine resins, alkoxymethylated glycoluril resins, and alkoxymethylated urea resins can be mentioned.

  Among these, alkoxymethylated melamine resin, alkoxymethylated benzoguanamine resin, alkoxymethylated glycoluril resin, and alkoxymethylated urea resin are known methylolated melamine resin, methylolated benzoguanamine resin, or methylol of methylolated urea resin. It can be obtained by converting a group into an alkoxymethyl group. Examples of the alkoxymethyl group include methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group and the like.

  As the compound in which the N-position is substituted with a methylol group and / or an alkoxymethyl group, specifically, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (manufactured by Mitsui Cytec Co., Ltd.), Nikarac MX-270, -280, -290, Nikarac MS-11, Nikarac MW-30, -100, -300,- 390, -750 (manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.

｛式中、Ｒ_１６及びＲ_１７は、それぞれ独立に、水素原子又は炭素数１〜８のアルキル基であり、そしてＲ_１８は、炭素数１〜３０の有機基である。｝ As the compound in which the N-position is substituted with a methylol group and / or an alkoxymethyl group, those having a structure represented by the following structure are preferable.

{In the formula, R ₁₆ and R ₁₇ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ₁₈ is an organic group having 1 to 30 carbon atoms. }

Further, the above-mentioned resin monomers can also be used as the (D) crosslinking agent, and examples thereof include the following compounds, hexamethoxymethylmelamine, and dimethoxymethylurea.

  The epoxy compound is a compound having a three-membered cyclic ether structure, and specific examples thereof include bisphenol A type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, glycidyl amine type epoxy resin, polysulfide type epoxy resin. Examples thereof include resins, but are not limited thereto.

  The oxetane compound is a compound having a 4-membered cyclic ether structure, and is capable of undergoing a cationic ring-opening polymerization reaction or an addition reaction with a carboxylic acid, thiol, or phenol. Specific examples of the oxetane compound include 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, bis [1-ethyl (3-oxetanyl)] methyl ether, 4,4′-bis. [(3-Ethyl-3-oxetanyl) methoxymethyl] biphenyl, 4,4'-bis (3-ethyl-3-oxetanylmethoxy) biphenyl, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, diethylene glycol bis (3-Ethyl-3-oxetanylmethyl) ether, bis (3-ethyl-3-oxetanylmethyl) diphenoate, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3). -Oxetanylmethyl) ether, poly [ 3-[(3-Ethyl-3-oxetanyl) methoxy] propyl] silasesquioxane] derivative, oxetanyl silicate, phenol novolac oxetane, 1,3-bis [(3-ethyloxetan-3-yl) methoxy] benzene, Examples thereof include OXT121 (Toagosei: Tradename), OXT221 (Toagosei: Tradename), and the like, but are not limited thereto.

  Among these compounds, from the viewpoint of heat resistance, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 4,4′-bis (3-ethyl-3-oxetanylmethoxy) Biphenyl and OXT121 (Toagosei: trade name) are preferred.

  Specific examples of the allyl compound include allyl alcohol, allyl anisole, allyl benzoate, allyl cinnamate, N-allyloxyphthalimide, allylphenol, allylphenyl sulfone, allylurea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate. , Diallyl maleate, diallyl isocyanurate, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallylamine, triallyl 1,3,5-benzenetricarboxylate, triallyl trimellitate (TRIAM705 manufactured by Wako Pure Chemical Industries, Ltd.), pyromellitic Triallyl acid (TRIAM805 manufactured by Wako Pure Chemical Industries, Ltd.), triallyl oxydiphthalate, triallyl phosphate, triallyl phosphite, and triallyl citrate. However, the present invention is not limited to these. From the viewpoint of sensitivity, triallyl trimellitate (TRIAM705 manufactured by Wako Pure Chemical Industries, Ltd.) and triallyl pyromellitic acid (TRIAM805 manufactured by Wako Pure Chemical Industries, Ltd.) are preferable.

  The cross-linking agent (D) may be used alone or in combination of two or more, and the compounding amount thereof may be 1 part by mass to 100 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin. It is more preferably 3 parts by mass to 50 parts by mass. When the blending amount is 1 part by mass or more, crosslinking proceeds satisfactorily and the patterning property becomes good, and when the blending amount is 100 parts by mass or less, the mechanical properties after curing are kept good.

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

  Examples of the carboxylic acid compound include 3-phenyllactic acid, 4-hydroxyphenyllactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid, 2-methoxy-2- ( 1-naphthyl) propionic acid, mandelic acid, atrolactic acid, acetylmandelic acid, α-methoxyphenylacetic acid, 3-phenyllactic acid, 4-hydroxyphenyllactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4 -Hydroxy-3-methoxymandelic acid, 2-methoxy-2- (1-naphthyl) propionic acid, mandelic acid, atrolactic acid, O-acetylmandelic acid, α-methoxyphenylacetic acid, 4-hydroxymandelic acid, 3, 4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid, Mandelic acid, atrolactic acid, O-acetyl mandelic acid, α-methoxyphenylacetic acid, O-acetylmandelic acid, α-methoxyphenylacetic acid, hexyl dihydroxybenzenecarboxylic acid, octyl dihydroxybenzenecarboxylic acid, dodecyl dihydroxybenzenecarboxylic acid, tridecyl Hexyl hydroxybenzenecarboxylate hexyl gallate and hexyl phloroglucinol carboxylate, octyl gallate octyl trihydroxybenzenecarboxylate and octyl phloroglucinol carboxylate, dodecyl gallate tridecylbenzenecarboxylate and dodecyl gallate Dodecyl rogulucinol carboxylate, hexadecyl gallate, which is hexadecyl trihydroxybenzene carboxylate, and hexyl phloroglucinol carboxylate Sadecyl etc. can be mentioned.

  As the phenolic compound, a ballast agent used in the photosensitive diazoquinone compound, and a linear phenol compound such as paracumylphenol, bisphenols, resorcinols, or MtrisPC, MtetraPC (manufactured by Honshu Chemical Industry Co., Ltd .: trade name ), TrisP-HAP, TrisP-PHBA, TrisP-PA and other non-linear phenol compounds (manufactured by Honshu Kagaku Kogyo Co., Ltd .: trade name), compounds in which 2 to 5 hydrogen atoms of the phenyl group of diphenylmethane are substituted with hydroxyl groups, Examples include compounds in which 1 to 5 hydrogen atoms of the phenyl group of 2,2-diphenylpropane are substituted with hydroxyl groups. By adding the phenolic compound, it is possible to improve the adhesiveness of the relief pattern during development and suppress the generation of residues. The ballast agent means a phenol compound used as a raw material for the above-mentioned photosensitive diazoquinone compound, which is a phenol compound in which a part of phenolic hydrogen atoms is naphthoquinone diazide sulfonic acid esterified.

  The addition amount of the (E) dissolution accelerator is preferably 1 part by mass to 50 parts by mass, and more preferably 1 part by mass to 30 parts by mass, relative to 100 parts by mass of the total alkali-soluble resin. When the addition amount is 50 parts by mass or less, the heat resistance of the film after thermosetting is good.

(F) Other Additives In the embodiment, the photosensitive resin composition for spin coating contains, if necessary, a dye, a fragrance, a surfactant for improving the in-plane uniformity of the coating film, and a silicon substrate. Alternatively, an additive such as an adhesion aid for enhancing the adhesiveness with the copper substrate may be contained.

  Examples of the dye include methyl violet, crystal violet, malachite green and the like. The blending amount of the dye is preferably 0.1 parts by mass to 10 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A). If the blending amount is 0.1 part by mass or more, the visualization effect is satisfactorily obtained, and if it is 10 parts by mass or less, the heat resistance of the film after thermosetting is good.

Examples of the fragrance include terpene compounds, and monoterpene compounds and sesquiterpene compounds are preferable from the viewpoint of solubility in a solvent.
Specifically, as a fragrance, for example, linalool, isophytol, dihydrolinalool, linalyl acetate, linalool oxide, geranyl linalool, lavandulol, tetrahydrolavandulol, lavandulol acetate, nerol, nerol acetate, geraniol, citral. , Geranyl acetate, geranylacetone, geranium acid, citral dimethyl acetal, citronellol, citronellal, hydroxycitronellal, dimethyl octanal, citronellic acid, citronellyl acetate, tageton, artemisiaketone, pulegol, isopulegol, menthol, menthol acetate, iso Menthol, Neomenthol, Menthanol, Mentantriol, Mentantetraol, Carbomenthol, Menthoxyacetic acid, Perillylalco , Perilaldehyde, carveol, piperitol, terpene-4-ol, terpineol, terpinenol, dihydroterpineol, sobreol, thymol, borneol, bornyl acetate, isoborneol, isobornyl acetate, cineol, pinol, pinocarbeol, myrtenol, myrtenal, Examples thereof include berbenol, pinocampheol, camphorsulfonic acid, nerolidol, terpinene, ionone, pinene, camphene, camphorene aldehyde, camphoronic acid, isocamphoronic acid, camphoric acid, abithienic acid, and glycyrrhetinic acid. These terpene compounds may be used alone or in combination of two or more.

  The blending amount of the fragrance is preferably 0.1 parts by mass to 70 parts by mass, and more preferably 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin. If the blending amount is 0.1 part by mass, the effect of the fragrance is satisfactorily obtained, 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, there may be mentioned fluorine-based surfactants such as Florard (Sumitomo 3M: trade name), Megafac (Dainippon Ink and Chemicals: trade name), Lumiflon (Asahi Glass Co., Ltd .: trade name), and the like. Furthermore, organic siloxane surfactants such as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name), DBE (manufactured by Chisso Co., Ltd .: trade name), Granol (manufactured by Kyoeisha Kagaku Co., Ltd .: trade name), and the like. Addition of the surfactant makes it more difficult to cause cissing of the coating film at the wafer edge during coating.

  The blending amount of the surfactant is preferably 0 to 10 parts by mass, and more preferably 0.01 part by mass to 1 part by mass, relative to 100 parts by mass of the (A) alkali-soluble resin. When the compounding amount is 10 parts by mass or less, the heat resistance of the film after thermosetting is good. When the blending amount is 0.01 part by mass or more, the effect of preventing cissing of the coating film is good.

  Examples of the adhesion aid for improving the adhesion between the cured resist pattern and the silicon substrate or the copper substrate include, for example, alkyl imidazoline, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy polymer, organosilicon compound, and triazole. And a heterocyclic compound such as tetrazole, oxazole, thiazole, and imidazole.

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

  Specific examples of the organosilicon compound include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name KBM803, Chisso Corporation: trade name Sila Ace S810), 3-mercaptopropyltriethoxysilane (Azmax Co., Ltd.). Made: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name LS1375, manufactured by Asmax Co., Ltd .: trade name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Asmax Co., Ltd. : Product name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Asmax Corporation: product name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydi Toxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltripropoxysilane. Methoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxy. Propoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-meth Captobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N- (3-triethoxysilylpropyl) urea (Shin-Etsu Chemical Co., Ltd .: trade name LS3610, Asmax Co., Ltd .: trade name SIU9055.0), N -(3-Trimethoxysilylpropyl) urea (manufactured by Asmax 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 Ropyl) 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 Asmax Corporation: trade name SLA0598.0). , M-aminophenyltrimethoxysilane (manufactured by ASMAX CORPORATION: product SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Asmax Co., Ltd .: trade name SLA0599.1) Aminophenyltrimethoxysilane (manufactured by Asmax Co., Ltd .: trade name SLA0599.2), 2- (trimethoxysilylethyl). Pyridine (manufactured by Asmax 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-butoxyaluminoxytriethoxyoxy. 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, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol, and the like. These may be used alone or in combination.

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

  The organosilicon compounds may be used alone or in combination of two or more. The blending amount of the organosilicon compound is preferably 1 to 40 parts by mass, more preferably 2 to 30 parts by mass, and 4 parts by mass to 100 parts by mass of the (A) alkali-soluble resin. 20 parts by mass is more preferable. When the compounding amount of the compound is 1 part by mass or more, the development residue in the exposed part is satisfactorily reduced and the adhesion to the silicon substrate is good, while when it is 40 parts by mass or less, the cured film It has a good tensile elongation and good adhesion and lithographic performance.

｛式中、Ｚ_１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成る群から選ばれる基であり、Ｚ_２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成る群から選ばれる少なくとも１つの基である。｝ Specific examples of the heterocyclic 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, dibenzothiazyl disulfide , Methylthiobenzimidazole, benzimidazole, phenylmercaptothiazoline, mercaptophenyltetrazole, and mercaptomethyltetrazole. Further, examples of the benzotriazoles include compounds represented by the following general formula.

{In the formula, Z ₁ is a group selected from the group consisting of a hydrogen atom, a monovalent hydrocarbon group having 1 to 5 carbon atoms, and a carboxyl group, and Z ₂ is a hydrogen atom, a hydroxyl group, a carbon atom. It is at least one group selected from the group consisting of monovalent hydrocarbon groups of the formulas 1 to 5 and aminoalkyl groups. }

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

  The compounding amount of the heterocyclic compound is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin. When the compounding amount of the heterocyclic structure compound is 0.1 part by mass or more, the adhesion of the film after thermosetting to the copper substrate is good, and when it is 30 parts by mass or less, the stability of the composition is good.

<Cured relief pattern and method for manufacturing semiconductor device>
Further, the present invention is a method for producing a cured relief pattern,
(A) a step of forming a photosensitive resin layer or a photosensitive film comprising the photosensitive resin composition for spin coating of the present invention on a substrate by a spin coating method,
(B) a step of exposing the photosensitive resin layer or the photosensitive film,
(C) a step of removing an exposed portion or an unexposed portion of the photosensitive resin layer or the photosensitive film with a developer to obtain a relief pattern, and (d) a step of heating the relief pattern,
A method including is provided.

The present invention also provides a cured relief pattern produced by the above method. The steps (a) to (d) will be specifically described below.
(A) a step of forming a photosensitive resin layer or a photosensitive film comprising the photosensitive resin composition for spin coating of the present invention on a substrate by a spin coating method;
The photosensitive resin composition for spin coating of the present invention is applied to a substrate such as a silicon wafer, a ceramic substrate or an aluminum substrate using a spin coater, and then using an oven or a hot plate at 50 ° C to 140 ° C. Dry with to remove the solvent.
(B) a step of exposing the photosensitive resin layer or the photosensitive film to light;
Next, the substrate obtained above is exposed to actinic rays through a mask using a contact aligner or a stepper, or is directly irradiated with a light beam, an electron beam or an ion beam.
(C) a step of removing an exposed portion or an unexposed portion of the photosensitive resin layer or the photosensitive film with a developing solution to obtain a relief pattern;
Next, the development can be carried out by selecting from a dipping method, a paddle method, a rotary spray method and the like. By development, the exposed portion (in the case of positive type) or the unexposed portion (in the case of negative type) can be eluted and removed from the applied photosensitive resin composition to obtain a relief pattern. Examples of the developer include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia water, organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide. An aqueous solution of a 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 can be used. Among these, an aqueous tetramethylammonium hydroxide solution is preferable, and the concentration of the tetramethylammonium hydroxide is preferably 0.5% by mass to 10% by mass, more preferably 1% by mass to 5% by mass. Is.
(D) heating the relief pattern;
Finally, the obtained relief pattern is cured to form a heat-resistant cured relief pattern made of a resin having a polybenzoxazole structure. An oven furnace, a hot plate, a vertical furnace, a belt conveyor furnace, a pressure oven or the like can be used as the heating device, and as a heating method, heating by hot air, infrared rays, electromagnetic induction or the like is recommended. The temperature is preferably 200 ° C to 450 ° C, more preferably 250 ° C to 400 ° C. The heating time is preferably 15 minutes to 8 hours, more preferably 15 minutes to 4 hours. The atmosphere during heating is preferably 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. As the cured film, 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-mentioned photosensitive resin composition on the passivation film, and a circuit formed on the semiconductor element Examples thereof include an insulating film such as an interlayer insulating film formed by forming a cured film of the above-mentioned photosensitive resin composition, an α-ray blocking film, a flattening film, protrusions (resin posts), and partition walls.

  The present invention also provides a display device including 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 applications of the display device include a protective film formed by forming a cured film of the above-mentioned photosensitive resin composition on a display device, an insulating film or a flattening film for a TFT device or a color filter, an MVA type. Examples thereof include protrusions for liquid crystal display devices, partition walls for organic EL device cathodes, and the like. The method of use is to form the patterned cured film of the photosensitive resin composition on the substrate on which the display element or the color filter is formed by the above method according to the application of the semiconductor device.

  The photosensitive resin composition of the present invention is also useful for applications such as interlayer insulation of multilayer circuits, cover coats of flexible copper clad boards, solder resist films, liquid crystal alignment films of display devices, and applications of light emitting devices. .

[Synthesis Example 1] Synthesis of hydroxypolyamide (P-1) 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane (hereinafter, also referred to as "6FAP") in a separable flask having a capacity of 2 L. ) 197.8 g (0.54 mol), pyridine 75.9 g (0.96 mol), and DMAc692 g were mixed and stirred at room temperature (25 ° C.) to dissolve them. A mixed solution prepared by dissolving 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride in 88 g of GBL was added dropwise to the obtained mixture through a dropping funnel. The time required for the dropping was 40 minutes, and the maximum temperature of the reaction solution was 28 ° C.
After completion of the dropwise addition, the flask was heated to 50 ° C. in a water bath and stirred for 18 hours, and then the IR spectrum of the reaction solution was measured to show that characteristic absorption of imide groups at 1385 cm ⁻¹ and 1772 cm ⁻¹ appeared. It was confirmed.
Next, the flask was cooled to 8 ° C. with a water bath, and a mixed solution prepared by dissolving 142.3 g (0.48 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride in 398 g of GBL was added dropwise from a dropping funnel. The time required for dropping was 80 minutes, and the temperature of the reaction solution was 12 ° C. at maximum. Three hours after the completion of the dropping, the reaction solution was dropped into 12 l of water under high-speed stirring to disperse and precipitate the polymer. The purified precipitate was collected, washed with water, dehydrated and then vacuum dried to obtain polyhydroxyamide (P-1). The weight average molecular weight of the hydroxypolyamide thus synthesized by gel permeation chromatography (GPC) was 14,000 in terms of polystyrene. The analysis conditions of GPC are described below.
Column: Showa Denko KK Trade name Shodex 805/804/803 Series Mobile phase: Tetrahydrofuran 40 ° C
Flow rate: 1.0 ml / min Detector: Showa Denko brand name Shodex RI SE-61

を有するＴＭＯＭ−ＢＰ（本州化学社製：商品名）２１．７ｇ（０．０６ｍｏｌ）、ピリジン９．４８ｇ（０．１２ｍｏｌ）及びＧＢＬ１３０ｇを０℃で混合攪拌した溶液に、別途ＧＢＬ１４２ｇ中にビス（クロロカルボニル）トリシクロ［５，２，１，０^２，６］デカンを４７．５ｇ（０．１８ｍｏｌ）を溶解させたものを、滴下ロートより滴下した。滴下に要した時間は４０分、反応液温は最大で１６℃であった。
滴下後、１時間攪拌した反応溶液を、滴下ロートを用いて、別途、テフロン（登録商標）製の碇型攪拌器を取り付けた容量２Ｌのセパラブルフラスコ中で、６ＦＡＰ５１．２ｇ（０．１４ｍｏｌ）、ピリジン１５．０ｇ（０．１９ｍｏｌ）、ＧＢＬ３０７ｇ及びＤＭＡｃ１０２ｇを室温（２５℃）で混合攪拌し溶解させ、その反応容器をメタノールにドライアイスを加えた容器に浸して−１５℃に冷却した反応溶液に、滴下した。反応系中は−１５〜０℃に保って４５分を要して反応容器に滴下した。滴下終了後、反応容器を氷浴に浸し、０〜１０℃に保って１時間攪拌した。さらにピリジン７．１２ｇ（０．０９ｍｏｌ）を加えた。その後、反応液を室温に戻し、５−ノルボルネン−２，３−ジカルボン酸無水物（東京化成工業社製）１９．７ｇ（０．１２ｍｏｌ）とピリジン９．４９ｇ（０．１２ｍｏｌ）を加え、５０℃の湯浴に浸して、反応液を５０℃とし１８時間攪拌した。
上記反応液にエタノールを加えて重合体を析出させた後、回収し、ＧＢＬ６２６ｇに溶解させた。次いで、陽イオン交換樹脂（オルガノ社製、アンバーリストＡ２１）６２．１ｇ、陰イオン交換樹脂（オルガノ社製、アンバーリスト１５）５９．６ｇでイオン交換した。この溶液をイオン交換水１２Ｌに高速攪拌下で滴下し、重合体を分散析出させ、回収し、適宜水洗、脱水の後に真空乾燥を施し、ＰＢＯ前駆体構造と架橋基含有構造を有するアルカリ可溶性重合体（Ｐ−２）の紛体を得た。
このようにして合成されたアルカリ可溶性重合体のＧＰＣによる重量平均分子量（Ｍｗ）は、ポリスチレン換算で１３２００の単一のシャープな曲線であり、単一組成物であった。 [Synthesis Example 2] Synthesis of hydroxypolyamide (P-2) In a three-necked flask having a capacity of 300 mL and equipped with an anchor type stirrer made of Teflon (registered trademark), the following structure:

21.7 g (0.06 mol) of TMOM-BP (trade name) manufactured by Honshu Kagaku Co., Ltd., 9.48 g (0.12 mol) of pyridine and 130 g of GBL were mixed and stirred at 0 ° C., and bis (was added to 142 g of GBL separately. Chlorocarbonyl) tricyclo [5,2,1,0 ^2,6 ] decane dissolved in 47.5 g (0.18 mol) was added dropwise from the dropping funnel. The time required for dropping was 40 minutes, and the reaction liquid temperature was 16 ° C. at the maximum.
After the dropping, the reaction solution stirred for 1 hour was separately charged using a dropping funnel in a separable flask having a capacity of 2 L and equipped with an anchor type stirrer made of Teflon (registered trademark), 6FAP (51.2 g, 0.14 mol). , 15.0 g (0.19 mol) of pyridine, 307 g of GBL and 102 g of DMAc were mixed and stirred at room temperature (25 ° C.) and dissolved, and the reaction container was immersed in a container of dry ice added to methanol and cooled to −15 ° C. Then, it was dropped. The temperature was kept at -15 to 0 ° C in the reaction system, and the reaction mixture was dropped into the reaction vessel over 45 minutes. After completion of the dropping, the reaction vessel was immersed in an ice bath and kept at 0 to 10 ° C and stirred for 1 hour. Further, 7.12 g (0.09 mol) of pyridine was added. Thereafter, the reaction solution was returned to room temperature, 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 9.49 g (0.12 mol) of pyridine were added, and 50 The reaction solution was heated to 50 ° C. and stirred for 18 hours by immersing it in a water bath at ℃.
Ethanol was added to the above reaction solution to precipitate a polymer, which was then collected and dissolved in 626 g of GBL. Next, 62.1 g of a cation exchange resin (Amberlist A21 manufactured by Organo) and 59.6 g of an anion exchange resin (Amberlist 15 manufactured by Organo) were used for ion exchange. This solution was added dropwise to 12 L of ion-exchanged water under high-speed stirring to disperse and precipitate the polymer, which was then collected, washed appropriately with water, dehydrated and then vacuum-dried to obtain an alkali-soluble polymer having a PBO precursor structure and a crosslinkable group-containing structure. A powder of coalesced (P-2) was obtained.
The weight average molecular weight (Mw) of the alkali-soluble polymer thus synthesized by GPC was 13200, which was a single sharp curve in terms of polystyrene, and was a single composition.

[Synthesis example 3] Synthesis of hydroxypolyamide (P-3) 6FAP (51.2 g, 0.14 mol) and pyridine (15.0 g) were placed in a separable flask having a capacity of 2 L and equipped with an anchor stirrer made of Teflon (registered trademark). (0.19 mol), GBL307g and DMAc102g were added, mixed and stirred at room temperature (25 ° C) to dissolve, and the reaction container was immersed in a container of dry ice in methanol and cooled to -15 ° C. Separately, a mixed solution prepared by dissolving 26.56 g (0.09 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride in 132 g of GBL was added dropwise from a dropping funnel. The temperature was kept at -15 to 0 ° C in the reaction system, and the solution was added dropwise to the reaction vessel over 45 minutes (reaction solution 1).
Separately, in a three-necked flask with a capacity of 300 mL equipped with a Teflon (registered trademark) anchor type stirrer, 10.9 g (0.03 mol) of TMOM-BP (Honshu Kagaku: trade name) and 4,4-biphenol 0 To a solution obtained by mixing and stirring 9.93 g (0.005 mol) pyridine 9.48 g (0.12 mol) and GBL 130 g at 0 ° C., separately, in GBL 142 g, bis (chlorocarbonyl) tricyclo [5,2,1,0 ^2,6 ]. What melt | dissolved 23.75g (0.09mol) of decane was dripped from the dropping funnel. The time required for dropping was 40 minutes, and the reaction liquid temperature was 16 ° C. at the maximum. After the dropping, the mixture was stirred for 1 hour (reaction liquid 2).
(Reaction solution 2) was added dropwise to (reaction solution 1) using a dropping funnel. The time required for the dropping was 40 minutes, and the reaction liquid temperature was 6 ° C. at the maximum. After the completion, the reaction vessel was immersed in an ice bath, kept at 0 to 10 ° C, and stirred for 1 hour. Further, 7.12 g (0.09 mol) of pyridine was added. Thereafter, the reaction solution was returned to room temperature, 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 9.49 g (0.12 mol) of pyridine were added, and 50 The reaction solution was heated to 50 ° C. and stirred for 18 hours by immersing it in a water bath at ℃.
Ethanol was added to the above reaction solution to precipitate a polymer, which was then collected and dissolved in 626 g of GBL. Next, 62.1 g of a cation exchange resin (Amberlist A21 manufactured by Organo) and 59.6 g of an anion exchange resin (Amberlist 15 manufactured by Organo) were used for ion exchange. This solution was added dropwise to 12 L of ion-exchanged water under high-speed stirring to disperse and precipitate the polymer, which was then collected, washed appropriately with water, dehydrated and then vacuum-dried to obtain an alkali-soluble polymer having a PBO precursor structure and a crosslinkable group-containing structure. A powder of coalesced (P-3) was obtained.
The weight average molecular weight (Mw) of the alkali-soluble polymer thus synthesized by GPC was 11300, which was a single sharp curve in terms of polystyrene, and was a single composition.

[Synthesis Example 4] Synthesis of polyamide (P-4) derived from tetracarboxylic acid and diamine and having a carboxyl group at the ortho position of the amide bond. Stirrer, thermometer, nitrogen introduction tube, Dimroth cooling tube A 5 liter flask was charged with 295.0 g of N-methyl-2-pyrrolidone, 55.3 g of 2-octanone and 36.9 g of diethyl ketone, and 26.21 g of 4,4′-diaminodiphenyl ether and bis (3-aminophenoxy). 14.70 g of phenyl) sulfone and 1.49 g of LP7100 (trade name, 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane manufactured by Shin-Etsu Chemical Co., Ltd.) were added and stirred. Dissolved. Next, 50.02 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added to this solution, and the mixture was reacted at 25 ° C. for 8 hours and then at 60 ° C. for 8 hours with stirring. The polyamic acid solution thus obtained was added dropwise to 5 L of ion-exchanged water under high-speed stirring to disperse and precipitate the polymer, which was then collected, washed appropriately with water, dehydrated and then vacuum dried to obtain an alkali having a polyamic acid structure. A powder of the soluble polymer (P-4) was obtained. The weight average molecular weight (Mw) of the alkali-soluble polymer thus synthesized by GPC was 26400, which was a single sharp curve in terms of polystyrene, and was a single composition.

[Synthesis Example 5] Synthesis of alkali aqueous solution-soluble polyimide (P-5) having a phenolic hydroxyl group in the side chain: 6FAP 32.N.C. was added to a four-necked flask equipped with a stirring rod, a Dean-Stark trap with a ball, and a nitrogen introduction tube. 96 g (90 mmol was added, 196 g of NMP and 40 g of toluene were added, and the mixture was stirred at room temperature. Then, 31.02 g (100 mmol) of 3,3,4,4-oxydiphthalic acid dianhydride was added, and the mixture was stirred at room temperature for 2 hours. Then, the mixture was heated and stirred at 180 ° C. and 180 rpm for 3 hours, and water as a by-product was azeotropically distilled with toluene during the reaction, and water accumulated at the bottom of the reflux pipe was removed every 30 minutes. The polystyrene-equivalent weight average molecular weight of the polyimide polymer thus produced was 24400. This reaction solution was added dropwise to 5 L of water under high-speed stirring, Rimmer allowed to disperse precipitate, which was collected, appropriately washed with water to obtain a powder of the alkali-soluble polymer having a soluble polyimide structure in an organic solvent subjected to vacuum drying after dehydration (P-5).

｛式中、Ｑは、全体数の８３％が下記式：

で表される構造であり、残りの１７％が水素原子である。｝
(Ｃ)２５℃における蒸気圧が１０Ｐａ〜２５０Ｐａであり、かつ２５℃における密度が０．７ｇ／ｃｍ^３〜１．０２ｇ／ｃｍ^３である溶媒として下記（Ｃ−１）〜（Ｃ−９）を用い、その他の溶媒として下記（Ｘ−１）〜（Ｘ−８）を用いた。 <Preparation of photosensitive resin composition>
(A) As the alkali-soluble resin, (P-1) to (P-5) obtained in Synthesis Examples 1 to 5 above, phenol resin (trade name EP4000B, m-cresol / p-cresol ratio = 60/40). Asahi Organic Materials Co., Ltd. (P-6), and polyhydroxystyrene (manufactured by Maruzen Petrochemical Co., Ltd .: trade name Marcalinker CST) (P-7), (B) as a photo-acid generator: Using a compound represented by the structure (hereinafter also referred to as PAC1),

{In the formula, 83% of Q is the following formula:

The remaining 17% is a hydrogen atom. }
(C) a 10Pa~250Pa vapor pressure at 25 ° C., and the following as the solvent is the density at 25 ° C. is ^{0.7g / cm 3 ~1.02g / cm 3} (C-1) ~ (C-9) The following (X-1) to (X-8) were used as other solvents.

The solvents used and their vapor pressures and densities at 25 ° C are shown below:
(C-1) 2-octanone (vapor pressure 233 Pa, density 0.81 g / cm ³ ).
(C-2) 2-nonanone (vapor pressure 85 Pa, density 0.82 g / cm ³ ).
(C-3) diisobutyl ketone (vapor pressure 197 Pa, density 0.81 g / cm ³ ).
(C-4) Isoamyl ether (vapor pressure 225 Pa, density 0.79 g / cm ³ ).
(C-5) 1-heptanol (vapor pressure 43 Pa, density 0.82 g / cm ³ ).
(C-6) 2-ethyl-1-hexanol (vapor pressure 27 Pa, density 0.82 g / cm ³ ).
(C-7) Propylene glycol monobutyl ether (vapor pressure 59 Pa, density 0.89 g / cm ³ ).
(C-8) Dipropylene glycol dimethyl ether (vapor pressure 70 Pa, density 0.91 g / cm ³ ).
(C-9) Dipropylene glycol methyl propyl ether (vapor pressure 30 Pa, density 0.90 g / cm ³ ).
(X-1) GBL (vapor pressure 36 Pa, density 1.13 g / cm ³ ).
(X-2) N-methylpyrrolidone (vapor pressure 40 Pa, density 1.03 g / cm ³ ).
(X-3) ethyl lactate (vapor pressure 155 Pa, density 1.05 g / cm ³ ).
(X-4) PGMEA (vapor pressure 420 Pa, density 0.96 g / cm ³ ).
(X-5) 2-heptanone (vapor pressure 630 Pa, density 0.81 g / cm ³ ).
(X-6) Dibutyl ether (vapor pressure 946 Pa, density 0.78 g / cm ³ ).
(X-7) Dipropylene glycol monobutyl ether (vapor pressure 8 Pa, density 0.93 g / cm ³ ).
(X-8) Propylene carbonate (vapor pressure 4 Pa, density 1.17 g / cm ³ ).

[Example 1]
P-1 synthesized in Synthesis Example 1 was used as the (A) alkali-soluble resin, and 15 parts by mass of (B) the photoacid generator PAC1 was blended with 100 parts by mass of P-1 and C- was used as the solvent. 1 was used to prepare a composition having a viscosity of 10P. A positive photosensitive resin composition was prepared by filtering with a polyethylene filter having pores of 0.2 μm.

[Example 2]
A positive photosensitive resin composition was prepared in the same manner by using P-2 synthesized in Synthesis Example 2 instead of P-1 used in Example 1.

[Example 3]
A positive type photosensitive resin composition was similarly prepared by using P-3 synthesized in Synthesis Example 3 instead of P-1 used in Example 1.

[Example 4]
A positive type photosensitive resin composition was prepared in the same manner by using P-4 synthesized in Synthesis Example 4 instead of P-1 used in Example 1.

[Example 5]
A positive photosensitive resin composition was prepared in the same manner by using P-5 synthesized in Synthesis Example 5 instead of P-1 used in Example 1.

[Example 6]
A positive photosensitive resin composition was prepared in the same manner by using the phenol resin P-6 instead of P-1 used in Example 1.

[Example 7]
A positive type photosensitive resin composition was prepared in the same manner by using polyhydroxystyrene P-7 instead of P-1 used in Example 1.

[Example 8]
A positive photosensitive resin composition was prepared in the same manner by using the solvent C-8 instead of the solvent C-1 used in Example 1.

[Example 9]
A positive photosensitive resin composition was similarly prepared by using P-2 synthesized in Synthesis Example 2 instead of P-1 used in Example 8.

[Example 10]
A positive photosensitive resin composition was similarly prepared by using P-3 synthesized in Synthesis Example 3 instead of P-1 used in Example 8.

[Example 11]
A positive photosensitive resin composition was similarly prepared by using P-4 synthesized in Synthesis Example 4 instead of P-1 used in Example 8.

[Example 12]
A positive photosensitive resin composition was prepared in the same manner by using P-5 synthesized in Synthesis Example 5 instead of P-1 used in Example 8.

[Example 13]
A positive photosensitive resin composition was prepared in the same manner by using phenol resin P-6 instead of P-1 used in Example 8.

[Example 14]
A positive type photosensitive resin composition was prepared in the same manner by using polyhydroxystyrene P-7 instead of P-1 used in Example 8.

[Example 15]
A positive photosensitive resin composition was prepared in the same manner by using the solvent C-2 instead of the solvent C-1 used in Example 1.

[Example 16]
A positive photosensitive resin composition was prepared in the same manner by using the solvent C-3 instead of the solvent C-1 used in Example 1.

[Example 17]
A positive photosensitive resin composition was prepared in the same manner by using the solvent C-4 instead of the solvent C-1 used in Example 1.

[Example 18]
A positive photosensitive resin composition was prepared in the same manner by using the solvent C-5 instead of the solvent C-1 used in Example 1.

[Example 19]
A positive photosensitive resin composition was prepared in the same manner by using the solvent C-6 instead of the solvent C-1 used in Example 1.

[Example 20]
A positive photosensitive resin composition was prepared in the same manner by using the solvent C-7 instead of the solvent C-1 used in Example 1.

[Example 21]
A positive photosensitive resin composition was prepared in the same manner by using the solvent C-9 instead of the solvent C-1 used in Example 1.

[Example 22]
As (A) an alkali-soluble resin, P-1 synthesized in Synthesis Example 1 and a phenol resin P-6 were mixed at a mass ratio of 100: 50 to prepare (A) an alkali-soluble resin, and B) 15 parts by mass of the photo-acid generator PAC1 was blended, and the composition was adjusted so that the viscosity was 10 P using C-8 as a solvent. A positive photosensitive resin composition was prepared by filtering with a polyethylene filter having pores of 0.2 μm.

[Example 23]
Positive-type photosensitivity was the same as in Example 22 except that (A) the alkali-soluble resin prepared by mixing P-1 synthesized in Synthesis Example 1 and the phenol resin P-6 in a mass ratio of 100: 100 was used. A resin composition was prepared.

[Example 24]
Positive type photosensitivity was the same as in Example 22 except that (A) the alkali-soluble resin prepared by mixing P-1 synthesized in Synthesis Example 1 and the phenol resin P-6 in a mass ratio of 100: 150 was used. A resin composition was prepared.

[Example 25]
Positive type photosensitivity was the same as in Example 22 except that (A) the alkali-soluble resin prepared by mixing P-3 synthesized in Synthesis Example 3 and the phenol resin P-6 in a mass ratio of 100: 50 was used. A resin composition was prepared.

[Example 26]
Positive type photosensitivity was the same as in Example 22 except that (A) alkali-soluble resin prepared by mixing P-3 synthesized in Synthesis Example 3 and phenol resin P-6 in a mass ratio of 100: 100 was used. A resin composition was prepared.

[Example 27]
Positive type photosensitivity was the same as in Example 22 except that (A) the alkali-soluble resin prepared by mixing P-3 synthesized in Synthesis Example 3 and the phenol resin P-6 at a mass ratio of 100: 150 was used. A resin composition was prepared.

[Example 28]
Using (P) -1 synthesized in Synthesis Example 1 as the (A) alkali-soluble resin, (B) 15 parts by mass of the photoacid generator PAC1 was blended with 100 parts by mass of P-1, and as a solvent. The composition was adjusted so that the viscosity was 10 P using a mixture of C-1 and X-1 in a mass ratio of 20:80. A positive photosensitive resin composition was prepared by filtering with a polyethylene filter having pores of 0.2 μm.

Example 29
A positive photosensitive resin composition was prepared in the same manner as in Example 28 except that the solvent used was a mixture of C-1 and X-1 at a mass ratio of 50:50.

[Example 30]
A positive photosensitive resin composition was prepared in the same manner as in Example 28, except that C-1 and X-1 were mixed as a solvent in a mass ratio of 80:20.

[Example 31]
A positive photosensitive resin composition was prepared in the same manner as in Example 28 except that the solvent used was a mixture of C-8 and X-1 at a mass ratio of 40:60.

[Example 32]
A positive-type photosensitive resin composition was prepared in the same manner as in Example 28 except that the solvent used was a mixture of C-8 and X-1 at a mass ratio of 50:50.

[Example 33]
A positive photosensitive resin composition was prepared in the same manner as in Example 28 except that the solvent used was a mixture of C-8 and X-1 at a mass ratio of 80:20.

Example 34
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that the viscosity of the varnish was adjusted to 5P.

Example 35
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that the viscosity of the varnish was adjusted to 20P.

[Comparative Example 1]
A positive photosensitive resin composition was prepared in the same manner by using the solvent X-1 instead of the solvent C-1 used in Example 1.

[Comparative Example 2]
A positive photosensitive resin composition was prepared in the same manner by using the solvent X-2 instead of the solvent C-1 used in Example 1.

[Comparative Example 3]
A positive photosensitive resin composition was prepared in the same manner by using the solvent X-3 in place of the solvent C-1 used in Example 1.

[Comparative Example 4]
A positive photosensitive resin composition was prepared in the same manner by using the solvent X-4 in place of the solvent C-1 used in Example 1.

[Comparative Example 5]
A positive photosensitive resin composition was prepared in the same manner by using the phenol resin P-6 in place of the alkali-soluble resin P-1 used in Example 1 and the solvent X-5 in place of the solvent C-1. .

[Comparative Example 6]
A positive photosensitive resin composition was prepared in the same manner by using the solvent X-6 instead of the solvent C-1 used in Example 1.

[Comparative Example 7]
A positive photosensitive resin composition was prepared in the same manner by using the solvent X-7 instead of the solvent C-1 used in Example 1.

[Comparative Example 8]
A positive photosensitive resin composition was prepared in the same manner by using the solvent X-8 instead of the solvent C-1 used in Example 1.

[Comparative Example 9]
A positive photosensitive resin composition was prepared in the same manner as in Example 28, except that C-1 and X-1 were mixed as the solvent in a mass ratio of 10:90.

[Comparative Example 10]
A positive photosensitive resin composition was prepared in the same manner as in Example 28, except that C-8 and X-1 were mixed at a mass ratio of 30:70 as a solvent.

[Comparative Example 11]
A positive photosensitive resin composition was prepared in the same manner as in Example 28, except that the solvent used was a mixture of X-1 and X-3 in a mass ratio of 70:30.

[Comparative Example 12]
A positive photosensitive resin composition was prepared in the same manner as in Example 28 except that the solvent used was a mixture of X-1 and X-4 at a mass ratio of 70:30.

[Comparative Example 13]
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that the viscosity of the varnish was adjusted to 4P.

[Comparative Example 14]
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that the viscosity of the varnish was adjusted to 22P.

<Method for measuring density of photosensitive resin composition>
2.5 cm ³ of the photosensitive resin composition was measured in a 3 cm ³ disposable syringe, and the mass thereof was measured by a precision balance. The density of the photosensitive resin composition was calculated from the following (Formula 1).
Density (g / cm ³ ) of the photosensitive resin composition = 2.5 cm ³ Mass (g) /2.5 (cm ³ ) of the photosensitive resin composition (Formula 1)

<Method of measuring viscosity of photosensitive resin composition>
The photosensitive resin composition prepared above was weighed in an amount of 2.0 cm ³ , and the viscosity was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd .: RE-80, trade name).

<Evaluation of uniformity of film thickness of photosensitive resin composition>
The photosensitive resin compositions obtained in Examples 1 to 35 and Comparative Examples 1 to 14 were spin-coated (manufactured by Tokyo Electron Ltd .: MARK-8, trade name) with a predetermined varnish at the center of an 8-inch silicon wafer. 2.5 g was dispensed, and the pre-baked film was spin-coated at a rotation speed such that the film had a thickness of 9.0 μm. Prebaking was performed on a hot plate at 125 ° C. for 180 seconds to form a prebaked film. The film thickness is measured with a film thickness measurement device (Dainippon Screen Mfg. Co., Ltd .: Lambda Ace, trade name), and the film thickness is measured at 13 points at 15 mm intervals from -90 mm to 90 mm with the center of the wafer at 0 mm, and The maximum and minimum values of the average film thickness and the measured film thickness were obtained.

<Evaluation method of coating area of photosensitive resin composition>
The photosensitive resin compositions obtained in Examples 1 to 35 and Comparative Examples 1 to 14 were spin-coated (manufactured by Tokyo Electron Ltd .: MARK-8, trade name) with a predetermined varnish at the center of an 8-inch silicon wafer. Was dispensed, and the pre-baked film was spin-coated at the number of rotations such that the thickness became 9.0 μm. Prebaking was performed on a hot plate at 125 ° C. for 180 seconds to form a circular coating film.
The diameter of this coating film was measured with a ruler (Mitutoyo Corporation: ABS Digimatic Caliper, trade name), and the coating area was calculated by the following formula.
Application area (cm ² ) = [(measured diameter (cm) / 2) ² × 3.14]
The larger this value is, the more spin-coating method can be used to obtain a pre-baked film having a predetermined film thickness with a smaller discharge mass.
In the examples and comparative examples, the coating area was evaluated as follows.
Application area 175 cm ² or more: ○
Application area less than 175 cm ² : x

<In-plane uniformity evaluation method of photosensitive resin composition>
The in-plane uniformity was calculated from the measured film thickness by the following formula.
In-plane uniformity (%) =
[[(Maximum value of measured film thickness)-(minimum value of measured film thickness)] / (average film thickness)] × 100
In this case, the in-plane uniformity was evaluated as follows.
In-plane uniformity 1.5% or less: ◎
In-plane uniformity over 1.5% and under 3%: ○
In-plane uniformity 3% over 5% or less: △
In-plane uniformity over 5%: ×

<Method of evaluating the film thickness of the edge portion of the substrate of the photosensitive resin composition>
From the measured film thickness, the film thickness of the edge portion of the substrate was obtained from the following formula.
Edge film thickness (nm) = (film thickness 2 mm from the edge of the substrate) − (average film thickness)
In this case, the film thickness of the edge portion was evaluated as follows.
Edge film thickness 200 nm or less: ◎
Edge film thickness over 200 nm and under 300 nm: ○
Edge film thickness over 300 nm and 400 nm or less: △
Edge film thickness exceeds 400 nm: ×
The prepared positive photosensitive resin compositions of Examples 1 to 35 and Comparative Examples 1 to 14 were evaluated for density, coating area, in-plane uniformity and film thickness of the substrate edge, and the results are shown in Table 2.

From the results of Table 2, with (C) a vapor pressure at 25 ° C. is 10Pa～250Pa, and solvent density at 25 ° C. is ^{0.7g / cm 3 ~1.02g / cm 3} , the resin Examples 1 to 35 using a photosensitive resin composition for spin coating, wherein the composition has a density of 0.75 to 1.1 g / cm ^{3 at} 25 ° C and a viscosity of 5P to 20P at 25 ° C. In comparison with the comparative example, it can be seen that the spin coating method can obtain a pre-baked film having a predetermined film thickness with a smaller discharge mass and is excellent in film thickness uniformity.

  The photosensitive resin composition of the present invention is a surface protective film for semiconductor devices, an interlayer insulating film, and an insulating film for rewiring, a protective film for flip-chip devices, a protective film for devices 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 board, a solder resist film, a liquid crystal alignment film, and the like.

Claims (14)

(A) Alkali-soluble resin;
The solvent and (C) vapor at 25 ° C. pressure is 10Pa～250Pa, and density at 25 ° C. is ^{0.7g / cm 3 ~1.02g / cm 3} ; (B) a photoacid generator;
A spin-coating a photosensitive resin composition comprising, density at 25 ° C. of the spin-coating a photosensitive resin composition ^is a ^{0.75g / cm 3 ~1.1g / cm 3} , and the spin-coating The photosensitive resin composition for spin coating, wherein the viscosity of the photosensitive resin composition for spin coating at 25 ° C. is 0.5 Pa · s to 2 Pa · s. Wherein (C) the density of the solvent ^{is 0.8g / cm 3 ~0.95g / cm 3} , a spinning photosensitive resin composition of claim 1.   The photosensitive resin composition for spin coating contains 30% by mass to 100% by mass of the (C) solvent with respect to the total mass of all the solvents contained in the photosensitive resin composition for spin coating. Item 3. The photosensitive resin composition for spin coating according to Item 1 or 2.   The photosensitive resin composition for spin coating according to any one of claims 1 to 3, wherein the solvent (C) is at least one selected from the group consisting of ketones, ethers, alcohols and glycols. The solvent (C) is represented by the following general formulas (1) to (4):

{In the formula, R ₁ and R ₂ are each independently an alkyl group having 1 to 9 carbon atoms, and the sum of the carbon atoms of R ₁ and R ₂ is 7 to 10. }

{In the formula, R ₃ and R ₄ are each independently an alkyl group having 1 to 11 carbon atoms, and the sum of the number of carbon atoms of R ₃ and R ₄ is 9 to 12. }

{In the formula, R ₅ is an alkyl group having 5 to 10 carbon atoms. }

{In the formula, R ₆ and R ₇ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or the following general formula (5):

(In the formula, R ₉ represents an alkyl group having 1 to 5 carbon atoms)
Represents a group X represented by, but R ₆ and R ₇ do not become the group X, R ₈ represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and n5 is 1 ≦ It is a number that satisfies n5 ≦ 3. }
The photosensitive resin composition for spin coating according to any one of claims 1 to 4, which is at least one selected from the group consisting of compounds represented by:   The (C) solvent is 2-octanone, 2-nonanone, diisobutyl ketone, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, di The photosensitive resin composition for spin coating according to any one of claims 1 to 5, which is at least one selected from the group consisting of propylene glycol dimethyl ether and dipropylene glycol methyl propyl ether.   7. The (A) alkali-soluble resin is at least one selected from the group consisting of alkali-soluble polyimides, polyimide precursors, polybenzoxazole precursors, and phenol resins, according to any one of claims 1 to 6. The photosensitive resin composition for spin coating as described above. The (A) alkali-soluble resin has the following general formula (6):

{In the formula, X ₁ and Y ₁ each independently represent a divalent to octavalent organic group having 2 to 60 carbon atoms, and R ₁₀ and R ₁₁ are each independently a hydrogen atom or a carbon atom. Represents an alkyl group of the numbers 1 to 10, m1 is an integer of 1 to 1000, n1 to n4 are each independently an integer of 0 to 4, and n1 and n3 are 0 ≦ (n1 + n3) ≦ 6. And n2 and n4 satisfy 0 ≦ (n2 + n4) ≦ 6, and all of n1 to n4 are not 0. }
The photosensitive resin composition for spin coating according to any one of claims 1 to 7, comprising a resin represented by and / or a phenol resin.   The spin-coat photosensitive material according to claim 8, wherein the (A) alkali-soluble resin contains 50 parts by mass to 150 parts by mass of a phenol resin with respect to 100 parts by mass of the resin represented by the general formula (6). Resin composition.   The photosensitive resin composition for spin coating according to any one of claims 1 to 9, wherein the photoacid generator (B) is a quinonediazide compound. below:
(A) A step of spin-coating the photosensitive resin composition for spin coating according to any one of claims 1 to 10 onto a substrate to form a photosensitive resin layer or a photosensitive film on the substrate,
(B) a step of exposing the photosensitive resin layer or the photosensitive film,
A cured relief pattern including (c) a step of removing an exposed part or an unexposed part of the photosensitive resin layer or the photosensitive film with a developer to obtain a relief pattern, and (d) a step of heating the relief pattern. Manufacturing method.   A cured relief pattern obtained by the method according to claim 11.   A semiconductor device comprising a semiconductor element and a cured film provided on the semiconductor element, wherein the cured film is the cured relief pattern according to claim 12.   A display device comprising a display element and a cured film provided on the display element, wherein the cured film is the cured relief pattern according to claim 12.