JP5825860B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition used for forming a surface protective film or an interlayer insulating film of a semiconductor element, and a novel phenol resin. More specifically, the present invention relates to a photosensitive resin composition used for forming a surface protective film (buffer coat film) and an interlayer insulating film (passivation film) of a semiconductor element. The present invention also relates to a method of manufacturing a semiconductor device using the above-described photosensitive resin composition as a relief pattern forming material, and a semiconductor device manufactured by the method.

  Conventionally, polyimide resins and polybenzoxazole resins having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like have been widely used for surface protective films and interlayer insulating films used in semiconductor devices. Since these resins have low solubility in various solvents, they are generally used as a composition dissolved in a solvent in the form of a precursor. Therefore, a step for cyclizing such a precursor is required in use. This cyclization step is performed by thermosetting in which the precursor is usually heated to 300 ° C. or higher.

  However, in recent years, semiconductor devices having lower heat resistance compared to conventional products have been developed, and the material for forming the surface protective film and the interlayer insulating film is required to have a lower thermosetting temperature, particularly at 250 ° C. or lower. The thermosetting property is often required.

  In response to such a request, Patent Document 1 below is obtained by condensing phenols and aldehydes that do not require a ring-closing step, are excellent in cost and photosensitivity, and are widely used as base resins in the resist field. A material using a phenol resin and crosslinkable fine particles for improving the thermal shock resistance of the phenol resin has been proposed. However, the effect of improving thermal shock resistance is not always sufficient.

  Further, in Patent Documents 2 and 3 below, a phenol compound having one phenolic hydroxyl group in the molecule and a phenol having two phenolic hydroxyl groups in the molecule are used in order to improve the flow performance when the phenol resin is used. The resulting phenolic resin is melted by copolymerizing a biphenyldiyl crosslinkable type polymer unit containing both of the compound and a methylene crosslinkable type polymer unit, and setting the ratio of the degree of polymerization of both to a specific range. A method for reducing the viscosity is proposed.

  Patent Document 4 discloses a material in which a phenol resin having a condensate of a biphenyldiyl compound and a phenol as a skeleton and a photoacid generator are used in combination. However, this composition is disclosed as a liquid crystal alignment control protrusion and / or spacer formation or as a liquid crystal alignment control protrusion and spacer formation simultaneously.

JP 2003-215789 A JP 2008-156553 A International Publication No. 2007/007827 Pamphlet JP 2008-292677 A

  In the materials disclosed in the above-mentioned patent documents, although thermal shock resistance or melt viscosity can be improved, elongation and dielectric constant which are important film properties when applied to a semiconductor device as a surface protective film or an interlayer insulating film In addition, the solubility in an aqueous alkali solution necessary for pattern processing has not been studied at all.

  In view of the present situation, the problem to be solved by the present invention is that, even when applied to a semiconductor device and cured with heat of, for example, 250 ° C. or less, the elongation is high and the dielectric constant is low. Photosensitive resin composition containing phenol resin that can be used as substitute material for oxazole resin, method for manufacturing semiconductor device using the photosensitive resin composition as a relief pattern forming material, semiconductor device obtained by the method, and novel phenol resin Is to provide.

  As a result of intensive investigations and repeated experiments to solve the above problems, the inventors of the present invention have excellent elongation and low properties even when the thermosetting temperature is as low as 250 ° C. or less, for example, when applied to a semiconductor device. The present inventors have completed the present invention by unexpectedly finding a material that can form a semiconductor protective film or an interlayer insulating film having a dielectric constant. That is, the present invention is as follows.

｛式中、
Ｒ₁及びＲ₂は、それぞれ独立に、ハロゲン原子；ニトロ基；シアノ基；不飽和結合を有していてもよい炭素数１〜１０の脂肪族基；炭素数３〜２０の脂環式基；炭素数６〜２０の芳香族基：又は、下記一般式群（３）：

（式中、Ｒ_3、Ｒ₄及びＲ₅は、それぞれ独立に、水素原子；不飽和結合を有していてもよい炭素数１〜１０の脂肪族基；炭素数３〜２０の脂環式基；又は炭素数６〜２０の芳香族基；を表し、Ｒ₆は、不飽和結合を有していてもよい炭素数１〜１０の脂肪族基；炭素数３〜２０の脂環式基；又は炭素数６〜２０の芳香族基；を表す。）のいずれかで表される基；を表し、
Ｘ及びＹは、それぞれ独立に、不飽和結合を有していてもよい炭素数１〜１０の脂肪族基；炭素数３〜２０の脂環式基；繰り返し単位数が１〜２０の整数であるエチレンオキシド基；又は芳香族基を有する有機基；を表し、
Ｒ_１〜Ｒ_６，Ｘ及びＹにおいて、水素原子がハロゲン原子、カルボキシル基、ニトロ基及びシアノ基からなる群から選ばれる少なくとも１つで置換されていてもよく、
ａ及びｂは、それぞれ独立に、２〜１，０００の間の整数であり、
ｍは１又は２であり、ｎは２又は３であり、但しｎ＞ｍであり、
ｐは、０〜３の整数であり、
ｑは、０〜２の整数である。｝
の両者を有する、上記［１］に記載の感光性樹脂組成物。
［３］ 上記一般式（１）及び（２）におけるＸ及びＹが、それぞれ独立に、下記一般式（４）：

｛式中、Ｒ₇〜Ｒ₁₀は、それぞれ独立に、水素原子；又はフッ素で置換されてもよい炭素数１〜１０の脂肪族基；を表す。｝
で表される基、又は下記一般式（５）：

｛式中、Ｒ₁₁〜Ｒ₁₄は、それぞれ独立に、水素原子；又はフッ素で置換されてもよい炭素数１〜１０の脂肪族基；を表し、Ｚは、単結合；フッ素で置換されてもよい炭素数１〜１０の脂肪族基；フッ素で置換されてもよい炭素数３〜２０の脂環式基；繰り返し単位数１〜２０のエチレンオキシド基；又は下記式群（６）：

のいずれかで表される基；を表す。｝
で表される基である、上記［１］又は［２］に記載の感光性樹脂組成物。
［４］ 上記一般式（１）及び（２）におけるＸ及びＹが、下記一般式（７）：

｛式中、Ｗは、単結合；フッ素で置換されてもよい炭素数１〜１０の脂肪族基；フッ素で置換されてもよい炭素数３〜２０の脂環式基；繰り返し単位数１〜２０のエチレンオキシド基；又は下記式群（８）：

のいずれかで表される基；を表す。｝
で表される基である、上記［１］〜［３］のいずれかに記載の感光性樹脂組成物。
［５］ 上記一般式（１）及び（２）において、ｂ／ａ＞１である、上記［１］〜［４］のいずれかに記載の感光性樹脂組成物。
［６］ 上記光酸発生剤（Ｂ）が、キノンジアジド化合物である、上記［１］〜［５］のいずれかに記載の感光性樹脂組成物。
［７］ 上記感光性樹脂組成物が、熱により若しくは上記光酸発生剤（Ｂ）から発生した酸により上記フェノール樹脂（Ａ）と反応しうる化合物、又は熱により若しくは上記光酸発生剤（Ｂ）から発生した酸により自己反応が起こりうる化合物である、架橋剤（Ｃ）：１〜６０質量部を更に含有する、上記［１］〜［６］のいずれかに記載の感光性樹脂組成物。
［８］ 以下の工程：
半導体基板上に、上記［１］〜［７］のいずれかに記載の感光性樹脂組成物からなる感光性樹脂層を形成する工程、
該感光性樹脂層を活性光線で露光する工程、
該露光された感光性樹脂層を現像してレリーフパターンを得る工程、及び
得られたレリーフパターンを加熱する工程
を含む、半導体装置の製造方法。
［９］ 上記［８］に記載の方法により製造された、半導体装置。
［１０］ 主鎖に、下記一般式（９）：

｛式中、Ｒ₁₅は、独立に、水素原子；フッ素原子；又はフッ素で置換されてもよい炭素数１〜１０の脂肪族基；を表し、ｃは、３〜１，０００の間の整数である。｝
で表される構造、及び下記一般式（１０）：

｛式中、Ｒ₁₆は、独立に、水素原子；フッ素原子；又はフッ素で置換されてもよい炭素数１〜１０の脂肪族基；を表し、ｄは、３〜１，０００の間の整数である。｝
で表される構造、の両者を有する、フェノール樹脂。 [1] A photosensitive resin composition for forming a surface protective film or an interlayer insulating film of a semiconductor element,
Phenol resin (A) which is a polymerization reaction product of a polymerization component containing two or more phenolic compounds having different numbers of phenolic hydroxyl groups: 100 parts by mass; and photoacid generator (B): 0.1-50 parts by mass;
The photosensitive resin composition containing this.
[2] The phenol resin (A) has a structure represented by the following general formula (1) and a structure represented by the following general formula (2):

{Where
R ₁ and R ₂ are each independently a halogen atom; a nitro group; a cyano group; an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond; an alicyclic group having 3 to 20 carbon atoms An aromatic group having 6 to 20 carbon atoms: or the following general formula group (3):

(In the formula, R _3, R ₄ and R ₅ are each independently a hydrogen atom; an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond; an alicyclic group having 3 to 20 carbon atoms. Or an aromatic group having 6 to 20 carbon atoms, and R ₆ is an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond; an alicyclic group having 3 to 20 carbon atoms. Or an aromatic group having 6 to 20 carbon atoms; a group represented by any one of
X and Y are each independently an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond; an alicyclic group having 3 to 20 carbon atoms; an integer having 1 to 20 repeating units. An ethylene oxide group; or an organic group having an aromatic group;
In R _{1 to} R ₆ , X and Y, the hydrogen atom may be substituted with at least one selected from the group consisting of a halogen atom, a carboxyl group, a nitro group and a cyano group,
a and b are each independently an integer between 2 and 1,000;
m is 1 or 2, n is 2 or 3, provided that n> m,
p is an integer of 0 to 3,
q is an integer of 0-2. }
The photosensitive resin composition according to the above [1], having both of the above.
[3] X and Y in the above general formulas (1) and (2) are each independently the following general formula (4):

{Wherein, R _{7 to} R ₁₀ each independently represents a hydrogen atom; or an aliphatic group having 1 to 10 carbon atoms which may be substituted with fluorine. }
Or a group represented by the following general formula (5):

{Wherein, R _{11 to} R ₁₄ each independently represents a hydrogen atom; or an aliphatic group having 1 to 10 carbon atoms which may be substituted with fluorine; Z represents a single bond; substituted with fluorine; An aliphatic group having 1 to 10 carbon atoms; an alicyclic group having 3 to 20 carbon atoms which may be substituted with fluorine; an ethylene oxide group having 1 to 20 repeating units; or the following formula group (6):

A group represented by any one of the following: }
The photosensitive resin composition as described in said [1] or [2] which is group represented by these.
[4] X and Y in the above general formulas (1) and (2) are the following general formula (7):

{Wherein W is a single bond; an aliphatic group having 1 to 10 carbon atoms which may be substituted with fluorine; an alicyclic group having 3 to 20 carbon atoms which may be substituted with fluorine; 20 ethylene oxide groups; or the following formula group (8):

A group represented by any one of the following: }
The photosensitive resin composition in any one of said [1]-[3] which is group represented by these.
[5] The photosensitive resin composition according to any one of [1] to [4], wherein b / a> 1 in the general formulas (1) and (2).
[6] The photosensitive resin composition according to any one of [1] to [5], wherein the photoacid generator (B) is a quinonediazide compound.
[7] The photosensitive resin composition is a compound that can react with the phenol resin (A) by heat or an acid generated from the photoacid generator (B), or by heat or the photoacid generator (B The photosensitive resin composition according to any one of the above [1] to [6], further comprising 1 to 60 parts by mass of a crosslinking agent (C) which is a compound capable of causing a self-reaction by an acid generated from .
[8] The following steps:
Forming a photosensitive resin layer comprising the photosensitive resin composition according to any one of [1] to [7] on a semiconductor substrate;
Exposing the photosensitive resin layer with actinic rays;
The manufacturing method of a semiconductor device including the process of developing this exposed photosensitive resin layer, obtaining a relief pattern, and the process of heating the obtained relief pattern.
[9] A semiconductor device manufactured by the method according to [8] above.
[10] In the main chain, the following general formula (9):

{In the formula, R ₁₅ independently represents a hydrogen atom; a fluorine atom; or an aliphatic group having 1 to 10 carbon atoms which may be substituted with fluorine; and c represents an integer between 3 and 1,000. It is. }
And the following general formula (10):

{In the formula, R ₁₆ independently represents a hydrogen atom; a fluorine atom; or an aliphatic group having 1 to 10 carbon atoms which may be substituted with fluorine; and d represents an integer between 3 and 1,000. It is. }
The phenol resin which has both of the structure represented by these.

  By using the photosensitive resin composition of the present invention that can be cured at a low temperature and has excellent mechanical and electrical properties of a cured film such as elongation and dielectric constant, a highly reliable semiconductor element and the A highly reliable semiconductor device using a semiconductor element can be manufactured.

<Photosensitive resin composition>
The photosensitive resin composition (hereinafter also simply referred to as “the present composition”) provided by one embodiment of the present invention is a polymerization reaction product of polymerization components containing two or more phenolic compounds having different numbers of phenolic hydroxyl groups. A certain phenol resin (A): 100 parts by mass; and a photoacid generator (B): 0.1 to 50 parts by mass.

  Hereinafter, although each component of the photosensitive resin composition of this invention is demonstrated in detail, this description is an illustration and this invention is not limited to this.

[Phenolic resin (A)]
The phenolic resin (A) (hereinafter also simply referred to as “phenolic resin”) is a copolymer obtained by reacting a polymerization component containing two or more types of phenolic compounds having different numbers of phenolic hydroxyl groups. The phenol resin (A) is a polymer having two or more types of repeating units due to the difference in the number of phenolic hydroxyl groups in the phenol compound in the main chain. Two or more different types of repeating units can be combined in any order, randomly or in blocks.

｛式中、
Ｒ₁及びＲ₂は、それぞれ独立に、ハロゲン原子；ニトロ基；シアノ基；不飽和結合を有していてもよい炭素数１〜１０の脂肪族基；炭素数３〜２０の脂環式基；炭素数６〜２０の芳香族基：又は、下記一般式群（３）：

（式中、Ｒ_3、Ｒ₄及びＲ₅は、それぞれ独立に、水素原子；不飽和結合を有していてもよい炭素数１〜１０の脂肪族基；炭素数３〜２０の脂環式基；又は炭素数６〜２０の芳香族基；を表し、Ｒ₆は、不飽和結合を有していてもよい炭素数１〜１０の脂肪族基；炭素数３〜２０の脂環式基；又は炭素数６〜２０の芳香族基；を表す。）のいずれかで表される基；を表し、
Ｘ及びＹは、それぞれ独立に、不飽和結合を有していてもよい炭素数１〜１０の脂肪族基；炭素数３〜２０の脂環式基；繰り返し単位数が１〜２０の整数であるエチレンオキシド基；又は芳香族基を有する有機基；を表し、
Ｒ_１〜Ｒ_６，Ｘ及びＹにおいて、水素原子がハロゲン原子、カルボキシル基、ニトロ基及びシアノ基からなる群から選ばれる少なくとも１つで置換されていてもよく、
ａ及びｂは、それぞれ独立に、２〜１，０００の間の整数であり、
ｍは１又は２であり、ｎは２又は３であり、但しｎ＞ｍであり、
ｐは、０〜３の整数であり、
ｑは、０〜２の整数である。｝
の両者を有する。 The phenol resin (A) has a structure represented by the following general formula (1) and a structure represented by the general formula (2):

{Where
R ₁ and R ₂ are each independently a halogen atom; a nitro group; a cyano group; an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond; an alicyclic group having 3 to 20 carbon atoms An aromatic group having 6 to 20 carbon atoms: or the following general formula group (3):

(In the formula, R _3, R ₄ and R ₅ are each independently a hydrogen atom; an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond; an alicyclic group having 3 to 20 carbon atoms. Or an aromatic group having 6 to 20 carbon atoms, and R ₆ is an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond; an alicyclic group having 3 to 20 carbon atoms. Or an aromatic group having 6 to 20 carbon atoms; a group represented by any one of
X and Y are each independently an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond; an alicyclic group having 3 to 20 carbon atoms; an integer having 1 to 20 repeating units. An ethylene oxide group; or an organic group having an aromatic group;
In R _{1 to} R ₆ , X and Y, the hydrogen atom may be substituted with at least one selected from the group consisting of a halogen atom, a carboxyl group, a nitro group and a cyano group,
a and b are each independently an integer between 2 and 1,000;
m is 1 or 2, n is 2 or 3, provided that n> m,
p is an integer of 0 to 3,
q is an integer of 0-2. }
Have both.

When the phenol resin (A) has both the structure represented by the general formula (1) and the structure represented by the general formula (2), the phenol resin (A) has a low dielectric constant and excellent elongation. , And contributes well to the excellent solubility in aqueous alkali solutions. The molar ratio of the unit structure repeated in number a in the general formula (1) and the unit structure repeated in number b in the general formula (2) present in the phenol resin (A) is the photosensitive resin composition. From the viewpoint of solubility in an alkaline developer, b / a is preferably greater than 1, and more preferably b / a is 1.1 or more and 10 or less. The molar ratio can be confirmed by ¹ H-NMR analysis.

M in the general formula (1), that is, the number of phenolic hydroxyl groups is 1 or 2.
Examples of phenolic compounds having 1 phenolic hydroxyl group include, for example, phenol, cresol, ethylphenol, propylphenol, butylphenol, amylphenol, cyclohexylphenol, hydroxybiphenyl, benzylphenol, nitrobenzylphenol, cyanobenzylphenol, adamantanephenol, Xylenol, nitrophenol, fluorophenol, chlorophenol, bromophenol, trifluoromethylphenol, N- (hydroxyphenyl) -5-norbornene-2,3-dicarboximide, N- (hydroxyphenyl) -5-methyl-5 -Norbornene-2,3-dicarboximide, trifluoromethylphenol, hydroxybenzoic acid, methyl hydroxybenzoate, hydroxy Ethyl benzoate, hydroxybenzoic acid benzyl, hydroxybenzamide, hydroxybenzaldehyde, hydroxyacetophenone, hydroxybenzophenone, and include hydroxy benzonitrile.

  Examples of phenolic compounds having 2 phenolic hydroxyl groups include catechol, methyl catechol, ethyl catechol, hexyl catechol, benzyl catechol, nitrobenzyl catechol, resorcinol, methyl resorcinol, ethyl resorcinol, hexyl resorcinol, benzyl resorcinol, nitrobenzyl resorcinol, hydroquinone , Caffeic acid, dihydroxybenzoic acid, methyl dihydroxybenzoate, ethyl dihydroxybenzoate, benzyl dihydroxybenzoate, dihydroxybenzamide, dihydroxybenzaldehyde, dihydroxyacetophenone, dihydroxybenzophenone, dihydroxybenzonitrile, N- (dihydroxyphenyl) -5-norbornene -2,3-dicarboximide, N (Dihydroxyphenyl) -5-methyl-5-norbornene-2,3-dicarboximide, nitrocatechol, fluorocatechol, chlorocatechol, bromocatechol, trifluoromethylcatechol, nitroresorcinol, fluororesorcinol, chlororesorcinol, bromoresorcinol, And trifluoromethylresorcinol. From the viewpoint of reducing the dielectric constant of the copolymer, it is desirable that the number of phenolic hydroxyl groups in the general formula (1) is 1.

  N in the general formula (2), that is, the number of phenolic hydroxyl groups is 2 or 3. Specific examples of the phenolic compound having 2 phenolic hydroxyl groups are the same as the specific examples of the phenolic compound having 2 phenolic hydroxyl groups given for the general formula (1). Specific examples of phenolic compounds having 3 phenolic hydroxyl groups include, for example, pyrogallol, phloroglucinol, 1,2,4-trihydroxybenzene, trihydroxybenzoic acid, methyl trihydroxybenzoate, and ethyl trihydroxybenzoate. Benzyl trihydroxybenzoate, trihydroxybenzamide, trihydroxybenzaldehyde, trihydroxyacetophenone, trihydroxybenzophenone, trihydroxybenzonitrile and the like. From the viewpoint of ensuring the solubility of the phenol resin (A) in an alkaline aqueous solution, the number of phenolic hydroxyl groups in the general formula (2) is preferably 3.

From the viewpoint of the solubility of the phenol resin (A) in an aqueous alkali solution and the viewpoint of less by-product formation during polymer synthesis, preferred R ₁ and R ₂ in the above general formulas (1) and (2) are: Each independently includes a methyl group, a halogen atom, a trifluoromethyl group, a nitro group, a cyano group, an acetyl group, a phenylcarbonyl group, a carboxyl group, an ester group, an amide group, and an imide group from the viewpoint of alkali solubility. Particularly preferred examples are a fluorine atom, a trifluoromethyl group, a carboxyl group, an ester group, and an imide group.

  P in the general formula (1) is an integer of 0 to 3, q in the general formula (2) is an integer of 0 to 2, and p and q are independently reactive during polymer synthesis. From the viewpoint, it is preferably 0 or 1.

  From the viewpoint of achieving both the low dielectric constant of the phenol resin (A) and the solubility in an alkaline aqueous solution, in the above general formulas (1) and (2), n> m. That is, when the number of phenolic hydroxyl groups in the general formula (1) is 1, the number of phenolic hydroxyl groups in the general formula (2) is 2 or 3, preferably 3. When the number of phenolic hydroxyl groups in the general formula (1) is 2, the number of phenolic hydroxyl groups in the general formula (2) is 3.

  In the general formulas (1) and (2), X and Y are each independently an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, or an alicyclic group having 3 to 20 carbon atoms. Group, an ethylene oxide group having a repeating unit number of 1 to 20, or an organic group having an aromatic group, and the hydrogen atoms of X and Y are selected from the group consisting of a halogen atom, a carboxyl group, a nitro group and a cyano group. It may be substituted with at least one selected. When X and Y are aliphatic groups, the number of carbon atoms is preferably 2 to 10 from the viewpoint of mechanical properties of the cured film.

  The phenol resin (A) typically includes two or more types of phenolic compounds having different numbers of phenolic hydroxyl groups and a polymerization component (specifically, an aldehyde compound, a ketone compound, a compound having two methylol groups in the molecule, One or more compounds selected from the group consisting of a compound having two alkoxymethyl groups in the molecule, a diene compound, and a compound having two haloalkyl groups in the molecule, and more typically The component) can be synthesized by a polymerization reaction. For example, when the phenol resin (A) has both the structure represented by the general formula (1) and the structure represented by the general formula (2), the phenol resin (A) has different numbers of phenolic hydroxyl groups. An aldehyde compound, a ketone compound, a compound having two methylol groups in the molecule, a compound having two alkoxymethyl groups in the molecule, a diene compound, and two or more types of phenol compounds and the above X or Y structure, and It can be obtained by polymerizing one or more compounds selected from the group consisting of compounds having two haloalkyl groups in the molecule. From the viewpoint of reaction control and the stability of the obtained phenolic resin and photosensitive resin composition, the preferred charge molar ratio of the phenolic compound and the polymerization component is from 5: 1 to 1.01: 1, more preferably moles. The ratio includes 2.5: 1 to 1.1: 1.

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

  Examples of the ketone compound include acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, dicyclohexyl ketone, dibenzyl ketone, cyclopentanone, cyclohexanone, bicyclohexanone, cyclohexanedione, butynone, norbornanone, adamantanone, and bis (oxocyclohexyl) propane. Is mentioned.

  Compounds having two methylol groups in the molecule include bis (hydroxymethyl) urea, ribitol, arabitol, allitol, bis (hydroxymethyl) butyric acid, benzyloxypropanediol, dimethylpropanediol, diethylpropanediol, monoacetin, methyl Nitropropanediol, norbornene dimethanol, pentaerythritol, phenylpropanediol, trimethylolethane, trimethylolpropane, bis (hydroxymethyl) durene, nitroxylylene glycol, dihydroxydecane, dihydroxydodecane, bis (hydroxymethyl) cyclohexane, bis ( Hydroxymethyl) cyclohexene, bis (hydroxymethyl) adamantane, benzenedimethanol, benzenedimethanol, (Hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) naphthalene, bis (hydroxymethyl) anthracene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) diphenylthioether, bis (hydroxymethyl) benzophenone, Hydroxymethylphenyl hydroxymethylbenzoate, hydroxymethylanilide hydroxymethylbenzoate, bis (hydroxymethyl) phenylurea, bis (hydroxymethyl) phenylurethane, bis (hydroxymethyl) biphenyl, dimethylbis (hydroxymethyl) biphenyl, bis (hydroxy Methylphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene Glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and the like. From the viewpoint of reactivity and mechanical properties of the obtained phenol resin, a compound having a benzene ring in the molecular skeleton is preferable, a compound having a biphenyldiyl skeleton is more preferable, and 4,4′-bis (hydroxymethyl) biphenyl is particularly preferable. .

  Examples of the compound having two alkoxymethyl groups in the molecule include bis (methoxymethyl) urea, bis (methoxymethyl) butyric acid, bis (methoxymethyl) norbornene, bis (methoxymethyl) cyclohexane, bis (methoxymethyl) cyclohexene, Bis (methoxymethyl) adamantane, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) naphthalene, bis (methoxymethyl) anthracene, bis (methoxymethyl) diphenyl ether, Bis (methoxymethyl) diphenylthioether, bis (methoxymethyl) benzophenone, methoxymethylphenyl methoxymethylbenzoate, methoxymethylanilide methoxymethylbenzoate, bis (meth Xymethyl) phenylurea, bis (methoxymethyl) phenylurethane, bis (methoxymethyl) biphenyl, dimethylbis (methoxymethyl) biphenyl, bis (methoxymethylphenyl) propane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene Examples include glycol dimethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, and tetrapropylene glycol dimethyl ether. The number of carbon atoms of the alkoxymethyl group is preferably 1 to 10 from the viewpoint of reaction activity. The number of carbon atoms is more preferably 1 to 2, and most preferably 1. From the viewpoint of reactivity and mechanical properties of the obtained phenol resin, those having a benzene ring in the molecular skeleton are preferred, compounds having a biphenyldiyl skeleton are more preferred, and 4,4′-bis (methoxymethyl) biphenyl is particularly preferred. It is.

  Examples of the diene compound include butadiene, pentadiene, hexadiene, heptadiene, octadiene, decadiene, methylbutadiene, butanediol dimethacrylate, hexadieneol, methylcyclohexadiene, cyclopentadiene, cyclohexadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene. , Hydroxydicyclopentadiene, methylcyclopentadiene, methyldicyclopentadiene, diallyl ether, diallyl sulfide, diallyl adipate, norbornadiene, tetrahydroindene, ethylidene norbornene, vinyl norbornene, diallyl oxalate, diallyl glutarate, diallyl adipate, cyanuric acid Triallyl, diallyl cyanurate, diallylpropyl cyanurate, Null triallyl isocyanuric acid, diallyl propyl etc. isocyanuric acid.

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

｛式中、Ｒ₇〜Ｒ₁₀は、それぞれ独立に、水素原子；又はフッ素で置換されてもよい炭素数１〜１０の脂肪族基；を表す。｝
で表される基、又は下記一般式（５）：

｛式中、Ｒ₁₁〜Ｒ₁₄は、それぞれ独立に、水素原子；又はフッ素で置換されてもよい炭素数１〜１０の脂肪族基；を表し、Ｚは、単結合；フッ素で置換されてもよい炭素数１〜１０の脂肪族基；フッ素で置換されてもよい炭素数３〜２０の脂環式基；繰り返し単位数１〜２０のエチレンオキシド基；又は下記式群（６）：

のいずれかで表される基；を表す。｝
で表される基であることが特に好ましく、下記一般式（７）：

｛式中、Ｗは、単結合；フッ素で置換されてもよい炭素数１〜１０の脂肪族基；フッ素で置換されてもよい炭素数３〜２０の脂環式基；繰り返し単位数１〜２０のエチレンオキシド基；又は下記式群（８）：

のいずれかで表される基；を表す。｝で表される基であることが最も好ましい。 From the viewpoint of heat resistance, X and Y in the above general formulas (1) and (2) are each independently the following general formula (4):

{Wherein, R _{7 to} R ₁₀ each independently represents a hydrogen atom; or an aliphatic group having 1 to 10 carbon atoms which may be substituted with fluorine. }
Or a group represented by the following general formula (5):

{Wherein, R _{11 to} R ₁₄ each independently represents a hydrogen atom; or an aliphatic group having 1 to 10 carbon atoms which may be substituted with fluorine; Z represents a single bond; substituted with fluorine; An aliphatic group having 1 to 10 carbon atoms; an alicyclic group having 3 to 20 carbon atoms which may be substituted with fluorine; an ethylene oxide group having 1 to 20 repeating units; or the following formula group (6):

A group represented by any one of the following: }
Is particularly preferably a group represented by the following general formula (7):

{Wherein W is a single bond; an aliphatic group having 1 to 10 carbon atoms which may be substituted with fluorine; an alicyclic group having 3 to 20 carbon atoms which may be substituted with fluorine; 20 ethylene oxide groups; or the following formula group (8):

A group represented by any one of the following: } Is most preferable.

  A and b in the above general formulas (1) and (2) represent the total number of each repeating unit in the polymer main chain, each independently an integer between 2 and 1,000, and the lower limit is Preferably it is 3, more preferably 4, and the upper limit is preferably 900, more preferably 800, and even more preferably 500. a and b are preferably 2 or more from the viewpoint of the toughness of the cured film, and preferably 1,000 or less from the viewpoint of solubility in an aqueous alkali solution.

  Next, a typical method for synthesizing the phenol resin (A) will be described in detail. Two or more types of phenolic compounds having different numbers of phenolic hydroxyl groups, polymerization components, specifically, aldehyde compounds, ketone compounds, compounds having two methylol groups in the molecule, compounds having two alkoxymethyl groups in the molecule A phenol resin (A) by heating and stirring one or more compounds selected from the group consisting of a diene compound and a compound having two haloalkyl groups in the molecule in the presence of a suitable polymerization catalyst. Can be obtained. The polymerization catalyst is not particularly limited, but an acid catalyst is preferable. Acid catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, oxalic acid and diethyl sulfate, Lewis such as boron trifluoride, anhydrous aluminum chloride and zinc chloride. An acid etc. are mentioned. The amount of the acid catalyst used is preferably in the range of 0.01 to 5 mol% with respect to the number of moles of the methylol compound, alkoxymethyl compound or diene compound. Examples of the alkaline catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, triethylamine, pyridine, 4-N, N-dimethylaminopyridine, piperidine, piperazine, 1,4- Diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, ammonia, hexamethylenetetramine, etc. Is mentioned.

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

  Moreover, when performing the synthetic reaction of a phenol resin (A), you may react by charging simultaneously the 2 or more types of phenolic compound from which the number of phenolic hydroxyl groups differs, and the said polymerization component. Among the phenol compounds, it is also possible to employ a method in which one or more kinds of phenol compounds and the above polymerization component are charged first and reacted to a certain molecular weight, and then another one or more kinds of phenol compounds are charged and continuously reacted.

  The weight average molecular weight of the phenol resin (A) is preferably 700 to 100,000, more preferably 1,500 to 80,000, still more preferably 2,000 to 50,000. The weight average molecular weight is preferably 700 or more from the viewpoint of elongation, and preferably 100,000 or less from the viewpoint of alkali solubility of the composition. The weight average molecular weight is a value obtained in terms of standard polystyrene using gel permeation chromatography.

  Moreover, as long as the effect of this invention is not affected, the photosensitive resin composition can further contain other alkaline aqueous solution soluble resin other than the said phenol resin (A). As other alkaline aqueous solution-soluble resin, specifically, a phenol resin, polyhydroxystyrene resin, polyamide, polyimide, which is a condensation reaction product of one type of phenol compound (that is, does not contain a copolymerized phenol resin structure), and Examples of these resins include derivatives, precursors, and copolymers.

  In addition, when using a phenol resin (A) mixed with other alkaline aqueous solution soluble resin, the content rate of a phenol resin (A) is 50 mass% or more from a viewpoint of elongation among composition of mixed resin. It is preferable that it is 60 mass% or more.

[Photoacid generator (B)]
The photosensitive resin composition of the present invention is not particularly limited as long as it is a composition that can form a resin pattern in response to actinic rays (radiation) represented by ultraviolet rays, electron beams, X-rays, and the like. Either a negative photosensitive resin composition or a positive photosensitive resin composition may be used.

  When the photosensitive resin composition of the present invention is used as a negative photosensitive resin composition, the photoacid generator (B) generates an acid upon irradiation with radiation, and the generated acid is the phenol resin ( A crosslinking reaction between A) and other components of the composition described later can be caused. Examples of such compounds include the following compounds:

(I) 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-trichloro Methyl) -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- - styryl) - bis (4,6-trichloromethyl) -s-triazine and the like;

(Ii) Diallyliodonium Diphenyliodonium tetrafluoroborate, diphenyliodonium tetrafluorophosphate, diphenyliodonium tetrafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, 4-methoxy Phenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, 4 −Me Toxiphenylphenyliodonium-p-toluenesulfonate, 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, etc .;

(Iii) Triallylsulfonium salts Triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluene Sulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenylsulfonium Trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoroarsenate, 4-phenylthiophenyldiphenyl Trifluoromethanesulfonate, 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, 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 diaryl iodonium salts include diphenyl iodonium trifluoroacetate, diphenyl iodonium trifluoromethane sulfone. Nato, 4-methoxyphenylphenyliodonium trifluoromethane For example, sulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, and triarylsulfonium salts include triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyl. Diphenylsulfonium trifluoroacetate, 4-phenylthiophenyl diphenyl trifluoromethanesulfonate, 4-phenylthiophenyl diphenyl trifluoroacetate and the like can be mentioned as suitable ones.

  In addition, the following compounds can also be used as the photoacid generator (B).

(1) Diazoketone compound Examples of the diazoketone compound include 1,3-diketo-2-diazo compound, diazobenzoquinone compound, diazonaphthoquinone compound, and the like. Specific examples include 1,2-naphthoquinonediazide of phenols. A 4-sulfonic acid ester compound can be mentioned.

(2) Sulfone compounds Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds and α-diazo compounds of these compounds. Specific examples include 4-trisphenacylsulfone, mesitylphena. Examples include silsulfone and bis (phenacylsulfonyl) methane.

(3) Sulfonic acid compound Examples of the sulfonic acid compound include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Preferred examples include benzoin tosylate, pyrogallol tris trifluoromethane sulfonate, o-nitrobenzyl trifluoromethane sulfonate, o-nitrobenzyl-p-toluene sulfonate, and the like.

(4) Sulfonimide compound Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- ( (Trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide and the like.

(5) Oxime ester compound As an oxime ester compound, specifically, 2- [2- (4-methylphenylsulfonyloxyimino)]-2,3-dihydrothiophene-3-ylidene] -2- (2-methyl Phenyl) acetonitrile (trade name “Irgacure PAG121” manufactured by Ciba Specialty Chemicals), [2- (propylsulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (Ciba Specialty) Chemicals trade name “Irgacure PAG103”), [2- (n-octanesulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (Ciba Specialty Chemicals trade name) "Irgacure PAG 108 ”), α- (n-octanesulfonyloxyimino) -4-methoxybenzyl cyanide (trade name“ CGI725 ”manufactured by Ciba Specialty Chemicals) and the like.

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

  From the viewpoint of sensitivity, the above (5) oxime ester compound is particularly preferable.

  When the phenol resin composition of the present invention is a negative type, the blending amount of the photoacid generator (B) with respect to 100 parts by mass of the phenol resin (A) is preferably 0.1 to 50 parts by mass. More preferably, it is -40 mass parts. If the blending amount is 0.1 parts by mass or more, a sensitivity improvement effect can be obtained satisfactorily. If the blending amount is 50 parts by mass or less, the mechanical properties of the cured film are good.

  The photosensitive resin composition of the present invention can also be used as a positive photosensitive resin composition. In this case, the photoacid generator (B) is preferably a quinonediazide compound. A naphthoquinone diazide compound (hereinafter also referred to as “NQD compound”), more specifically a naphthoquinone diazide derivative, is more preferable. Examples of the naphthoquinonediazide derivative include compounds having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure, and these compounds include, for example, US Pat. No. 2,772,972, US This is known from Japanese Patent No. 2,797,213 and US Pat. No. 3,669,658. The naphthoquinonediazide derivative is obtained from 1,2-naphthoquinonediazide-4-sulfonic acid ester of a polyhydroxy compound having a specific structure described in detail below, and 1,2-naphthoquinonediazide-5-sulfonic acid ester of the polyhydroxy compound. At least one compound selected from the group consisting of:

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

  Examples of preferable NQD compounds from the viewpoint of cured film properties such as sensitivity and elongation include those represented by the following general formula group.

｛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が同時に水素原子であることはない。｝。

{Wherein Q is a hydrogen atom or the following group of formulas:

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

  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. A mixture with an ester compound can also be used.

  The naphthoquinonediazide derivatives may be used alone or in combination of two or more.

  The usage-amount of the photo-acid generator (B) in the photosensitive resin composition of this invention is 0.1-50 mass parts with respect to 100 mass parts of phenol resins (A) of this composition, Preferably 1-40 mass parts, More preferably, it is 5-30 mass parts. If the amount used is 0.1 parts by mass, good sensitivity is obtained, and if it is 50 parts by mass or less, the mechanical properties of the cured film are good.

[Crosslinking agent (C)]
The photosensitive resin composition of the present invention is a compound capable of reacting with the phenol resin (A) by heat or an acid generated from the photoacid generator (B) as a crosslinking agent (C), or by heat or photoacid. You may contain the compound in which a self-reaction can occur with the acid generated from the generator (B). By using the crosslinking agent (C) in addition to the phenol resin (A) and the photoacid generator (B), when the coating film of the photosensitive resin composition of the present invention is heat-cured, mechanical properties, heat resistance, The film performance such as chemical resistance can be enhanced. In order to enhance the film performance satisfactorily, the crosslinking agent (C) is preferably an epoxy group, an oxetane group, a —N— (CH ₂ —OR) group {wherein R is a hydrogen atom or a carbon number of 1 Represents an alkyl group of ˜4. } And a —C— (CH ₂ —OR) group {wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. } Is a compound having at least two groups selected from the group consisting of:

In the molecular structural formula of the crosslinking agent (C), an N— (CH ₂ —OR) group (wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). }, For example, a melamine resin and a urea resin in which the N-position is substituted with a methylol group or an alkoxymethyl group are exemplified. Specifically, melamine resin, benzoguanamine resin, glycoluril resin, hydroxyethylene urea resin, urea resin, glycol urea resin, alkoxymethylated melamine resin, alkoxymethylated benzoguanamine resin, alkoxymethylated glycoluril resin, alkoxymethylated urea Examples thereof include resins. Among these, alkoxymethylated melamine resins, alkoxymethylated benzoguanamine resins, alkoxymethylated glycoluril resins, and alkoxymethylated urea resins are known methylolated melamine resins, methylolated benzoguanamine resins, and methylol groups of methylolated urea resins. Are each converted to an alkoxymethyl group.

  Examples of the alkoxymethyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, and the like, but commercially available Cymel 300, 301, 303, 370, 325. 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR 65, 300 (manufactured by Mitsui Cytec Co., Ltd.), Nicarax MX-270, -280,- 290, Nicarak MS-11, Nicarak MW-30, -100, -300, -390, -750 (above, manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used. These compounds can be used alone or in admixture of two or more.

In the molecular structural formula of the crosslinking agent (C), a C— (CH ₂ —OR) group (wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). }, For example, 1,4-bis (methoxymethyl) benzene, 4,4′-biphenyldimethanol, 4,4′-bis (methoxymethyl) biphenyl, commercially available 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A (manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML- PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, dimethylol-Bis-C, dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z, DML-PFP, DML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, ML-Bis25X-PCHP, 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymer-p-cresol, TriML-P, TriML-35XL, Examples include TriML-TrisCR-HAP, HML-TPPHBA, HML-TPPHAP, HMOM-TPPHBA, HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.). These compounds can be used alone or in admixture of two or more.

  In the molecular structural formula of the crosslinking agent (C), examples of those having two or more epoxy groups or oxetane groups include 1,1,2,2-tetra (p-hydroxyphenyl) ethanetetraglycidyl ether, glycerol Triglycidyl ether, ortho-secondary butylphenyl glycidyl ether, 1,6-bis (2,3-epoxypropoxy) naphthalene, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, isocyanuric acid triglycidyl, Denacol EX-201, EX-313 , EX-314, EX-321, EX-411, EX-511, EX-512, EX-612, EX-614, EX-614B, EX-731, EX-810, EX-911, EM-150 (or more , Product name, Nagase Chemte , Inc., Ltd.) epoxy compounds such as xylylene bisoxetane, 3-ethyl-3 {[(3-ethyloxetane - yl) methoxy] methyl} oxetane compound oxetane, and the like. These compounds can be used alone or in admixture of two or more.

  The amount of these crosslinking agents (C) used is preferably 1 to 60 parts by mass, more preferably 3 to 50 parts by mass with respect to 100 parts by mass of the phenol resin (A). When the amount used is 1 part by mass or more, the crosslinking proceeds well, and the effect of enhancing the film properties can be obtained satisfactorily. On the other hand, if the amount used is 60 parts by mass or less, the elongation is kept good.

  In addition, the photosensitive resin composition of this invention is 2,2'-bis (2-oxazoline), 2,2'-isopropylidenebis (4-phenyl) as crosslinking agents other than the said crosslinking agent (C), for example. -2-oxazoline), 1,3-bis (4,5-dihydro-2-oxazolyl) benzene, 1,4-bis (4,5-dihydro-2-oxazolyl) benzene, Epocross K-2010E, K-2020E , K-2030E, WS-500, WS-700, RPS-1005 (above, trade name, manufactured by Nippon Shokubai Co., Ltd.) and other oxazoline compounds, carbodilite SV-02, V-01, V-02, V-03, V Carbodiimide compounds such as -04, V-05, V-07, V-09, E-01, E-02, LA-1 (trade name, manufactured by Nisshinbo Chemical Co., Ltd.), formaldehyde, gluta Aldehydes such as aldehydes, hexamethylenetetramine, trioxane, glyoxal, malondialdehyde, succindialdehyde, and modified aldehydes, 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, 1,3-phenylenebismethylene diisocyanate, dicyclohexylmethane 4,4'-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, Takenate 500, 600, Cosmonate NBDI, ND (above, trade name, manufactured by Mitsui Chemicals), Duranate 17B-60PX, TPA-B80E, MF-B60X, MF -Isocyanate crosslinking agents such as K60X, E402-B80T (trade name, manufactured by Asahi Kasei Chemical Co., Ltd.), acetylacetone aluminum (III) salt, acetyl Seton titanium (IV) salt, acetylacetone chromium (III) salt, acetylacetone magnesium (II) salt, acetylacetone nickel (II) salt, trifluoroacetylacetone aluminum (III) salt, trifluoroacetylacetone titanium (IV) salt, trifluoroacetylacetone chromium ( III) Metal chelating agents such as salt, trifluoroacetylacetone magnesium (II) salt, trifluoroacetylacetone nickel (II) salt, vinyl acetate, trimethylolpropane trimethacrylate, triallyl 1,3,5-benzenetricarboxylate, trimellitic acid Triallyl, pyromellitic acid tetraallyl ester, pentaerythritol pentaacrylate, dipentaerythritol pentaacrylate, trimethylolpropane tri An unsaturated bond-containing compound such as acrylate, ditrimethylolpropane tetraacrylate, BANI-M, and BANI-X (trade name, manufactured by Maruzen Petrochemical Co., Ltd.) can be contained.

[solvent]
The photosensitive resin composition of the present invention may contain a solvent. Examples of the solvent include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons and the like. More specifically, for example, as a solvent, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopenta Non, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl Alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 1,2-dichloro Ethane, 1,4-dichloro butane, chlorobenzene, o- dichlorobenzene, anisole, hexane, may be used heptane, benzene, toluene, xylene, mesitylene and the like.

  The usage-amount of the solvent in this composition becomes like this. Preferably it is 100-1000 mass parts with respect to 100 mass parts of phenol resins (A), More preferably, it is 120-700 mass parts, More preferably, it is 150-500. It is the range of mass parts.

[Other ingredients]
If necessary, the photosensitive resin composition of the present invention may contain a dye, a surfactant, an adhesion aid for enhancing adhesion to the substrate, a dissolution accelerator, a crosslinking accelerator, and the like.

  Examples of the dye include methyl violet, crystal violet, and malachite green. As a compounding quantity of dye, 0.1-30 mass parts is preferable with respect to 100 mass parts of phenol resin (A).

  As the surfactant, for example, non-ionic surfactant made of polyglycols such as polypropylene glycol and polyoxyethylene lauryl ether or derivatives thereof, for example, Fluorard (registered trademark, trade name, manufactured by Sumitomo 3M) Fluorosurfactants such as Megafac (registered trademark, trade name, manufactured by Dainippon Ink & Chemicals), Lumiflon (registered trademark, trade name, manufactured by Asahi Glass Co., Ltd.), such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) ), DBE (trade name, manufactured by Chisso Corporation), granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), and other organosiloxane surfactants.

  As a compounding quantity in the case of using surfactant, 0.01-10 mass parts is preferable with respect to 100 mass parts of phenol resins (A).

  Examples of the adhesion assistant include alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy silane, epoxy polymer, and various alkoxy silanes.

  Preferred examples of alkoxysilane include tetraalkoxysilane, bis (trialkoxysilyl) methane, bis (trialkoxysilyl) ethane, bis (trialkoxysilyl) ethylene, bis (trialkoxysilyl) hexane, and bis (trialkoxysilyl). Octane, bis (trialkoxysilyl) octadiene, bis [3- (trialkoxysilyl) propyl] disulfide, N-phenyl-3-aminopropyltrialkoxysilane, 3-mercaptopropyltrialkoxysilane, 2- (trialkoxysilylethyl) ) Pyridine, 3-methacryloxypropyltrialkoxysilane, 3-methacryloxypropyl dialkoxyalkylsilane, vinyltrialkoxysilane, 3-ureidopropyltrialkoxysilane, 3- Socyanate propyltrialkoxysilane, 3- (trialkoxysilyl) propyl succinic anhydride, N- (3-trialkoxysilylpropyl) -4,5-dihydroimidazole, 2- (3,4-epoxycyclohexyl) ethyltri Alkoxysilane, 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyl dialkoxyalkylsilane, 3-aminopropyltrialkoxyalkylsilane and 3-aminopropyl dialkoxyalkylsilane and acid anhydrides or acid dianhydrides. Examples include reactants, 3-aminopropyltrialkoxysilane or 3-aminopropyl dialkoxyalkylsilane in which the amino group is converted to a urethane group or a urea group. In addition, examples of the alkyl group in the above compound include a methyl group, an ethyl group, a propyl group, and a butyl group, and examples of the acid anhydride include maleic acid anhydride, phthalic acid anhydride, 5-norbornene-2,3- Examples of the acid dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, and 4,4′-oxydiphthalic dianhydride. Examples of the urethane group include a t-butoxycarbonylamino group, and examples of the urea group include a phenylaminocarbonylamino group.

  As a compounding quantity in the case of using an adhesion assistant, 0.1-30 mass parts is preferable with respect to 100 mass parts of phenol resins (A).

  As the dissolution accelerator, a compound having a hydroxyl group or a carboxyl group is preferable. Examples of the compound having a hydroxyl group include a ballast agent, paracumylphenol, bisphenols, resorcinols, and linear phenolic compounds such as MtrisPC and MtetraPC, which are used in the above-mentioned naphthoquinonediazide compounds, TrisP-HAP, TrisP- Non-linear phenolic compounds such as PHBA and TrisP-PA (all manufactured by Honshu Chemical Industry Co., Ltd.), 2-5 phenol substitutes of diphenylmethane, 1-5 phenol substitutes of 3,3-diphenylpropane, 2 , 2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane and 5-norbornene-2,3-dicarboxylic anhydride, a one-to-two reaction product, bis- (3-amino-4-hydroxyphenyl) ) 1 of sulfone and 1,2-cyclohexyldicarboxylic anhydride 2 reactants, N- hydroxysuccinimide, N- hydroxy phthalimide, and the like N- hydroxy 5-norbornene-2,3-dicarboxylic acid imide.

  Examples of the compound having a carboxyl group include 3-phenyl lactic acid, 4-hydroxyphenyl lactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid, 2-methoxy-2. -(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-methoxy Examples include mandelic acid, mandelic acid, atrolactic acid, O-acetylmandelic acid, α-methoxyphenylacetic acid, O-acetylmandelic acid, α-methoxyphenylacetic acid and the like.

  As a compounding quantity in the case of using a solubility promoter, 0.1-50 mass parts is preferable with respect to 100 mass parts of phenol resins (A).

  As the crosslinking accelerator, those that generate radicals by heat or light are preferable. Examples of radicals generated by heat or light include alkylphenones such as Irgacure 651, 184, 2959, 127, 907, 369, 379 (above, trade name, manufactured by BASF Japan Ltd.), Irgacure 819 (trade name, BASF Japan). Acylphosphine oxide such as Irgacure 784 (trade name, manufactured by BASF Japan), and oxime esters such as Irgacure OXE01, 02 (trade name, manufactured by BASF Japan).

<Method for forming cured relief pattern>
Hereinafter, an example of a method for forming a cured relief pattern on a substrate using the photosensitive resin composition according to the present invention will be described.

  First, the photosensitive resin composition of the present invention is applied to a suitable support such as a silicon wafer, ceramic, aluminum substrate, copper substrate and the like. At this time, in order to ensure the water-resistant adhesion between the pattern to be formed and the support, an adhesion assistant such as a silane coupling agent may be applied to the support in advance. The composition can be applied by spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, or the like. The photosensitive resin layer which consists of the photosensitive resin composition of this invention is formed by said procedure.

  Next, after pre-baking at 80 to 140 ° C. to dry the coating film, actinic rays (actinic radiation) are irradiated using an exposure apparatus such as a contact aligner, mirror projection, or stepper. As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable. From the viewpoint of pattern resolution and handleability, the light source wavelength is preferably a g-line, h-line or i-line of a mercury lamp, and may be a single or a mixture of two or more actinic rays. As the exposure apparatus, a contact aligner, a mirror projection, and a stepper are particularly preferable.

  Next, the exposed photosensitive resin layer is developed to obtain a relief pattern. The developing method can be selected from methods such as an immersion method, a paddle method, and a rotary spray method. Developers include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide. An aqueous solution containing a suitable amount of a water-soluble organic solvent or surfactant such as methanol or ethanol can be used if necessary. In particular, an aqueous tetramethylammonium hydroxide solution is preferable, and the concentration thereof is typically 0.5 to 10% by mass, and preferably 1.0 to 5% by mass.

  After development, the pattern film can be obtained by washing with a rinse solution and removing the developer. As a rinse liquid, distilled water, methanol, ethanol, isopropanol, etc. can be used individually or in combination of 2 or more types.

  Finally, a cured relief pattern can be obtained by heating the relief pattern thus obtained. The heating temperature is preferably 150 ° C. or higher.

  In a general method of forming a cured relief pattern using a polyimide or polybenzoxazole precursor composition, the precursor is converted to polyimide or polybenzoxazole by heating to 300 ° C. or more to advance a dehydration cyclization reaction. There is no need for dehydration cyclization in the process of the present invention. Therefore, the present invention can be suitably applied to a semiconductor device or the like that is vulnerable to heat. For example, the present invention relates to a semiconductor device having an insulating layer made of an oxide of a high-melting-point metal and a ferroelectric material having a process temperature constraint, such as titanium, tantalum, and hafnium. It can be suitably applied.

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

<Method for Manufacturing Semiconductor Device and Semiconductor Device>
Another aspect of the present invention includes the following steps: forming a photosensitive resin layer comprising the above-described photosensitive resin composition according to the present invention on a semiconductor substrate, and exposing the photosensitive resin layer with actinic rays. Provided is a method for manufacturing a semiconductor device, including a step, a step of developing the exposed photosensitive resin layer to obtain a relief pattern, and a step of heating the obtained relief pattern. Another aspect of the present invention provides a semiconductor device manufactured by the above-described method. Each step in the above method for manufacturing a semiconductor device can be performed by the procedure described above in the method for forming a cured relief pattern. However, in the method for manufacturing a semiconductor device of the present invention, a photosensitive resin layer made of a photosensitive resin composition is formed on a semiconductor substrate. In the manufacturing method of a known semiconductor device, the above-described cured relief pattern is used as a protective film for a surface protective film, an interlayer insulating film, a rewiring insulating film, a flip-chip device protective film, or a device having a bump structure. By combining with the process, the semiconductor device of the present invention can be manufactured.

｛式中、Ｒ₁₅は、独立に、水素原子；フッ素原子；又はフッ素で置換されてもよい炭素数１〜１０の脂肪族基；を表し、ｃは、３〜１，０００の間の整数である。｝
で表される構造、及び下記一般式（１０）：

｛式中、Ｒ₁₆は、独立に、水素原子；フッ素原子；又はフッ素で置換されてもよい炭素数１〜１０の脂肪族基；を表し、ｄは、３〜１，０００の間の整数である。｝
で表される構造、の両者を有する。 <New phenolic resin>
Another aspect of the present invention provides a novel phenolic resin. The novel phenol resin provided by the present invention has, in the main chain, the following general formula (9):

{In the formula, R ₁₅ independently represents a hydrogen atom; a fluorine atom; or an aliphatic group having 1 to 10 carbon atoms which may be substituted with fluorine; and c represents an integer between 3 and 1,000. It is. }
And the following general formula (10):

{In the formula, R ₁₆ independently represents a hydrogen atom; a fluorine atom; or an aliphatic group having 1 to 10 carbon atoms which may be substituted with fluorine; and d represents an integer between 3 and 1,000. It is. }
It has both of the structure represented by these.

  The above novel phenol resin having a specific repeating structure can be synthesized by condensation polymerization of a phenol compound having 1 phenolic hydroxyl group, a phenol compound having 3 phenolic hydroxyl groups, and a compound having a biphenyldiyl structure.

In the general formulas (9) and (10), R ₁₅ and R ₁₆ each independently represent a hydrogen atom; a fluorine atom; or an aliphatic group having 1 to 10 carbon atoms which may be substituted with fluorine. From the viewpoint of solubility of the polymer in an aqueous alkali solution, R ₁₅ and R ₁₆ are preferably each independently a fluorine atom; or an aliphatic group having 1 to 4 carbon atoms which may be substituted with fluorine. More preferably, they are a fluorine atom, a methyl group, or a trifluoromethyl group.

  Examples of phenolic compounds having 1 phenolic hydroxyl group used to synthesize the novel phenolic resin of the present invention include phenol, fluorophenol, cresol, ethylphenol, propylphenol, butylphenol, octylphenol, nonylphenol and the like. Examples include various o-, m-, and p-isomers of alkylphenols, and various o-, m-, and p-isomers of the above alkylphenols substituted with fluorine. From the viewpoint of solubility of the polymer in an alkaline aqueous solution, fluorophenol, cresol, and trifluoromethylphenol are particularly preferable.

  Examples of the phenolic compound having 3 phenolic hydroxyl groups used in the novel phenol resin of the present invention include pyrogallol, phloroglucinol, 1,2,4-trihydroxybenzene, and the like. From the viewpoint of alkali developability of the phenol resin, pyrogallol is preferable.

  Examples of the compound having a biphenyldiyl structure used for synthesizing the novel phenol resin of the present invention include 4,4′-bischloromethylbiphenyl, 4,4′-biphenyldimethanol, 4,4′-bis ( From the viewpoint of mechanical properties of the cured product, 4,4′-bis (methoxymethyl) biphenyl is preferable.

  In the general formulas (9) and (10), c and d are each independently an integer between 2 and 1,000, preferably 3 to 900, and more preferably 4 to 800. c and d are 2 or more from the viewpoint of the toughness of the film after curing, and 1,000 or less from the viewpoint of solubility in an aqueous alkali solution.

The molar ratio of the unit structure repeated in the number c in the general formula (9) and the unit structure repeated in the number d in the general formula (10) present in the phenol resin is a photosensitive resin composition. From the viewpoint of solubility in an alkaline developer, d / c> 1 is preferable, and d / c is more preferably 1.1 to 10. The molar ratio can be confirmed by ¹ H-NMR analysis.

  The method for synthesizing the novel phenol resin of the present invention will be described. The novel phenol resin of the present invention is obtained by heating and stirring a phenol compound having 1 phenolic hydroxyl group, a phenol compound having 3 phenolic hydroxyl groups, and a compound having a biphenyldiyl structure in the presence of an appropriate polymerization catalyst. Can do. The polymerization catalyst is not particularly limited, but an acid catalyst is preferable. Acid catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, oxalic acid and diethyl sulfate, Lewis such as boron trifluoride, anhydrous aluminum chloride and zinc chloride. An acid etc. are mentioned. The amount of the acid catalyst used is preferably in the range of 0.01 to 5 mol% with respect to the number of moles of the compound having a biphenyldiyl structure.

  When performing the synthesis reaction of the novel phenol resin of this invention, an organic solvent can be used as needed. Specific examples of organic solvents that can be used include diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl cellosolve, ethyl cellosolve, toluene, xylene, γ-butyrolactone, and N-methyl-2-pyrrolidone. However, it is not limited to these. The amount of the organic solvent used is usually 10 to 1000 parts by mass, preferably 20 to 500 parts by mass with respect to 100 parts by mass of the total mass of the raw materials charged. Moreover, reaction temperature is 40-250 degreeC normally, and the range of 100-200 degreeC is more preferable. The reaction time is usually 1 to 10 hours.

Further, when the synthesis reaction of the phenol resin of the present invention is carried out, the reaction may be carried out by simultaneously charging a phenol compound having 1 phenolic hydroxyl group, a phenol compound having 3 phenolic hydroxyl groups and a compound having a biphenyldiyl structure. Also, a method is adopted in which a phenol compound having 1 phenolic hydroxyl group and a compound having a biphenyldiyl structure are charged and reacted to a certain molecular weight, and then a phenol compound having 3 phenolic hydroxyl groups is charged and continuously reacted. it can.
As described above, the phenol resin of the present invention can be synthesized. The phenol resin of this invention can be used conveniently as a phenol resin (A) of the photosensitive resin composition mentioned above.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

Synthesis of phenol resin (A) <Synthesis Example 1>
While purging with nitrogen, m-cresol (hereinafter also referred to as “mC”) 9.73 g (0.09 mol), 4,4′-bis (in a separable flask with a Dean-Stark apparatus having a capacity of 0.5 L) Methoxymethyl) biphenyl (hereinafter also referred to as “BPDM”) 10.90 g (0.045 mol), diethyl sulfate (hereinafter also referred to as “DES”) 1.05 g (0.00675 mol), diethylene glycol dimethyl ether (hereinafter “DMDG”) 30 g) was mixed and stirred at 50 ° C. to dissolve the solid matter.

  The mixed solution was heated to 140 ° C. using an oil bath, and generation of methanol was confirmed from the reaction solution. The reaction solution was stirred at 140 ° C. for 4 hours. Thereafter, the reaction liquid was cooled to room temperature, and pyrogallol (hereinafter also referred to as “PyG”) 26.48 g (0.21 mol), BPDM 32.71 g (0.135 mol), DMDG 50 g, DES 0.35 g (0 .00225 mol) was added, and the reaction solution was heated again to 130 ° C. with an oil bath, and further stirred and reacted for 1.5 hours.

Next, the reaction vessel was cooled in the atmosphere, and 100 g of tetrahydrofuran was separately added thereto and stirred. The reaction diluted solution is dropped into 8 L of water under high-speed stirring to disperse and precipitate the resin, which is recovered, appropriately washed with water and dehydrated, and then vacuum-dried to obtain the phenol resin (A) (P-1) in a yield. Obtained at 78%. The weight average molecular weight of P-1 by GPC (gel permeation chromatography) was 22,698 in terms of polystyrene. In addition, a ¹ H-NMR spectrum of P-1 as a copolymer was measured using an Avance 600 FT-NMR apparatus manufactured by Bruker Biospin. ^{From the 1} H-NMR analysis, the molar ratio of “PyG” / “mC” in the skeleton of the obtained polymer P-1 was 2.7.

<Synthesis Example 2>
While purging with nitrogen, mC 16.55 g (0.15 mol), BPDM 18.17 g (0.075 mol), DES 1.15 g (0.0075 mol), DMDG 40 g in a separable flask with 0.5 L Dean-Stark apparatus Were mixed and stirred at 50 ° C. to dissolve the solid matter. Similar to Synthesis Example 1, the reaction solution was reacted at 140 ° C. for 4 hours, and then PyG 18.92 g (0.15 mol), BPDM 30.29 g (0.125 mol), DMDG 43.6 g, DES 0.39 g (0. 0025 mol) was added, and the reaction solution was heated again to 130 ° C. with an oil bath, and further stirred for 1.5 hours.

Next, the reaction vessel was cooled in the atmosphere, and 100 g of tetrahydrofuran was separately added thereto and stirred. The reaction diluted solution is dropped into 8 L of water under high-speed stirring to disperse and precipitate the resin, which is recovered, appropriately washed with water and dehydrated, and then vacuum dried to obtain the phenol resin (A) (P-2) in a yield. Obtained at 76%. The weight average molecular weight of P-2 by GPC was 18,800 in terms of polystyrene. ^{From the 1} H-NMR analysis, the molar ratio of “PyG” / “mC” in the skeleton of the obtained polymer P-2 was 1.17.

<Synthesis Example 3>
Synthesis was performed in the same manner as in Synthesis Example 2 except that 16.82 g (0.15 mol) of 2-fluorophenol (hereinafter also referred to as “2FP”) was used instead of m-cresol in Synthesis Example 2. Resin (A) (P-3) was obtained with a yield of 73%. The weight average molecular weight of P-3 by GPC was 16,253 in terms of polystyrene. ^{From the 1} H-NMR analysis, the molar ratio of “PyG” / “2FP” in the skeleton of the obtained polymer P-3 was 1.32.

  The polymers synthesized in Synthesis Examples 1 to 3 are summarized in Table 1 below.

  In addition, the weight average molecular weight of the polymer synthesized in the above synthesis example and the commercially available phenol resin used in the comparative example to be described later was determined by gel permeation chromatography (GPC) using standard polystyrene (Organic solvent standard produced by Showa Denko KK). Sample STANDARD SM-105) was calculated in terms of conversion.

The GPC apparatus used and the measurement conditions were as follows.
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40 ° C
Column: Shodex KD-806M Two in series Mobile phase: 0.1 mol / l EtBr / NMP
Flow rate: 1 ml / min.

<Preparation of photosensitive resin composition>
[Examples 1 to 3, Comparative Example 1]
Each component used in the examples and comparative examples of the present invention was as follows.

Phenolic resin component (corresponding to the phenolic resin (A) in the present invention in the examples)
P-1 to P-3: Polymers of P-1 to P-3 obtained in the above synthesis example P-4: MEH-7851 4H (weight average molecular weight = 9986) manufactured by Meiwa Kasei Co., Ltd. (commercially available having the following structure) Product)

｛式中、Ｑの内８３％が下記構造：

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

{In the formula, 83% of Q has the following structure:

The remainder is a hydrogen atom. }

Cross-linking agent (C)
C-1: Nikaluck MX-270 (commercial product having the following structure) manufactured by Sanwa Chemical Co., Ltd.

Solvent γ-Butyrolactone (GBL)

The preparation of the photosensitive resin compositions of Examples 1 to 3 and Comparative Example 1 was performed as a photoacid generator (B) with respect to 100 parts by mass of the phenol resin (corresponding to the phenol resin (A) in the examples). After mixing and dissolving 12 parts by mass of the B-1 component, 20 parts by mass of the C-1 component as the crosslinking agent (C), and 110 parts by mass of GBL as the solvent, the mixture was filtered with a 0.2 μm Teflon (registered trademark) filter. A photosensitive varnish was obtained.
Table 2 shows the evaluation results of the obtained photosensitive varnish.

  Each physical property was evaluated as follows.

<Solubility in alkaline aqueous solution>
The photosensitive resin compositions obtained in Examples and Comparative Examples were spin-coated on a 6-inch silicon wafer substrate so as to have a film thickness of about 10 μm, and pre-baked at 120 ° C. for 180 seconds with a hot plate. A film was formed. The film thickness was measured with a film thickness measuring device (Lambda Ace) manufactured by Dainippon Screen Mfg. Then, 600 mJ / cm ² full wavelength exposure was performed in the i-line region using a high pressure mercury lamp. Next, the exposed film was dipped in a 2.38 mass% TMAH aqueous solution (AZ300MIF manufactured by AZ Electronic Materials). When the coating film was completely dissolved within 5 minutes, the solubility in the alkaline aqueous solution was “OK”. When the coating film was not completely dissolved within 5 minutes, the solubility in the alkaline aqueous solution was “NG”.

<Relative permittivity evaluation>
The photosensitive resin compositions obtained in Examples and Comparative Examples were spin-coated on a 6-inch silicon wafer substrate having a resistivity of 0.02 Ω · cm or less so that the film thickness after curing was about 5 μm. Pre-baking was performed on a hot plate at 180 ° C. for 180 seconds to form a coating film. The film thickness was measured with a film thickness measuring device (Lambda Ace) manufactured by Dainippon Screen Mfg. This coating film was heated at 250 ° C. for 1 hour in a nitrogen atmosphere to obtain a film having a thickness of 5 μm. The relative dielectric constant measurement conditions were as follows.
Apparatus: Mercury probe CV / IV measuring apparatus SSM495 manufactured by Nippon Semilab Co., Ltd.
Measurement frequency: 1MHz

<Elongation evaluation>
A sample for measuring elongation according to the present invention was produced by the following method.
The photosensitive resin compositions obtained in Examples and Comparative Examples were spin-coated on a 6-inch silicon wafer substrate provided with an aluminum vapor deposition layer on the outermost surface so that the film thickness after curing was about 10 μm, and 120 ° C. Then, pre-baking was performed on a hot plate for 180 seconds to form a coating film. The film thickness was measured with a film thickness measuring device (Lambda Ace) manufactured by Dainippon Screen Mfg. This coating film was heated at 250 ° C. for 1 hour in a nitrogen atmosphere to obtain a film having a thickness of 10 μm. The obtained cured resin film was cut to a width of 3 mm with a dicing saw, and then peeled off from the wafer with a dilute hydrochloric acid aqueous solution, and the obtained 20 samples were left in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours or more. The elongation was measured with a tensile tester (Tensilon). The measurement conditions of the tensile tester were as follows.

Temperature: 23 ° C
Relative humidity: 50%
Initial sample length: 50 mm
Test speed: 40 mm / min
Load cell rating: 2kgf

  From Table 2 above, Examples 1 to 3 gave good results in the balance of solubility in alkaline aqueous solution, relative dielectric constant, and elongation, whereas Comparative Example 1 showed relative dielectric constant and elongation. Although it was good, it could not be used as a photosensitive resin composition because it did not dissolve in an alkaline aqueous solution.

  A photosensitive resin composition for forming a surface protective film or an interlayer insulating film of a semiconductor element according to the present invention is used as a surface protective film for a semiconductor element, a surface protective film for a semiconductor device and a light emitting device, and a protection for a flip chip device. It can be suitably used as a protective film for a device having a film and a bump structure, and can also be suitably used as an insulating film for rewiring, an interlayer insulating film of a multilayer circuit, etc. as an interlayer insulating film.

Claims (8)

A photosensitive resin composition for forming a surface protective film or an interlayer insulating film of a semiconductor element,
Phenol resin (A) which is a polymerization reaction product of a polymerization component containing two or more phenolic compounds having different numbers of phenolic hydroxyl groups: 100 parts by mass; and photoacid generator (B): 0.1-50 parts by mass;
The photosensitive resin composition containing this. The phenol resin (A) has a structure represented by the following general formula (1) and a structure represented by the following general formula (2):

{Where
R ₁ and R ₂ are each independently a halogen atom; a nitro group; a cyano group; an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond; an alicyclic group having 3 to 20 carbon atoms An aromatic group having 6 to 20 carbon atoms: or the following general formula group (3):

(In the formula, R _3, R ₄ and R ₅ are each independently a hydrogen atom; an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond; an alicyclic group having 3 to 20 carbon atoms. Or an aromatic group having 6 to 20 carbon atoms, and R ₆ is an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond; an alicyclic group having 3 to 20 carbon atoms. Or an aromatic group having 6 to 20 carbon atoms; a group represented by any one of
X and Y are each independently an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond; an alicyclic group having 3 to 20 carbon atoms; an integer having 1 to 20 repeating units. An ethylene oxide group; or an organic group having an aromatic group;
In R _{1 to} R ₆ , X and Y, a hydrogen atom may be substituted with at least one selected from the group consisting of a halogen atom, a carboxyl group, a nitro group and a cyano group,
a and b are each independently an integer between 2 and 1,000;
m is 1 or 2, n is 2 or 3, provided that n> m,
p is an integer of 0 to 3,
q is an integer of 0-2. }
The photosensitive resin composition of Claim 1 which has both of these. X and Y in the general formulas (1) and (2) are each independently the following general formula (4):

{Wherein, R _{7 to} R ₁₀ each independently represents a hydrogen atom; or an aliphatic group having 1 to 10 carbon atoms which may be substituted with fluorine. }
Or a group represented by the following general formula (5):

{Wherein, R _{11 to} R ₁₄ each independently represents a hydrogen atom; or an aliphatic group having 1 to 10 carbon atoms which may be substituted with fluorine; Z represents a single bond; substituted with fluorine; An aliphatic group having 1 to 10 carbon atoms; an alicyclic group having 3 to 20 carbon atoms which may be substituted with fluorine; an ethylene oxide group having 1 to 20 repeating units; or the following formula group (6):

A group represented by any one of the following: }
The photosensitive resin composition of Claim 1 or 2 which is group represented by these. X and Y in the general formulas (1) and (2) are the following general formula (7):

{Wherein W is a single bond; an aliphatic group having 1 to 10 carbon atoms which may be substituted with fluorine; an alicyclic group having 3 to 20 carbon atoms which may be substituted with fluorine; 20 ethylene oxide groups; or the following formula group (8):

A group represented by any one of the following: }
The photosensitive resin composition of any one of Claims 1-3 which is group represented by these.   The photosensitive resin composition of any one of Claims 1-4 which is b / a> 1 in the said General formula (1) and (2).   The photosensitive resin composition of any one of Claims 1-5 whose said photo-acid generator (B) is a quinonediazide compound.   The photosensitive resin composition is a compound that can react with the phenol resin (A) by heat or an acid generated from the photoacid generator (B), or generated by heat or from the photoacid generator (B). The photosensitive resin composition of any one of Claims 1-6 which further contains 1-60 mass parts of crosslinking agents (C) which are compounds in which a self-reaction can occur with the acid. The following steps:
Forming a photosensitive resin layer comprising the photosensitive resin composition according to any one of claims 1 to 7 on a semiconductor substrate;
Exposing the photosensitive resin layer with actinic rays;
The manufacturing method of a semiconductor device including the process of developing this exposed photosensitive resin layer, obtaining a relief pattern, and the process of heating the obtained relief pattern.