JP2010079065A - Photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition capable of forming a surface protection film and an inter-layer insulation film with excellent flatness owing to a high film remaining ratio after a heat treatment. <P>SOLUTION: The photosensitive resin composition contains (a) 100 pts.mass of an alkaline soluble resin having at least one repeating unit selected from the group consisting of formula (1) and a specific polyamide residue having a hydroxy group, (b) 0.01-20 pts.mass of a compound to generate an acid by irradiation with radiation, (c) 0.1-50 pts.mass of a compound having a group crosslinkable by an acid, and (d) 10-500 pts.mass of a compound having a (meth)acryloyl group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition used for a surface protective film (buffer coat film), an interlayer insulating film (passivation film) and the like of a semiconductor element, and a cured product (insulator) obtained by curing the same. More specifically, the present invention relates to a negative photosensitive resin composition for forming a heat-resistant cured film for protecting a semiconductor circuit surface having excellent flatness due to a high residual film ratio after heat treatment.

Conventionally, polyimides and polybenzoxazole resins having excellent heat resistance and mechanical properties are widely used for surface protective films, interlayer insulating films, and the like used in semiconductor devices of electronic devices. In addition, in order to improve film formation accuracy by high integration of semiconductor elements, photosensitive polyimide (precursor) resin composition and photosensitive polybenzoxazole (precursor) resin composition provided with photosensitivity are provided. Various proposals have been made. Among them, as a composition having an alkali developing negative type photosensitive property, for example, a method of combining a polybenzoxazole precursor with a crosslinkable compound under a photoacid generator has been proposed (hereinafter referred to as Patent Document 1). See However, these compositions require a ring-closing step (curing) at a high temperature of 300 ° C. or higher, and volatile components are released at that time, resulting in a low residual film rate after curing. There was the fault that flatness was impaired. Therefore, a method for ring closure at a temperature lower than 300 ° C. has been proposed. As an example, there is a method using the reactivity of a combination of both a base resin and a cross-linking agent (refer to Patent Document 2 below), but at low temperatures, the addition of a compound must be relied on and ring closure is insufficient. However, there is still concern about mechanical properties.
JP 2001-125267 A JP 2007-256525 A

  The object of the present invention is to solve the problems associated with the prior art as described above, and a photosensitive resin composition capable of forming a surface protective film and an interlayer insulating film excellent in flatness due to a high residual film ratio after heat treatment. Is to provide things.

In order to solve the above-mentioned problems, the present inventors have conducted extensive experiments and as a result of studying, as a result, in a specific alkali-soluble resin composition, a (meth) acryloyl group (here, a (meth) acryloyl group is an acryloyl group). Or a methacryloyl group. The same applies hereinafter.) By coexisting with a compound having a methacryloyl group), it was unexpectedly discovered that the remaining film ratio after curing can be kept high even if it does not depend on low-temperature ring closure conditions. Thus, the present invention has been completed.
That is, the present invention is as follows [1] to [4]:

｛式中、Ｒ_１は、芳香族環又は脂肪族環を有する４価の有機基であり、そしてＲ_２は、４価の芳香族環を有する有機基である。｝及び下記式（２）：

｛式中、Ｒ_３は、２価の芳香族環又は脂肪族環を有する有機基であり、そしてＲ_４は、４価の芳香族環を有する有機基である。｝から成る群から選ばれる少なくとも一種の繰り返し単位を有するアルカリ可溶性樹脂：１００質量部、
（ｂ）放射線照射により酸を発生する化合物：０．０１〜２０質量部、
（ｃ）酸により架橋反応しうる基を有する化合物：０．１〜５０質量部、及び
（ｄ）（メタ）アクリロイル基を有する化合物：１０〜５００質量部、
を含む感光性樹脂組成物。 [1] (a) The following formula (1):

{Wherein R ₁ is a tetravalent organic group having an aromatic ring or an aliphatic ring, and R ₂ is an organic group having a tetravalent aromatic ring. } And the following formula (2):

{Wherein R ₃ is an organic group having a divalent aromatic ring or an aliphatic ring, and R ₄ is an organic group having a tetravalent aromatic ring. } Alkali-soluble resin having at least one repeating unit selected from the group consisting of:
(B) Compound that generates acid upon irradiation: 0.01 to 20 parts by mass;
(C) a compound having a group capable of undergoing a crosslinking reaction with an acid: 0.1 to 50 parts by mass, and (d) a compound having a (meth) acryloyl group: 10 to 500 parts by mass,
A photosensitive resin composition comprising:

[2] A forming step of forming a photosensitive resin layer comprising the photosensitive resin composition according to [1] on a substrate, an exposure step of exposing the photosensitive resin layer with actinic rays, and the exposed photosensitivity. A method for forming a cured relief pattern, comprising a heating step of heating a resin layer, a developing step of developing, and a heating step of heating the obtained relief pattern.

[3] A semiconductor device having a cured relief pattern formed on the silicon wafer substrate by the method for forming a cured relief pattern according to [2].

[4] A method for manufacturing a semiconductor device, comprising the method for forming a cured relief pattern according to [2] as a part of the process.

  Since the photosensitive resin composition of the present invention has a high residual film ratio after heat treatment, the flatness of a surface protective film (buffer coat film) or an interlayer insulating film (passivation film) for semiconductor applications, semiconductor elements and the like is particularly high. It can be suitably used for required applications.

｛式中、Ｒ_１は、芳香族環又は脂肪族環を有する４価の有機基であり、そしてＲ_２は、４価の芳香族環含有有機基である。｝及び下記式（２）：

｛式中、Ｒ_３は、２価の芳香族環含有有機基であり、そしてＲ_４は、４価の芳香族環含有有機基である。｝からなる群より選ばれる少なくとも一種の繰り返し単位を有するアルカリ可溶性樹脂。 The present invention will be specifically described below.
<Photosensitive resin composition>
The photosensitive resin composition of the present invention essentially comprises the following components (a), (b), (c) and (d).
(A) The following formula (1):

{Wherein R ₁ is a tetravalent organic group having an aromatic ring or an aliphatic ring, and R ₂ is a tetravalent aromatic ring-containing organic group. } And the following formula (2):

{Wherein R ₃ is a divalent aromatic ring-containing organic group, and R ₄ is a tetravalent aromatic ring-containing organic group. } An alkali-soluble resin having at least one repeating unit selected from the group consisting of:

｛式中、Ｘは以下：

（式中、Ｙは水素原子またはフッ素原子を表す。）

に示されるものの中から選ばれる２価の基である。｝

｛式中、Ｒ_５は、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−ＣＨ_２−ＣＨ_２−又は、−ＣＨ＝ＣＨ−である。｝

｛式中、Ｒ_６は、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−又は−ＣＨ_２−ＣＨ_２−である。｝

｛式中、Ｒ_７は、−ＣＨ_２−又は−ＣＨ_２−ＣＨ_２−である。｝。

In the above formula (1), R ₁ is preferably a tetravalent organic group having an aromatic ring or aliphatic ring having 6 to 40 carbon atoms, and examples thereof include a tetravalent organic group having the following structure. :

{Where X is:

(In the formula, Y represents a hydrogen atom or a fluorine atom.)

Is a divalent group selected from those shown in the above. }

{Wherein, _{R 5 is, -CH 2 -, - C (} CH 3) 2 -, - C (CF 3) 2 -, - CH 2 -CH 2 - or a -CH = CH-. }

{Wherein, _{R 6 is, -CH 2 -, - C (} CH 3) 2 -, - C (CF 3) 2 - or _-CH 2 -CH ₂ -. }

{Wherein R ₇ represents —CH ₂ — or —CH ₂ —CH ₂ —. }.

を有する４価の有機基が挙げられる。 More preferably, the following structure:

And tetravalent organic groups having

｛式中、Ｘは、以下：

（式中、Ｙは、水素原子又はフッ素原子を表す。）

に示されるものの中から選ばれる２価の基である。｝

を有する有機基であることが、アルカリ溶解性の観点から好ましい。 In the above formulas (1) and (2), R ₂ and R ₄ have the following structure having a tetravalent aromatic ring having 6 to 40 carbon atoms:

{Where X is the following:

(In the formula, Y represents a hydrogen atom or a fluorine atom.)

Is a divalent group selected from those shown in the above. }

It is preferable from an alkali solubility viewpoint that it is an organic group which has.

｛式中、Ａは、−ＣＨ_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−）等から選ばれる基である。｝

を有する２価の有機基、及びこれらベンゼン環上に置換基、例えば、アルキル基、アルコキシ基、アルキルアミノ基を有する有機基が挙げられる。 In the above formula (2), R ₃ is preferably a divalent organic group having an aromatic ring having 6 to 40 carbon atoms, for example, the following structure:

{In the formula, A is a group selected from —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —) and the like. }

And a divalent organic group having a substituent on the benzene ring, for example, an organic group having an alkyl group, an alkoxy group, or an alkylamino group.

を有する２価の有機基であることがより好ましい。 Among them, in the above formula (2), R ₃ represents the following structure from the viewpoint of affinity with the solvent and light transmittance:

More preferably, it is a divalent organic group having

The method for synthesizing the alkali-soluble resin having the repeating unit of the above formula (1) is obtained by omitting the second stage acid chloride addition in the synthesis method described later.
Hereinafter, a method for synthesizing an alkali-soluble resin having a repeating unit of the above formula (2) (hereinafter also referred to as “hydroxypolyamide”) will be described.
This hydroxypolyamide is typically synthesized by the following method. That is, condensation of an aromatic or alicyclic dicarboxylic acid dichloride or an active ester of a dicarboxylic acid with an aromatic dihydroxydiamino compound, or an aromatic or alicyclic dicarboxylic acid in the presence of a suitable condensing agent or carboxylic acid activator. It can be obtained by the condensation of an aromatic dihydroxydiamino compound.

As a specific synthesis method, for example, when dicarboxylic acid dichloride is used, a dihydroxydiamino compound and acid scavenger pyridine or triethylamine are dissolved in an appropriate solvent in advance, and dicarboxylic acid dichloride dissolved in the solvent is added thereto. In addition, it can be manufactured. Examples of the solvent used in this synthesis include N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, γ-butyrolactone, and dimethyldiglycol.
The molecular weight of the hydroxy polyamide is preferably 1,000 to 100,000 in terms of weight average molecular weight.

に示される基が代表的な例として挙げられるが、末端基で封止していなくてもよい。 As end groups of hydroxypolyamide, the following structural formula:

Although the group shown by is mentioned as a typical example, it is not necessary to seal with the terminal group.

｛式中、Ｒ_１は脂肪族環を有する４価の有機基である。｝に示す脂肪族環を有するテトラカルボン酸二無水物と、下記式（４）：

｛式中、Ｒ_２は４価の芳香族環含有有機基である。｝に示すジヒドロキシジアミンとを有機溶媒の中、モル比１：１．０５〜２で、−１０℃〜５０℃下１〜２４時間反応させた後、５０℃〜１９０℃下２〜４８時間加熱し、前記式（１）の繰り返し単位を有するポリイミドオリゴマーを得る。必要に応じて、５０℃〜１９０℃下で加熱する前に、トルエン、キシレン、デカリンなどを添加して、共沸により生成する水を除去してもよい。 Hereinafter, a method for synthesizing the alkali-soluble resin having the repeating units of the above formulas (1) and (2) will be described.
First, the following formula (3):

{In the formula, R ₁ is a tetravalent organic group having an aliphatic ring. } A tetracarboxylic dianhydride having an aliphatic ring represented by the following formula (4):

{Wherein R ₂ represents a tetravalent aromatic ring-containing organic group. Is reacted in an organic solvent at a molar ratio of 1: 1.05 to 2 at −10 ° C. to 50 ° C. for 1 to 24 hours, and then heated at 50 ° C. to 190 ° C. for 2 to 48 hours. And the polyimide oligomer which has a repeating unit of the said Formula (1) is obtained. If necessary, before heating at 50 ° C. to 190 ° C., toluene, xylene, decalin, or the like may be added to remove water generated by azeotropic distillation.

｛式中、Ｒ_５は−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−ＣＨ_２−ＣＨ_２−又は−ＣＨ＝ＣＨ−である。｝

｛式中、Ｒ_６は−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−又は−ＣＨ_２−ＣＨ_２−である。｝

｛式中、Ｒ_７は−ＣＨ_２−又は−ＣＨ_２−ＣＨ_２−である。｝

から成る群から選ばれる化合物であることが好ましい。 Among the above-mentioned formula (3), the tetracarboxylic dianhydride having a tetravalent aliphatic ring group R ₁ that is suitably used includes the following compounds:

{Wherein, _{R 5} is _{-CH 2 -, - C (CH} 3) 2 -, - C (CF 3) 2 -, - CH 2 -CH 2 - or -CH = a CH-. }

{Wherein R ₆ represents —CH ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ — or —CH ₂ —CH ₂ —. }

{In the formula, R ₇ represents —CH ₂ — or —CH ₂ —CH ₂ —. }

A compound selected from the group consisting of:

Further, of the above formula (4), as the dihydroxy diamine compound containing a suitably tetravalent aromatic ring group _{R 2} to be used, for example, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4, 4′-diamino-3,3′-dihydroxybiphenyl, 3,3′-diamino-4,4′-dihydroxydiphenylsulfone, 4,4′-diamino-3,3′-dihydroxydiphenylsulfone, bis- (3- Amino-4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2 -Bis- (4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis- ( -Amino-3-hydroxyphenyl) propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3 '-Dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3- And diamino-4,6-dihydroxybenzene. These dihydroxydiamine compounds may be used alone or in combination.

  Moreover, as an organic solvent used for the above-mentioned reaction, amides, sulfoxides, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons are preferable. Examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane. , Chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene, N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), N, N-dimethylformamide (DMF), dimethyl Examples thereof include sulfoxide, tetramethylurea, gamma butyrolactone (GBL), sulfolane and the like. Among these, those that completely dissolve the polyimide oligomer are more preferable. Examples include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, gamma butyrolactone, sulfolane. These solvents can be used alone or as a mixture as required.

  Second, to the polyimide oligomer reaction solution obtained by the above method, dicarboxylic acid is added in the presence of dicarboxylic acid dichloride, or an appropriate condensing agent or carboxylic acid activator, and the above formula ( An alkali-soluble resin (hereinafter referred to as “polymer A”) having the repeating units of 1) and (2) is obtained. From the viewpoint of heat resistance and mechanical properties when the polymer A is used, the second monomer used preferably contains an aromatic ring group.

｛式中、Ｗは、ＯＨ基又は塩素であり、そしてＲ_３は、２価の芳香族環含有有機基である。｝
で表されるジカルボン酸又は他のジカルボン酸ジクロリドとの混合物を使用する。 Specifically, when dicarboxylic acid dichloride is used, a tertiary amine compound such as pyridine or triethylamine is added as an acid scavenger to the polyimide oligomer reaction liquid obtained in the first reaction, and then the reaction solution Is cooled to a temperature range of about 0 ° C. to −20 ° C., and dicarboxylic acid dichloride previously dissolved or dispersed in a solvent is added dropwise. Thereafter, the polymer A can be obtained by reacting at a preferred reaction temperature of about −15 ° C. to 40 ° C. and a preferred reaction time of about 2 to 24 hours. As the dicarboxylic acid dichloride used in the reaction at this stage, the following formula (5):

{Wherein W is an OH group or chlorine, and R ₃ is a divalent aromatic ring-containing organic group. }
Or a mixture with other dicarboxylic acid dichlorides.

｛式中、Ｒ_４は、４価の芳香族環基である。｝で示す、４価の芳香族環基Ｒ_４を有するジヒドロキシジアミンを添加してもよい。添加モル数比は、前記第一の反応に使用された式（４）で示すジヒドロキシジアミンのモル数から、前記第一の反応に使用された式（３）で示す酸二無水物のモル数を差し引いた差に対して最大で１０である。好ましくは最大で８であり、より好ましくは最大で５である。硬化膜としたときの応力上昇防止の観点から、当該モル数比は１０以下であることが好ましい。 Examples of the dicarboxylic acid having a divalent aromatic group R ₃ preferably used include 4,4′-biphenyldicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, terephthalic acid, and isophthalic acid. A compound obtained by chlorinating these dicarboxylic acids may be used.
In order to adjust the physical properties, before adding a tertiary amine compound as an acid scavenger to the second reaction, if necessary, the following general formula (6):

{Wherein R ₄ is a tetravalent aromatic ring group. }, A dihydroxydiamine having a tetravalent aromatic ring group R ₄ may be added. The molar ratio of addition is the number of moles of acid dianhydride represented by formula (3) used in the first reaction from the number of moles of dihydroxydiamine represented by formula (4) used in the first reaction. The maximum is 10 for the difference minus. Preferably it is 8 at the maximum, and more preferably 5 at the maximum. From the viewpoint of preventing an increase in stress when a cured film is used, the molar ratio is preferably 10 or less.

As a compound suitably used as the dihydroxydiamine containing the tetravalent aromatic group R ₄ represented by the general formula (6), for example, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4 '-Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino -4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2- Bis- (4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-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-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1, Examples include 3-diamino-4,6-dihydroxybenzene. These dihydroxydiamines may be used alone or in combination.

After completion of the co-condensation reaction, the reaction solution is added dropwise to ion-exchanged water with high-speed stirring to disperse and precipitate the polymer, and this is recovered, appropriately washed with water and dehydrated, followed by vacuum drying to obtain polymer A. . When further purification of the polymer is necessary, after the co-condensation reaction, the reaction solution may be passed through a column packed with an ion exchange resin swollen with an organic solvent to remove ionic impurities.
The molecular weight of the polymer A obtained by the synthesis method is preferably 4,000 to 150,000, more preferably 8,000 to 100,000, in terms of weight average molecular weight. The weight average molecular weight is preferably 4000 or more from the viewpoint of securing the mechanical properties and heat resistance of the material, and preferably 150,000 or less from the viewpoint of the alkali solubility of the material and the development speed.

｛式中、Ｒ_８は、アルキレン基、脂肪族環又は芳香族環を有する有機基である。｝で表される、酸無水物を使用し、上記アミノ基と反応して形成された有機基であってもよい。得られたポリマーＡの保存安定性及び耐熱性の観点から、酸無水物と末端アミノ基との反応で形成される結合は、イミド結合であることが好ましい。 The terminal group of the polymer A may be an amino group derived from dihydroxydiamine, or the following formula (7):

{Wherein, R ₈ is an organic group having an alkylene group, an aliphatic or aromatic ring. }, An organic group formed by reacting with the amino group using an acid anhydride. From the viewpoint of storage stability and heat resistance of the obtained polymer A, the bond formed by the reaction between the acid anhydride and the terminal amino group is preferably an imide bond.

から成る群から選ばれる化合物が好ましい。 Of the acid anhydrides represented by the general formula (7), the following compound group:

Compounds selected from the group consisting of

  When the acid anhydride represented by the above formula (7) is used and reacted with the terminal amino group, the acid anhydride is directly added to the copolymer reaction solution obtained by the above synthesis method and reacted. be able to. Alternatively, the copolymer can be purified from the reaction solution and dried, and then the polymer can be reacted again by dissolving it in an organic solvent and adding an acid anhydride.

When the acid anhydride is directly added to the reaction solution of the copolymer to cause the reaction, the mole ratio of the acid anhydride used is the total number of moles of dihydroxydiamine used in the first reaction and the second reaction. From 10 to 300% of the difference obtained by subtracting the total number of moles of the acid dianhydride used in the first reaction and the dicarboxylic acid or dicarboxylic acid dichloride used in the second reaction. The preferred addition temperature when adding the acid anhydride is about -25 ° C to 25 ° C, and the more preferred addition temperature is about -10 ° C to 0 ° C. After completion of acid anhydride addition, the preferred reaction temperature is about 0 ° C to 80 ° C, and the more preferred reaction temperature is about 25 ° C to 60 ° C. The preferred reaction time is about 1 to 48 hours. An organic or inorganic base may be added as a catalyst. Examples of suitable organic amine bases include pyridine, triethylamine, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1,5-diazabicyclo [4.3.0] non-5. Examples include, but are not limited to, ene (DBN), dimethylpyridine, dimethylaniline, and the like. Examples of other suitable bases include sodium hydroxide, sodium carbonate, sodium silicate.
The alkali-soluble resin may be used alone, or a plurality of different resins may be prepared as necessary, and mixed at an appropriate ratio when preparing the composition.

(B) Compound that generates an acid upon irradiation Next, component (b) of the photosensitive resin composition of the present invention will be described. The component (b) used in the present invention is a compound that generates an acid upon irradiation, and examples of such a compound 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-trichloromethyl)- s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methylthiophenyl) (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-trichloro Methyl) -s-triazine and the like;

ii) diallyliodonium 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- Meto Siphenylphenyliodonium-p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium tetrafluoroborate, bis (4-tert-butylphenyl) iodonium hexafluoroarsenate, bis (4-tert-butylphenyl) iodonium Trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium trifluoroacetate, bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate, etc .;

iii) 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 tri Fluoroacetate, -Methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoroarsenate, 4-phenylthiophenyldiphenyltrifluoro L-methanesulfonate, 4-phenylthiophenyl diphenyl trifluoroacetate, 4-phenylthiophenyl diphenyl-p-toluenesulfonate, and the like.

Among these compounds, as trichloromethyl-S-triazines, 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-trichloro Methyl) -S-triazine, 2- (4-methoxynaphthyl) -bis (4,6-trichloromethyl) -S-triazine and the like as diaryliodonium salts, diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfur As the triarylsulfonium salts, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenylsulfonium Preferred examples include trifluoroacetate, 4-phenylthiophenyl diphenyl trifluoromethanesulfonate, 4-phenylthiophenyl diphenyl trifluoroacetate, and the like.

In addition, the following compounds can also be used:
(1) Diazoketone compound Examples of the diazoketone compound include 1,3-diketo-2-diazo compound, diazobenzoquinone compound, diazonaphthoquinone compound and the like, and specific examples include 1,2-naphthoquinonediazide of phenols. 4-Sulphonic acid ester compounds are mentioned.

(2) Examples of sulfone compounds include sulfone compounds such as β-ketosulfone compounds, β-sulfonylsulfone compounds, and α-diazo compounds of these compounds. Specific examples include 4-trisphenacylsulfone and 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 compounds Specific examples of sulfonimide compounds 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 can be mentioned.

(5) 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-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (trade name" Irgacure PAG103 ", Ciba Specialty Chemicals) Can be mentioned.

(6) Diazomethane compound Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, and the like.
Moreover, the compound which generate | occur | produces an acid by irradiation can also be used suitably in combination with a sensitizer. Examples of such a sensitizer include, for example, coumarins having a substituent at the 3-position and / or 7-position, flavones, dibenzalacetones, dibenzalcyclohexanes, chalcones, xanthones, and thioxanthones. , Porphyrins, phthalocyanines, acridines, anthracene having a substituent at the 9-position, and the like.
Among these, the oxime ester compound group (5) described above is preferable from the viewpoints of solubility in a solvent and photosensitivity.

  It is preferable that content of the said (b) component in the photosensitive resin composition is 0.01-20 mass parts with respect to 100 mass parts of said (a) alkali-soluble resin. From the viewpoint of photosensitivity, 0.01 part by mass or more is preferable, and from the viewpoint of solubility in a solvent, 20 part by mass or less is preferable, and a more preferable content is 1 to 10 parts by mass.

(C) Compound having a group capable of undergoing a crosslinking reaction with an acid Next, the component (c) of the composition of the present invention will be described. The component (c) used in the present invention is preferably selected from a melamine resin substituted at the N-position with a methylol group and / or an alkoxymethyl group and a monomer thereof, and a urea resin and a monomer thereof. Examples of these include alkoxymethylated melamine resins, alkoxymethylated benzoguanamine resins, alkoxymethylated glycoluril resins, alkoxymethylated urea resins, and monomers thereof. Among these, alkoxymethylated melamine resin, alkoxymethylated benzoguanamine resin, alkoxymethylated glycoluril resin, alkoxymethylated urea resin, and these monomers are the corresponding known methylolated melamine resin, methylolated benzoguanamine resin. , Methylolated urea resins, and methylol groups of monomers thereof can be obtained by converting them into alkoxymethyl groups.

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

  It is preferable that content of the said (c) component in the photosensitive resin composition is 0.1-50 mass parts with respect to 100 mass parts of said (a) alkali-soluble resin. From the viewpoint of crosslinkability, 0.1 part by mass or more is preferable, and from the viewpoint of developability and mechanical properties of the cured relief pattern, 50 parts by mass or less is preferable. The more preferable content of the component (c) in the photosensitive resin composition is 3 to 40 parts by mass.

(D) Compound having (meth) acryloyl group Next, the component (d) of the photosensitive resin composition of the present invention will be described. (D) component used for this invention is a compound which has a (meth) acryloyl group, Comprising: What has radical polymerizability especially is preferable. Such compounds can include the following:
2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, caprolactone 2- ( Methacryloyloxy) ethyl ester, dicaprolactone 2- (methacryloyloxy) ethyl ester, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate , Trimethylolpropanedia Relate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, hexyl acrylate, isooctyl acrylate, isovol Nyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol Dimethacrylate, 1,6-hexanediol diacrylate, 1,6-he Sundiol methacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,3-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, dimethacryloyloxyurea, dipentaerythritol hexa Acrylate, dipentaerythritol hexamethacrylate, isocyanuric acid EO-modified triacrylate, isocyanate Examples include anuric acid EO-modified trimethacrylate. These can be used alone or in combination of two or more.

  Among these, from the viewpoints of the remaining film ratio and alkali developability, particularly preferable examples of the component (d) include 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4- Hydroxybutyl methacrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,3-methacryloyloxy-2-hydroxypropane, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, Dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetraacrylate Methacrylate, isocyanuric acid EO-modified triacrylate, a isocyanuric acid EO-modified trimethacrylate. These may be used alone or in combination of two or more.

The functional group ((meth) acryloyl group) number density present in the photosensitive resin composition is defined as follows and can be used for reactivity comparison.
Functional group ((meth) acryloyl group) number density = 1,000 × [(number of (meth) acryloyl groups in compound molecule) × (mass part of compound)] ÷ [(compound molecular weight) × (mass part of the entire composition) )]
This functional group number density is preferably 0.5 or more from the viewpoint of the reaction efficiency of the (meth) acryloyl group.

  The content of the component (d) in the photosensitive resin composition is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (a), from the viewpoint of improving the remaining film ratio. It is preferably 10 parts by mass or more, and (a) 500 parts by mass or less is preferable from the viewpoint of compatibility with the alkali-soluble resin and heat resistance. The content is more preferably 10 to 200 parts by mass, still more preferably 20 to 100 parts by mass.

In order to enhance the effect of the component (d), an allyl compound can be added to the photosensitive resin composition of the present invention. Examples of the allyl compound include triallyl trimellitic acid, tetramellitic pyromellitic acid, allyl phenyl ether, allyl phenol, diallyl ether, diethylene glycol diallyl ether, diallyl hexahydrophthalate, and allyl glycidyl ether.
When the allyl compound is added to the photosensitive resin composition, the addition amount of the allyl compound is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (a), and the remaining film ratio is improved. From the viewpoint of, 10 parts by mass or more is preferable, and from the viewpoint of compatibility, 100 parts by mass or less is preferable.

In the photosensitive resin composition of the present invention, an adhesion assistant, a sensitizer, a photo radical generator, a thermal radical generator, a leveling agent, a polymerization inhibitor, and the like can be contained as other additives.
In order to make the photosensitive resin composition of the present invention into a photosensitive resin composition solution, a solvent can be used.
Examples of the solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, propylene carbonate, tetramethyl Urea, 1,3-dimethylimidazolidinone, 2-methoxyethanol, diethylene glycol, diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate , Methyl-1,3-butylene glycol acetate, 1,3-butylene glycol acetate, cyclohexanone, cyclopentanone, methyl ester Ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran, toluene, xylene, mesitylene, anisole, trimethoxy benzene, hexane, octane, decane and the like. These may be used alone or in combination.
It is preferable that content of a solvent is 10-1000 mass parts with respect to 100 mass parts of (a) alkali-soluble resin.

If necessary, a sensitizer for improving photosensitivity can be added to the negative photosensitive resin composition of the present invention.
Examples of such a sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzylidene) cyclopentanone, and 2,6-bis (4′-diethylamino). Benzylidene) cyclohexanone, 2,6-bis (4′-dimethylaminobenzylidene) -4-methylcyclohexanone, 2,6-bis (4′-diethylaminobenzylidene) -4-methylcyclohexanone, 4,4′-bis (dimethylamino) ) Chalcone, 4,4′-bis (diethylamino) chalcone, 2- (4′-dimethylaminocinnamylidene) indanone, 2- (4′-dimethylaminobenzylidene) indanone, 2- (p-4′-dimethylamino) Biphenyl) benzothiazole, 1,3-bis (4-dimethylaminobenzylide) N) acetone, 1,3-bis (4-diethylaminobenzylidene) acetone, 3,3′-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethyl Aminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, N, N-bis (2-hydroxyethyl) aniline, 4-morpholinobenzophenone, isoamyl 4-dimethylaminobenzoate, isoamid 4-diethylaminobenzoate , Benztriazole, 2-mercaptobenzimidazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, 1-cyclohexyl-5-mercapto-1,2,3,4-tetrazole, 1- ( tert-butyl) -5-mercapto-1,2,3,4-tetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2 -(P-dimethylaminostyryl) naphtho (1,2-p) thiazole, 2- (p-dimethylaminobenzoyl) styrene and the like. Among these, benztriazole, 2-mercaptobenzimidazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, 1-cyclohexyl-5-mercapto-1,2,3,4-tetrazole, And 1- (tert-butyl) -5-mercapto-1,2,3,4-tetrazole, coumarins having a substituent at the 3-position and / or 7-position, flavones, dibenzalacetones, di Adding one or more sensitizers selected from the group consisting of benzalcyclohexanes, chalcones, xanthones, thioxanthones, porphyrins, phthalocyanines, acridines, anthracene having a substituent at the 9-position Is preferred. In use, it may be used alone or as a mixture of two or more.

The addition amount of the sensitizer is preferably 0 to 15 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the (a) alkali-soluble resin.
If necessary, a polymerization inhibitor can be added to the photosensitive resin composition in order to improve the viscosity of the composition solution during storage and the stability of photosensitivity.
Examples of such polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl) -N-sulfopropylamino) phenol, N-nitroso-N-phenylhydroxyamine ammonium salt, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt, Screw( - such as hydroxy-3,5-di-tert- butyl) phenyl methane can be given.
The addition amount of the polymerization inhibitor is preferably 0 to 5 parts by mass and more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the copolymer.

A silane coupling agent can be added to the photosensitive resin composition as needed.
Specific examples of the silane coupling agent include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name KBM803, manufactured by Chisso Corporation: trade name of Sylla Ace S810), 3-mercaptopropyltriethoxysilane (AZMAX Corporation). Product name: SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: product name LS1375, manufactured by Azmax Co., Ltd .: product name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Co., Ltd.) : Trade name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropyl eth Xylodimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercapto Ethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercapto Ethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, -Mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N- (3-triethoxysilylpropyl) urea (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name LS3610, manufactured by Azmax Corporation: trade name SIU9055.0), N- (3-trimethoxysilylpropyl) urea (manufactured by Azmax Co., Ltd .: trade name SIU9058.0), N- (3-diethoxymethoxysilylpropyl) urea, N- (3-ethoxydimethoxysilylpropyl) urea, N -(3-tripropoxysilylpropyl) urea, N- (3-diethoxypropoxysilylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N- (3-dimethoxypropoxysilylpropyl) urea, N -(3-Methoxydipropoxy Silylpropyl) 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, N-phenyl-N ′-[3- (triethoxysilyl) propyl] urea, N-phenyl- N ′-[3- (trimethoxysilyl) propyl] urea, 3- (m-aminophenoxy) propyltrime Toxisilane (manufactured by Azmax Co., Ltd .: trade name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SLA0599) .1), aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SLA0599.2), 2- (trimethoxysilylethyl) pyridine (manufactured by Azmax Co., Ltd .: trade name SIT8396.0), 2- (triethoxysilyl) Ethyl) pyridine, 2- (dimethoxysilylmethylethyl) pyridine, 2- (diethoxysilylmethylethyl) pyridine, N- [3- (triethoxysilyl) propyl] phthalamic acid, 3- (triethoxysilyl) -N- (T-butoxyca And rubonyl) propylamine.
The addition amount of the silane coupling agent is preferably 0 to 20 parts by mass and more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the (a) alkali-soluble resin.

<Method for forming cured relief pattern>
The said photosensitive resin composition is apply | coated to a support body (a silicon wafer, a glass substrate, etc.), and it dries and volatilizes mainly a solvent component etc. and forms a coating film. Thereafter, exposure is performed through a desired mask pattern, and heat treatment (hereinafter, this heat treatment is referred to as “PEB”) is performed to promote the reaction of the components (a), (b), (c), and (d). . Subsequently, it develops with an alkali developing solution, A desired pattern can be obtained by melt | dissolving and removing an unexposed part. Furthermore, a cured film can be obtained by performing a heat treatment at a high temperature (hereinafter, this heat treatment is referred to as “cure”) in order to exhibit the cured film characteristics.

Hereinafter, a method for forming a cured relief pattern will be described.
(1) Forming process for forming a photosensitive resin layer comprising a photosensitive resin composition on a substrate As a method for forming a photosensitive resin composition on a substrate, for example, a silicon wafer or a glass substrate, for example, spraying, bar coating A coating method such as a coating method, a roll coating method, or a spin coating method can be used. Moreover, the thickness of application | coating can be suitably controlled by adjusting the solid content concentration and viscosity of an application | coating means and a composition solution.
(2) Exposure process of exposing the photosensitive resin layer with actinic rays Examples of actinic rays used for exposure include ultraviolet rays, electron beams, laser beams, etc., such as low pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and the exposure amount is For example, in the case of UV irradiation from a high-pressure mercury lamp, the thickness is about 100 to 2,000 mJ / cm ² when the resin thickness is 1 to 50 μm. Examples of the exposure apparatus include a mask aligner, a mirror projection, and a stepper.

(3) Heating step for heating the exposed photosensitive resin layer After the exposure, a crosslinking reaction between (a) an alkali-soluble resin and (c) a compound having a group capable of undergoing a crosslinking reaction with an acid is performed by the generated acid. In order to promote, heat treatment (post-exposure bake is abbreviated as PEB) is performed. The PEB conditions vary depending on the blending amount of the resin composition and the used film thickness, but are usually 70 to 150 ° C., preferably 80 to 130 ° C., and about 1 to 10 minutes.
(4) Development process to develop It develops with an alkaline developing solution, and forms a desired relief pattern by melt | dissolving and removing an unexposed part. Examples of the developing method in this case include a shower developing method, a spray developing method, an immersion developing method, and a paddle developing method. The developing conditions are usually 20 to 40 ° C. and about 30 seconds to 10 minutes.
Examples of the alkaline developer include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, aqueous ammonia, tetramethylammonium hydroxide, and choline, so that the concentration is about 1 to 10% by weight. And an alkaline aqueous solution dissolved in the aqueous solution. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution. In addition, after developing with an alkaline developer, it is washed with water and dried.

(5) Heating process for heating the obtained relief pattern In order to develop the characteristics as an insulating film after development, the resulting relief pattern is subjected to a heat treatment (hereinafter also referred to as “cure”). It can be cured sufficiently. Although such heating conditions are not particularly limited, depending on the application of the cured relief pattern, the composition can be cured by heating at a temperature of about 150 to 350 ° C. for about 30 minutes to 5 hours. it can.
If it is the said heating conditions, a general oven, an infrared furnace, etc. can be used as heating equipment.

Hereinafter, the present invention will be described in detail by way of examples. In addition, unless otherwise indicated, the part in a following example and a comparative example means a mass part.
The measuring method of a weight average molecular weight is as follows.
The weight average molecular weight (Mw) was measured by gel permeation chromatography (hereinafter also referred to as “GPC”) (converted to standard polystyrene (Showex STANDARD SM-105 manufactured by Showa Denko KK)). The analysis conditions for GPC are described below.
Column: Trade name Shodex 805M / 806M series manufactured by Showa Denko Co., Ltd. Liquid separation: N-methyl-2-pyrrolidone 40 ° C
Flow rate: 1.0 ml / min Detector: Showa Denko brand name Shodex RI-930

Moreover, each characteristic of hardened | cured material was implemented in the following way.
Residual film rate after heat treatment:
A photosensitive resin composition was applied to a 6-inch silicon wafer with a spin coater ("D-Spin" manufactured by Dainippon Screen) and heated on a hot plate at 110 ° C for 3 minutes to produce a uniform coating film. . The thickness of this film was measured with a step gauge (Ta). After that, using an aligner (Canon PLA), UV light from a high-pressure mercury lamp was exposed so that the exposure amount at a wavelength of 365 nm was 300 mJ / cm ^2, and then heated at 120 ° C for 3 minutes on a hot plate (PEB) did.
Next, development is performed by a paddle development method using a 2.38% tetramethylammonium hydroxide aqueous solution as a developing solution at 25 ° C. in a spin developing device (D-Spin, manufactured by Dainippon Screen). Rinse with.
Thereafter, a heat treatment was performed at 300 ° C. for 2 hours under nitrogen in a curing oven to obtain a cured film, and then the film thickness was measured (Tb).
Tb / Ta was obtained by calculation as the remaining film ratio after curing.

と２，２−ビス（３−アミノ−４−ヒドロキシフェニル）−ヘキサフルオロプロパンの１：２の混合物を収率９５％で得た。ＮＭＤがイミド化していることはＩＲチャートで、１６５０及び１５５０ｃｍ^−１付近のアミド基を示す吸収がないこと、１３８４及び１７７０ｃｍ^−１のイミド基の特性吸収が現れたことにより確認した。 Synthesis Example 1: Synthesis of hydroxypolyamide having repeating unit of formula (2) In a separable flask having a capacity of 1 L, tetrahydrofuran (THF) 396 g, pyridine 9.49 g (0.12 mol), 2,2-bis (3 -Amino-4-hydroxyphenyl) -hexafluoropropane 131.85 g (0.36 mol) was mixed and stirred at room temperature (25 ° C.) to dissolve the diamine. A solution prepared by dissolving 19.70 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic anhydride in 59.1 g of THF was added dropwise thereto from a dropping funnel. The time required for the dropping was 80 minutes, and the maximum reaction solution temperature was 26 ° C.
After stirring for 6 hours from the end of dropping, the reaction solution was passed through a glass column packed with 30 g of cation exchange resin: Amberlyst 15 (manufactured by Organo Corporation) to remove pyridine. Next, THF is distilled off from this solution under reduced pressure, and then vacuum-dried to obtain a compound having the following structure:

And a 1: 2 mixture of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane with a yield of 95%. It was confirmed by the IR chart that NMD was imidized by the absence of absorption indicating amide groups in the vicinity of 1650 and 1550 cm ⁻¹ , and the appearance of characteristic absorption of imide groups at 1384 and 1770 cm ⁻¹ .

  Next, 74.76 g of this mixture, 231 g of N, N-dimethylacetamide (DMAc) and 7.91 g (0.1 mol) of pyridine were mixed and stirred at room temperature (25 ° C.) in a 1 L separable flask. It was set as the solution. Separately, 44.27 g (0.15 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride dissolved in 133 g of diethylene glycol dimethyl ether (DMDG) was dropped from the dropping funnel. At this time, the separable flask was cooled in a water bath at 15 to 20 ° C. The time required for dropping was 40 minutes, and the temperature of the reaction solution was 30 ° C. at the maximum.

3 hours after the completion of dropping, the reaction solution was dropped into 2 L of water under high-speed stirring to disperse and precipitate the polymer, and this was recovered, washed with water, dehydrated appropriately, and then vacuum-dried to give a GPC weight average molecular weight of 9000 (polystyrene). (Converted) hydroxy polyamide was obtained.
Further, when further purification of the polymer was necessary, it could be carried out by the following method. That is, a polymer solution obtained by re-dissolving the polymer obtained above in 400 g DMDM was washed with ion exchange water, and then placed on a glass column packed with 49 g and 41 g cation exchange resin and anion exchange resin substituted with DMDG, respectively. Processing was performed by flowing. The purified polymer solution was dropped into 5 L of ion-exchanged water, and the polymer precipitated at that time was separated, washed, and then vacuum dried to obtain a purified polymer (a-1). .
It was confirmed by the IR chart that characteristic absorption of imide groups at 1385 and 1772 cm ⁻¹ appeared in the IR chart that the terminal of the obtained polymer was an imide group.

Synthesis example 2: 2 L separable equipped with a synthetic stirrer of alkali-soluble resin having a repeating unit of formulas (1) and (2), a thermometer sensor, a nitrogen gas introduction pipe, and a ball cooling pipe equipped with a moisture separation trap In the flask, 109.9 g (0.30 mol) of 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter also referred to as “6FAP”) and N-methyl-2-pyrrolidone (hereinafter referred to as “6FAP”). (It is also referred to as “NMP”) was charged with 600 g and dissolved with stirring while purging nitrogen gas at a flow rate of about 100 ml / min. After 6FAP was completely dissolved, the solution was cooled to 0 ° C. or lower. At 0 ° C., 37.2 g (0.15 mol) of bicyclo [2,2,2] oct-2-ene-2,3,5,6-tetracarboxylic dianhydride was added to the temperature of the reaction solution. Was added in small portions so as not to exceed 5 ° C. Thereafter, the reaction solution was returned to room temperature, charged with 100 g of toluene, then heated to 185 ° C. in an oil bath and stirred for 3 hours to be reacted. At the end of the reaction at 185 ° C., the produced water and toluene from the azeotrope were removed as much as possible. The reaction solution was cooled to room temperature, 10 g (0.13 mol) of pyridine was added, and the reaction solution was again cooled to 0 ° C. or less. A solution of 36.9 g (0.125 mol) of 4,4′-dicarboxydiphenyl ether chloride dissolved in 100 g NMP was added dropwise so that the reaction solution temperature did not exceed 5 ° C. After completion of the dropwise addition, the temperature was returned to room temperature, and when the reaction liquid temperature reached 10 ° C., 9.8 g (0.12 mol) of pyridine was further added. Stirring was continued for 4 hours at room temperature. The obtained reaction solution was added dropwise to ion-exchanged water with stirring, the polymer was allowed to settle, the precipitated copolymer was filtered, and washed with ion-exchanged water until the pH value of the filtrate reached 7. Thereafter, the copolymer was vacuum-dried at 50 ° C. for 48 hours to obtain a copolymer (a-2). The copolymer had a weight average molecular weight of 17,800.

[Examples 1 to 11 and Comparative Examples 1 to 3]
A photosensitive resin composition having the composition shown in Table 1 below was prepared, and these characteristics were measured by the above evaluation method. The results obtained are shown in Table 1 below.

Each title in Table 1 represents the following compound.
b-1: Irgacure PAG121 (Ciba Specialty Chemicals)

b-2: Irgacure PAG103 (Ciba Specialty Chemicals)

c-1: Nicarak MW390 (manufactured by Sanwa Chemical)

c-2: Nikaluck MX-270 (manufactured by Sanwa Chemical)

d-1: Trimethylolpropane trimethacrylate (TMPTM) (manufactured by Wako Pure Chemical Industries)

d-2: NK ester D-TMP (manufactured by Shin-Nakamura Chemical)

d-3: Aronix M-315 (manufactured by Toagosei)

d-4: Hydroxypropyl methacrylate (HPMA) (manufactured by Tokyo Chemical Industry)

d-5: Light acrylate DPE-6A (manufactured by Kyoeisha Chemical)

e-1: GBL (gamma butyrolactone)

e-2: Ethyl lactate

f-1: N-phenyl-N ′-[3- (triethoxysilyl) propyl] urea

  The composition of the present invention is suitably used in the field of photosensitive resin compositions used for surface protective films (buffer coating films) and interlayer insulating films (passivation films) for semiconductor elements and the like and cured products obtained by curing the same. Available.

Claims (4)

(A) The following formula (1):

{Wherein R ₁ is a tetravalent organic group having an aromatic ring or an aliphatic ring, and R ₂ is an organic group having a tetravalent aromatic ring. } And the following formula (2):

{Wherein R ₃ is an organic group having a divalent aromatic ring or an aliphatic ring, and R ₄ is an organic group having a tetravalent aromatic ring. } Alkali-soluble resin having at least one repeating unit selected from the group consisting of:
(B) Compound that generates acid upon irradiation: 0.01 to 20 parts by mass;
(C) a compound having a group capable of undergoing a crosslinking reaction with an acid: 0.1 to 50 parts by mass, and (d) a compound having a (meth) acryloyl group: 10 to 500 parts by mass,
A photosensitive resin composition comprising:   The formation process which forms the photosensitive resin layer which consists of the photosensitive resin composition of Claim 1 on a board | substrate, the exposure process which exposes this photosensitive resin layer with actinic rays, and heats this exposed photosensitive resin layer A method for forming a cured relief pattern, comprising: a heating step for developing, a developing step for developing, and a heating step for heating the obtained relief pattern.   A semiconductor device having a cured relief pattern formed on a silicon wafer substrate by the method for forming a cured relief pattern according to claim 2.   A method for manufacturing a semiconductor device, comprising the method for forming a cured relief pattern according to claim 2 as a part of the process.