JP5571990B2 - Negative photosensitive resin composition, cured relief pattern forming / manufacturing method, and semiconductor device - Google Patents

Description

  The present invention relates to a photosensitive resin composition used for forming a relief pattern such as an insulating material of an electronic component or a passivation film, a buffer coat film, an interlayer insulating film in a semiconductor device, a relief pattern forming / manufacturing method using the same, and The present invention relates to a semiconductor device.

  Conventionally, polyimide resins having excellent heat resistance, electrical characteristics, and mechanical characteristics have been used for insulating materials for electronic components, passivation films, surface protective films, interlayer insulating films, and the like for semiconductor devices. Among these polyimide resins, those provided in the form of photosensitive polyimide precursors can easily form a heat-resistant relief pattern film by applying, exposing, developing, and thermal imidization treatment. it can. Such a photosensitive polyimide precursor composition has a feature that the process can be greatly shortened as compared with the case of using a conventional non-photosensitive polyimide.

  On the other hand, in recent years, a method for mounting a semiconductor device on a printed wiring board has also changed from the viewpoint of improvement in integration degree, function, and reduction in chip size. There is a structure in which polyimide coating directly contacts solder bumps, such as BGA (ball gripped array) and CSP (chip size packaging), which can be mounted at higher density than conventional mounting methods using metal pins and lead-tin eutectic solder. It has come to be used. When forming such a bump structure, the film is required to have high heat resistance and chemical resistance, but by adding a thermal crosslinking agent to a composition containing a polyimide precursor or a polybenzoxazole precursor, A method for improving the heat resistance of a polyimide film or a polybenzoxazole film has been disclosed (see Patent Document 1).

  Furthermore, with the progress of miniaturization of semiconductor devices, the wiring resistance of semiconductor devices cannot be ignored. Therefore, the gold or aluminum wiring used so far has been changed to a copper or copper alloy wiring having a lower resistance. However, in the conventional photosensitive resin composition, since the compound in the composition easily reacts with copper or a copper alloy, there is a problem that discoloration or corrosion of the copper or copper alloy occurs. As a means for solving the above, a method for suppressing discoloration and corrosion occurring in copper or a copper alloy by adding triazole or a derivative thereof to a composition containing a polyimide precursor is disclosed (see Patent Document 2). . However, it has been difficult to suppress the discoloration of copper or a copper alloy while maintaining high lithography performance and to satisfy the stability of the photosensitive resin composition at the same time.

JP 2003-287889 A JP 2005-10360 A

  The present invention is a negative photosensitive resin composition excellent in sensitivity and stability without causing discoloration even on copper or a copper alloy, and pattern formation / manufacturing for forming a polyimide pattern using the photosensitive resin composition It is an object to provide a method and a semiconductor device.

  The present inventors obtained a photosensitive resin composition excellent in both stability and sensitivity without causing discoloration even on copper or a copper alloy by using a compound having a specific structure or a polymer thereof. As a result, the present invention has been completed. That is, the present invention is as follows.

｛式中、Ｘ₁は、４価の有機基であり、Ｙ₁は、２価の有機基であり、ｎは、２〜１５０の整数であり、Ｒ₁及びＲ₂は、それぞれ独立に、水素原子又は下記一般式（２）：

（式中、Ｒ₃は、水素原子又は炭素数１〜３の有機基であり、Ｒ₄及びＲ₅は、それぞれ独立に、水素原子又は炭素数１〜３の有機基であり、そしてｍは、２〜１０の整数である。）で表される一価の有機基、又は炭素数１〜４の飽和脂肪族基である。但し、Ｒ₁及びＲ₂の両者は同時に水素原子であることはない。｝で表される構造単位を有するポリイミド前駆体：１００質量部、
（Ｂ）光重合開始剤：１〜２０質量部、及び
（Ｃ）下記一般式（３）：

｛式中、Ａは酸素原子または硫黄原子であり、Ｒ₆及びＲ₇は、それぞれ独立に、炭素数１〜１０の直鎖若しくは分岐のアルキル基、アルコキシ基若しくはヒドロキシ基で置換された直鎖若しくは分岐のアルキル基、炭素数６〜１５の芳香族基、又はアルコキシ基で置換された炭素数６〜１５の芳香族基である。Ｒ₈及びＲ₉は、それぞれ独立に、水素原子、炭素数１〜１０の直鎖若しくは分岐のアルキル基、アルコキシ基若しくはヒドロキシ基で置換された直鎖若しくは分岐のアルキル基、炭素数６〜１５の芳香族基、又はアルコキシ基で置換された炭素数６〜１５の芳香族基である。｝で表される化合物、若しくはその重合体及び下記一般式（４）：

｛式中、Ａは酸素原子または硫黄原子であり、Ｒ₁₀及びＲ₁₁は、それぞれ独立に、炭素数１〜１０の直鎖若しくは分岐のアルキル基、アルコキシ基若しくはヒドロキシ基で置換された直鎖若しくは分岐のアルキル基、炭素数６〜１５の芳香族基、又はアルコキシ基で置換された炭素数６〜１５の芳香族基である。Ｒ₁₂は、炭素数１〜１０のアルキル基若しくは芳香族基、若しくはアルキルエーテル基、又は、アルコキシ基で置換された炭素数１〜１０のアルキル基である。｝で表される化合物、若しくはその重合体からなる群より選ばれる少なくとも一種の化合物、若しくはその重合体：０．１〜３０質量部、
を含むネガ型感光性樹脂組成物。 [1] The following:
(A) The following general formula (1):

{Wherein X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n is an integer of _{2 to} 150, and R ₁ and R ₂ are each independently Hydrogen atom or the following general formula (2):

Wherein R ₃ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is It is an integer of 2-10.) The monovalent organic group represented by this, or a C1-C4 saturated aliphatic group. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. } Polyimide precursor having a structural unit represented by: 100 parts by mass,
(B) Photopolymerization initiator: 1 to 20 parts by mass, and (C) the following general formula (3):

{In the formula, A is an oxygen atom or a sulfur atom, and R ₆ and R ₇ are each independently a straight chain substituted with a linear or branched alkyl group, alkoxy group or hydroxy group having 1 to 10 carbon atoms. Or it is a branched alkyl group, a C6-C15 aromatic group, or a C6-C15 aromatic group substituted by the alkoxy group. R ₈ and R ₉ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkyl group substituted with an alkoxy group or a hydroxy group, or 6 to 15 carbon atoms. Or an aromatic group having 6 to 15 carbon atoms substituted with an alkoxy group. } Or a polymer thereof and the following general formula (4):

{In the formula, A is an oxygen atom or a sulfur atom, and R ₁₀ and R ₁₁ are each independently a straight chain substituted with a linear or branched alkyl group, alkoxy group or hydroxy group having 1 to 10 carbon atoms. Or it is a branched alkyl group, a C6-C15 aromatic group, or a C6-C15 aromatic group substituted by the alkoxy group. R ₁₂ is an alkyl group having 1 to 10 carbon atoms, an aromatic group, an alkyl ether group, or an alkyl group having 1 to 10 carbon atoms substituted with an alkoxy group. }, Or at least one compound selected from the group consisting of polymers thereof, or polymers thereof: 0.1 to 30 parts by mass,
A negative photosensitive resin composition comprising:

｛式中、Ｒ₁₃及びＲ₁₄は、それぞれ独立に、炭素数１〜１０の直鎖若しくは分岐のアルキル基、ヒドロキシ基で置換された直鎖若しくは分岐のアルキル基、炭素数６〜１５の芳香族基、又はアルコキシ基で置換された炭素数６〜１５の芳香族基である。Ｒ₁₅及びＲ₁₆は、それぞれ独立に、水素原子、炭素数１〜１０の直鎖若しくは分岐のアルキル基、アルコキシ基若しくはヒドロキシ基で置換された直鎖若しくは分岐のアルキル基、炭素数６〜１５の芳香族基、又はアルコキシ基で置換された炭素数６〜１５の芳香族基である。｝で表される化合物、若しくはその重合体及び下記一般式（６）：

｛式中、Ｒ₁₇及びＲ₁₈は、それぞれ独立に、炭素数１〜１０の直鎖若しくは分岐のアルキル基、アルコキシ基若しくはヒドロキシ基で置換された直鎖若しくは分岐のアルキル基、炭素数６〜１５の芳香族基、又はアルコキシ基で置換された炭素数６〜１５の芳香族基である。Ｒ₁₉は、炭素数１〜１０のアルキル基若しくは芳香族基、若しくはアルキルエーテル基、又は、アルコキシ基で置換された炭素数１〜１０のアルキル基である。｝で表される化合物、若しくはその重合体からなる群より選ばれる、前記［１］に記載のネガ型感光性樹脂組成物。 [2] (C) The compound represented by the above general formulas (3) and (4) or a polymer thereof is represented by the following general formula (5):

{In the formula, each of R ₁₃ and R ₁₄ independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkyl group substituted with a hydroxy group, or an aromatic group having 6 to 15 carbon atoms. Or an aromatic group having 6 to 15 carbon atoms substituted with an alkoxy group or an alkoxy group. R ₁₅ and R ₁₆ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkyl group substituted with an alkoxy group or a hydroxy group, or 6 to 15 carbon atoms. Or an aromatic group having 6 to 15 carbon atoms substituted with an alkoxy group. } Or a polymer thereof and the following general formula (6):

{In the formula, R ₁₇ and R ₁₈ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkyl group substituted with an alkoxy group or a hydroxy group, and 6 to 6 carbon atoms. It is a C6-C15 aromatic group substituted by 15 aromatic groups or an alkoxy group. R ₁₉ is an alkyl group having 1 to 10 carbon atoms, an aromatic group, an alkyl ether group, or an alkyl group having 1 to 10 carbon atoms substituted with an alkoxy group. } The negative photosensitive resin composition as described in said [1] selected from the group which consists of a compound or its polymer represented by this.

｛式中、Ｒ₂₀は、炭素数１〜１０の直鎖若しくは分岐のアルキル基、ヒドロキシ基で置換された直鎖若しくは分岐のアルキル基、炭素数６〜１５の芳香族基、又はアルコキシ基で置換された炭素数６〜１５の芳香族基である。Ｒ₂₁は、炭素数１〜１０の直鎖若しくは分岐のアルキル基、ヒドロキシ基で置換された直鎖若しくは分岐のアルキル基である。Ｒ₂₀、Ｒ₂₁は、互いに異なっていても同じであってもよい。Ｒ₂₂及びＲ₂₃は、それぞれ独立に、水素原子、炭素数１〜１０の直鎖若しくは分岐のアルキル基、アルコキシ基若しくはヒドロキシ基で置換された直鎖若しくは分岐のアルキル基、炭素数６〜１５の芳香族基、又はアルコキシ基で置換された炭素数６〜１５の芳香族基である。｝で表される、前記［１］に記載のネガ型感光性樹脂組成物。 [3] (C) The compound represented by the above general formulas (3) and (4) or a polymer thereof is represented by the following general formula (7):

{In the formula, R ₂₀ represents a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkyl group substituted with a hydroxy group, an aromatic group having 6 to 15 carbon atoms, or an alkoxy group. It is a substituted aromatic group having 6 to 15 carbon atoms. R ₂₁ is a linear or branched alkyl group having 1 to 10 carbon atoms or a linear or branched alkyl group substituted with a hydroxy group. R ₂₀ and R ₂₁ may be different from each other or the same. R ₂₂ and R ₂₃ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkyl group substituted with an alkoxy group or a hydroxy group, or 6 to 15 carbon atoms. Or an aromatic group having 6 to 15 carbon atoms substituted with an alkoxy group. } The negative photosensitive resin composition as described in [1] above.

  [4] (C) The negative type according to claim 1, wherein the compound represented by the general formulas (3) and (4) or a polymer thereof is 1,3-dimethylolurea or a polymer thereof. Photosensitive resin composition.

｛式中、Ｒ₂₄及びＲ₂₅は、それぞれ独立に、水素原子、炭素数１〜４０の直鎖若しくは分岐のアルキル基、又はカルボキシル基、ヒドロキシ基、アミノ基若しくはニトロ基で置換された炭素数１〜４０のアルキル基若しくは芳香族基である。Ｒ₂₆は、水素原子、フェニル基、アミノ基若しくはシリル基で置換された炭素数１〜４０のアルキル基若しくは芳香族基である。｝及び下記一般式（９）：

｛式中、Ｒ₂₇は、水素原子、カルボキシル基、ヒドロキシ基、アミノ基、ニトロ基、炭素数１〜４０の直鎖若しくは分岐のアルキル基、又はカルボキシル基、ヒドロキシ基、アミノ基若しくはニトロ基で置換された炭素数１〜４０のアルキル基若しくは芳香族基であり、Ｒ₂₈は、水素原子、フェニル基、アミノ基若しくはシリル基で置換された炭素数１〜４０のアルキル基若しくは芳香族基である。｝及び下記一般式（１０）：

｛式中、Ｒ₂₉は、水素原子、炭素数１〜４０の直鎖若しくは分岐のアルキル基、又はカルボキシル基、ヒドロキシ基、アミノ基若しくはニトロ基で置換された炭素数１〜４０のアルキル基若しくは芳香族基であり、Ｒ₃₀は、水素原子、フェニル基、アミノ基若しくはシリル基で置換された炭素数１〜４０のアルキル基若しくは芳香族基である。｝で表されるアゾール化合物０．１〜２０質量部をさらに含有する、前記［１］〜［４］のいずれかに記載のネガ型感光性樹脂組成物。 [5] The negative photosensitive resin composition is (D) the following general formula (8):

{Wherein R ₂₄ and R ₂₅ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, or a carbon number substituted with a carboxyl group, a hydroxy group, an amino group or a nitro group. 1 to 40 alkyl groups or aromatic groups. R ₂₆ is a C 1-40 alkyl group or aromatic group substituted with a hydrogen atom, a phenyl group, an amino group or a silyl group. } And the following general formula (9):

{In the formula, R ₂₇ represents a hydrogen atom, a carboxyl group, a hydroxy group, an amino group, a nitro group, a linear or branched alkyl group having 1 to 40 carbon atoms, or a carboxyl group, a hydroxy group, an amino group, or a nitro group. A substituted or unsubstituted alkyl group or aromatic group having 1 to 40 carbon atoms, and R ₂₈ is a substituted or unsubstituted alkyl group or aromatic group having 1 to 40 carbon atoms substituted with a hydrogen atom, phenyl group, amino group or silyl group. is there. } And the following general formula (10):

{In the formula, R ₂₉ represents a hydrogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, or an alkyl group having 1 to 40 carbon atoms substituted with a carboxyl group, a hydroxy group, an amino group, or a nitro group; It is an aromatic group, and R ₃₀ is an alkyl group having 1 to 40 carbon atoms or an aromatic group substituted with a hydrogen atom, a phenyl group, an amino group or a silyl group. } The negative photosensitive resin composition in any one of said [1]-[4] which further contains 0.1-20 mass parts of azole compounds represented by these.

  [6] The negative photosensitive resin composition according to any one of [1] to [5], wherein the negative photosensitive resin composition further contains 0.1 to 20 parts by mass of (E) a hindered phenol compound. Resin composition.

｛式中、Ｒ₃₁は、t-ブチル基であり、Ｒ₃₂及びＲ₃₄は、それぞれ独立に、水素原子、又はアルキル基であり、Ｒ₃₃は、水素原子、アルキル基、アルコキシ基、ヒドロキシアルキル基、ジアルキルアミノアルキル基、ヒドロキシ基、又はカルボキシル基で置換されたアルキル基であり、Ｒ₃₅は、水素原子、又はアルキル基である。｝で表される化合物；
下記一般式（１２）：

｛式中、Ｒ₃₆は、t-ブチル基であり、Ｒ₃₇、Ｒ₃₈及びＲ₃₉は、それぞれ独立に、水素原子、又はアルキル基であり、Ｒ₄₀は、アルキレン基、硫黄原子、ジメチレンチオエーテル基、又は下記一般式（１３）：

（式中、Ｒ₄₁は、炭素数１〜６のアルキル基、ジエチレンチオエーテル基、又は下記式（１４）：

で表される基である。）若しくは下記式（１５）：

で表される基である。｝で表される化合物；
下記一般式（１６）：

｛式中、Ｒ₄₂は、t-ブチル基、シクロヘキシル基、又はメチルシクロヘキシル基であり、Ｒ₄₃、Ｒ₄₄、及びＲ₄₅は、それぞれ独立に、水素原子、又はアルキル基であり、そしてＲ₄₆は、アルキレン基、硫黄原子、又はテレフタル酸エステルである。｝で表される化合物；
下記一般式（１７）：

｛式中、Ｒ₄₇は、t-ブチル基であり、Ｒ₄₈、Ｒ₄₉及びＲ₅₀は、それぞれ独立に、水素原子、又はアルキル基であり、そしてＲ₅₁は、アルキル基、フェニル基、イソシアヌレート基又はプロピオネート基である。｝で表される化合物；並びに
下記一般式（１８）：

｛式中、Ｒ₅₂及びＲ₅₃は、それぞれ独立に、水素原子又は炭素数１〜６の１価の有機基であり、Ｒ₅₅は、アルキル基、フェニル基、イソシアヌレート基又はプロピオネート基であり、Ｒ₅₄は、下記一般式（１９）：

（式中、Ｒ₅₆、Ｒ₅₇及びＲ₅₈は、それぞれ独立に、水素原子、又は炭素数１〜６の１価の有機基である。但し、Ｒ₅₆、Ｒ₅₇及びＲ₅₈のうち少なくとも２つは炭素数１〜６の１価の有機基である。）で表される基、又はフェニル基である。｝で表される化合物からなる群から選ばれる、前記［６］に記載のネガ型感光性樹脂組成物。 [7] The (E) hindered phenol compound has the following general formula (11):

{Wherein R ₃₁ is a t-butyl group, R ₃₂ and R ₃₄ are each independently a hydrogen atom or an alkyl group, and R ₃₃ is a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyalkyl group. Group, a dialkylaminoalkyl group, a hydroxy group, or an alkyl group substituted with a carboxyl group, and R ₃₅ is a hydrogen atom or an alkyl group. } A compound represented by
The following general formula (12):

{In the formula, R ₃₆ represents a t-butyl group; R ₃₇ , R ₃₈ and R ₃₉ each independently represents a hydrogen atom or an alkyl group; and R ₄₀ represents an alkylene group, a sulfur atom, or dimethylene. Thioether group or the following general formula (13):

(In the formula, R ₄₁ represents an alkyl group having 1 to 6 carbon atoms, a diethylenethioether group, or the following formula (14):

It is group represented by these. ) Or the following formula (15):

It is group represented by these. } A compound represented by
The following general formula (16):

{Wherein R ₄₂ is a t-butyl group, a cyclohexyl group, or a methylcyclohexyl group, R ₄₃ , R ₄₄ , and R ₄₅ are each independently a hydrogen atom or an alkyl group, and R ₄₆ Is an alkylene group, a sulfur atom, or a terephthalic acid ester. } A compound represented by
The following general formula (17):

{In the formula, R ₄₇ is a t-butyl group; R ₄₈ , R ₄₉ and R ₅₀ are each independently a hydrogen atom or an alkyl group; and R ₅₁ is an alkyl group, a phenyl group, an isocyanate group. It is a nurate group or a propionate group. }; And the following general formula (18):

{Wherein R ₅₂ and R ₅₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, and R ₅₅ is an alkyl group, a phenyl group, an isocyanurate group or a propionate group. , R ₅₄ is represented by the following general formula (19):

(In the formula, R ₅₆ , R ₅₇ and R ₅₈ are each independently a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, provided that at least 2 of R ₅₆ , R ₅₇ and R ₅₈ are present. Is a monovalent organic group having 1 to 6 carbon atoms.) Or a phenyl group. } The negative photosensitive resin composition as described in [6] above, selected from the group consisting of compounds represented by:

[8] The negative photosensitive resin according to any one of [1] to [7], wherein the negative photosensitive resin composition further contains 0.05 to 10 parts by mass of (F) an organic titanium compound. Composition.

[9] The negative photosensitive resin composition according to [8], wherein the (F) organic titanium compound is at least one selected from the group consisting of a titanium chelate compound, a tetraalkoxytitanium compound, and a titanocene compound.

[10] The following steps:
(1) Applying the negative photosensitive resin composition according to any one of [1] to [9] to a substrate,
(2) irradiating the negative photosensitive resin composition with actinic rays,
(3) The negative photosensitive resin composition after the irradiation is developed to form a relief pattern, and (4) The relief pattern is heated.
A method for forming a cured relief pattern.

[11] The following:
(1) forming a photosensitive resin layer comprising the photosensitive resin composition according to any one of [1] to [9] on a substrate;
(2) exposing the photosensitive resin layer;
(3) removing the unexposed portion after the exposure to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising a step of heat-treating the relief pattern.

  [12] A semiconductor device having a cured relief pattern obtained by the production method according to [11].

｛式中、Ａは酸素原子または硫黄原子であり、Ｒ₁₀及びＲ₁₁は、それぞれ独立に、炭素数１〜１０の直鎖若しくは分岐のアルキル基、アルコキシ基若しくはヒドロキシ基で置換された直鎖若しくは分岐のアルキル基、炭素数６〜１５の芳香族基、又はアルコキシ基で置換された炭素数６〜１５の芳香族基である。Ｒ₁₂は、炭素数１〜１０のアルキル基若しくは芳香族基、若しくはアルキルエーテル基、又は、アルコキシ基で置換された炭素数１〜１０のアルキル基である。｝で表される化合物、若しくはその重合体。 [13] The following general formula (4):

{In the formula, A is an oxygen atom or a sulfur atom, and R ₁₀ and R ₁₁ are each independently a straight chain substituted with a linear or branched alkyl group, alkoxy group or hydroxy group having 1 to 10 carbon atoms. Or it is a branched alkyl group, a C6-C15 aromatic group, or a C6-C15 aromatic group substituted by the alkoxy group. R ₁₂ is an alkyl group having 1 to 10 carbon atoms, an aromatic group, an alkyl ether group, or an alkyl group having 1 to 10 carbon atoms substituted with an alkoxy group. } Or a polymer thereof.

  By adding a compound having a specific structure or a polymer thereof to the negative photosensitive resin composition, it is highly sensitive and extremely stable, and at the same time, it can suppress discoloration on copper or copper alloy. A negative photosensitive resin composition can be obtained, and a pattern forming / manufacturing method for forming a polyimide pattern using the photosensitive resin composition and a semiconductor device can be provided.

The present invention will be specifically described below.
The negative photosensitive resin composition of the present invention has, as an essential component, (A) a polyimide precursor having a repeating unit represented by the following general formula (1) (hereinafter also referred to as (A) a polyimide precursor) 100 mass Part, (B) 1-20 parts by mass of a photopolymerization initiator, (C) at least one compound selected from the group consisting of compounds represented by the following general formulas (3) and (4), or polymers thereof, or The polymer consists of 0.1 to 30 parts by mass.

｛式中、Ｘ₁は、４価の有機基であり、Ｙ₁は、２価の有機基であり、ｎは、２〜１５０の整数であり、Ｒ₁及びＲ₂は、それぞれ独立に、水素原子又は下記一般式（２）：

（式中、Ｒ₃は、水素原子又は炭素数１〜３の有機基であり、Ｒ₄及びＲ₅は、それぞれ独立に、水素原子又は炭素数１〜３の有機基であり、そしてｍは、２〜１０の整数である。）で表される一価の有機基、又は炭素数１〜４の飽和脂肪族基である。但し、Ｒ₁及びＲ₂の両者は同時に水素原子であることはない。｝。 (A) Polyimide precursor (A) The polyimide precursor used for this invention is demonstrated. The resin component in the photosensitive resin composition of the present invention is a polyamide having a structural unit represented by the following general formula (1). (A) A polyimide precursor is converted into a polyimide by performing a cyclization treatment (for example, 200 ° C. or higher).
The following general formula (1):

{Wherein X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n is an integer of _{2 to} 150, and R ₁ and R ₂ are each independently Hydrogen atom or the following general formula (2):

Wherein R ₃ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is It is an integer of 2-10.) The monovalent organic group represented by this, or a C1-C4 saturated aliphatic group. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. }.

の構造が挙げられるが、これらに限定されるものではない。また、これらは単独でも、二種以上が組み合わされても構わない。これらのＸ₁基は耐熱性と感光特性を両立するという点で好ましい。 In the general formula (1), the tetravalent organic group represented by X ₁ is preferably an organic group having 6 to 40 carbon atoms, and more preferably —COOR ₁ group, —COOR ₂ group and — The CONH-group is an aromatic group or an alicyclic aliphatic group in the ortho position relative to each other. More preferably, the following formula (20):

However, it is not limited to these. These may be used alone or in combination of two or more. These X ₁ groups are preferable in terms of achieving both heat resistance and photosensitive properties.

や下記一般式（２２）：

の構造が挙げられるが、これらに限定されるものではない。また、これらは単独でも、二種以上が組み合わされても構わない。これらのＹ₁基は、耐熱性と感光特性を両立するという点で好ましい。 In the general formula (1), the divalent organic group represented by Y ₁ is preferably an aromatic group having 6 to 40 carbon atoms. For example, the following formula (21):

Or the following general formula (22):

However, it is not limited to these. These may be used alone or in combination of two or more. These Y ₁ groups are preferable in terms of achieving both heat resistance and photosensitive properties.

The polyimide precursor represented by the above chemical formula (1) of the present invention is firstly tetracarboxylic dianhydride containing a tetravalent organic group X ₁ and alcohols having a photopolymerizable unsaturated double bond. And a partially esterified tetracarboxylic acid (hereinafter referred to as an acid / ester) by reacting with a saturated aliphatic alcohol having 1 to 4 carbon atoms and a divalent organic group Y ₁ . It can be obtained by amide polycondensation with diamines.

(Preparation of acid / ester)
Examples of the tetracarboxylic dianhydride containing a tetravalent organic group X ₁ preferably used in the present invention include pyromellitic anhydride, diphenyl ether-3,3 ′, 4,4′-tetracarboxylic dianhydride. Benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride, biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, diphenylsulfone-3,3 ′, 4 4'-tetracarboxylic dianhydride, diphenylmethane-3,3 ', 4,4'-tetracarboxylic dianhydride, 2,2-bis (3,4-phthalic anhydride) propane, 2,2-bis Examples include (3,4-phthalic anhydride) -1,1,1,3,3,3-hexafluoropropane, but are not limited thereto. These may be used alone or in combination of two or more.

  Examples of alcohols having a photopolymerizable unsaturated double bond that can be suitably used in the present invention include 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, and methylol. Vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propiyl Alcohol, 2-methacrylamidoethyl alcohol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2 -Hydroxy-3-t-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate and the like can be mentioned.

  The alcohols may be used by partially mixing a saturated aliphatic alcohol having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and the like.

  By stirring and dissolving the tetracarboxylic dianhydride suitable for the present invention and alcohols in a suitable solvent in the presence of a basic catalyst such as pyridine at a temperature of 20 to 50 ° C. for 4 to 10 hours. The esterification reaction of the acid anhydride proceeds, and the desired acid / ester product can be obtained.

  The reaction solvent is preferably a solvent that completely dissolves the acid / ester and a polyimide precursor that is an amide polycondensation product of this with a diamine component. For example, N-methyl-2-pyrrolidone, N, N- Examples thereof include dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, and gamma butyrolactone.

  Other reaction solvents include ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons such as 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 and the like. These may be used alone or in combination as required.

(Preparation of polyimide precursor)
To the acid / ester solution, an appropriate dehydration condensing agent such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1 is cooled under ice cooling. , 2,3-benzotriazole, N, N′-disuccinimidyl carbonate and the like, and the acid / ester is converted into a polyanhydride, and then the divalent organic group Y suitably used in the present invention is used. _A target polyimide precursor can be obtained by adding dropwise a diamine containing ₁ separately dissolved or dispersed in a solvent and subjecting it to amide polycondensation.

Examples of diamines containing a divalent organic group Y ₁ that are preferably used in the present invention include p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3, 3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone 3,3′-diaminodiphenyl sulfone, 4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 4,4′-diaminobenzophenone, 3,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 4,4′-diaminodipheni Methane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis ( 3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4-bis (4-aminophenoxy) biphenyl, 4, 4-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenyl) Benzene, 1,3-bis (4-aminophenyl) benzene, 9,10-bis (4-aminophenyl) anthracene, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl) propane, 2,2- Bis [4- (4-aminophenoxy) phenyl) hexafluoropropane, 1,4-bis (3-aminopropyldimethylsilyl) benzene, ortho-tolidine sulfone, 9,9-bis (4-aminophenyl) fluorene, and Those in which some of the hydrogen atoms on these benzene rings are substituted with a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a halogen, etc., for example, 3,3′-dimethyl-4,4′-diaminobiphenyl 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 2, Examples include '-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyloxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof. However, the present invention is not limited to this.

  In addition, diaminosiloxanes such as 1,3-bis (3-aminopropyl) tetramethyldisiloxane and 1,3-bis (3-aminopropyl) tetraphenyldisiloxane for the purpose of improving adhesion to various substrates. Can also be copolymerized.

  After completion of the reaction, the water-absorbing by-product of the dehydrating condensing agent coexisting in the reaction solution was filtered off if necessary, and a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof was obtained. The polymer component is put into the polymer component, and the polymer component is precipitated. Further, the polymer is purified by repeating redissolution and reprecipitation, and the target polyimide precursor is isolated by vacuum drying. In order to improve the degree of purification, the polymer solution may be passed through a column packed with an anion-cation exchange resin swollen with a suitable organic solvent to remove ionic impurities.

  The molecular weight of the polyimide precursor is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, as measured by polystyrene-reduced weight average molecular weight by gel permeation chromatography. . When the weight average molecular weight is 8,000 or more, the mechanical properties are improved, and when it is 150,000 or less, the dispersibility in the developer is improved, and the resolution performance of the relief pattern is improved. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from standard organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko.

(B) Photopolymerization initiator (B) The photopolymerization initiator used in the present invention will be described. Examples of the photopolymerization initiator used as the component (B) include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, and fluorenone, and 2,2 ′. -Acetophenone derivatives such as diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, benzyldimethyl Benzyl derivatives such as ketal, benzyl-β-methoxyethyl acetal, benzoin derivatives such as benzoin and benzoin methyl ether, 1-phenyl-1,2-butanedione 2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) ) Oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione Preferred examples include oximes such as -2- (o-benzoyl) oxime, N-aryl glycines such as N-phenylglycine, peroxides such as benzoyl perchloride, and aromatic biimidazoles. It is not limited. Moreover, in using these, it may be individual or a mixture of 2 or more types. Among the above photopolymerization initiators, oximes are more preferable particularly from the viewpoint of photosensitivity.

  The addition amount of these photoinitiators is 1-20 mass parts with respect to 100 mass parts of polyimide precursors, and 2-15 mass parts is preferable from a viewpoint of a photosensitivity characteristic. By adding 1 part by mass or more of the photoinitiator to 100 parts by mass of the (A) polyimide precursor, the photosensitivity is excellent, and by adding 20 parts by mass or less, the thick film curability is excellent.

｛式中、Ａは酸素原子または硫黄原子であり、Ｒ₆及びＲ₇は、それぞれ独立に、炭素数１〜１０の直鎖若しくは分岐のアルキル基、アルコキシ基若しくはヒドロキシ基で置換された直鎖若しくは分岐のアルキル基、炭素数６〜１５の芳香族基、又はアルコキシ基で置換された炭素数６〜１５の芳香族基である。Ｒ₈及びＲ₉は、それぞれ独立に、水素原子、炭素数１〜１０の直鎖若しくは分岐のアルキル基、アルコキシ基若しくはヒドロキシ基で置換された直鎖若しくは分岐のアルキル基、炭素数６〜１５の芳香族基、又はアルコキシ基で置換された炭素数６〜１５の芳香族基である。｝で表される化合物、若しくはその重合体；
一般式（４）：

｛式中、Ａは酸素原子または硫黄原子であり、Ｒ₁₀及びＲ₁₁は、それぞれ独立に、炭素数１〜１０の直鎖若しくは分岐のアルキル基、アルコキシ基若しくはヒドロキシ基で置換された直鎖若しくは分岐のアルキル基、炭素数６〜１５の芳香族基、又はアルコキシ基で置換された炭素数６〜１５の芳香族基である。Ｒ₁₂は、炭素数１〜１０のアルキル基若しくは芳香族基、若しくはアルキルエーテル基、又は、アルコキシ基で置換された炭素数１〜１０のアルキル基である。｝。 (C) The compound represented by the general formulas (3) and (4), or a polymer thereof. The component (C) used in the present invention will be described. In the present invention, a compound having a specific structure, or a polymer thereof, that is, a compound represented by the following general formula (3), a polymer thereof and a compound represented by the following general formula (4), or By using at least one compound selected from the group consisting of polymers, or polymers thereof, the sensitivity and stability of the polyimide precursor resin composition (highly maintained even after a long period of time after preparing the photosensitive resin composition). It is possible to maintain a sensitive relief pattern forming ability) and to obtain an advantage of preventing discoloration on copper.
General formula (3):

{In the formula, A is an oxygen atom or a sulfur atom, and R ₆ and R ₇ are each independently a straight chain substituted with a linear or branched alkyl group, alkoxy group or hydroxy group having 1 to 10 carbon atoms. Or it is a branched alkyl group, a C6-C15 aromatic group, or a C6-C15 aromatic group substituted by the alkoxy group. R ₈ and R ₉ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkyl group substituted with an alkoxy group or a hydroxy group, or 6 to 15 carbon atoms. Or an aromatic group having 6 to 15 carbon atoms substituted with an alkoxy group. } Or a polymer thereof;
General formula (4):

{In the formula, A is an oxygen atom or a sulfur atom, and R ₁₀ and R ₁₁ are each independently a straight chain substituted with a linear or branched alkyl group, alkoxy group or hydroxy group having 1 to 10 carbon atoms. Or it is a branched alkyl group, a C6-C15 aromatic group, or a C6-C15 aromatic group substituted by the alkoxy group. R ₁₂ is an alkyl group having 1 to 10 carbon atoms, an aromatic group, an alkyl ether group, or an alkyl group having 1 to 10 carbon atoms substituted with an alkoxy group. }.

  Examples of the component (C) include 1,3-dimethylurea, 1,3-dimethylthiourea, 1,3-dimethylolurea, 1,3-dimethylolthiourea, 1,3-dimethoxymethylurea, 1,3. -Dimethoxymethylthiourea, 1,3-diethylurea, 1,3-diethylthiourea, 1,3-diisopropylurea, 1,3-diisopropylthiourea, 1,3-di-n-propylurea, 1,3-di -N-propylthiourea, 1,3-dibutylurea, 1,3-dibutylthiourea, 1,3-bis (2-methylpropyl) urea, 1,3-bis (2-methylpropyl) thiourea, 1,3 -Bis (1-methylpropyl) urea, 1,3-bis (1-methylpropyl) thiourea, 1,3-dicyclopentylurea, 1,3-dicyclopentylthiourea, 1,3-di-n-pe Tylurea, 1,3-di-n-pentylthiourea, 1,3-bis (1-methylbutyl) urea, 1,3-bis (1-methylbutyl) thiourea, 1,3-bis (2-methylbutyl) urea 1,3-bis (2-methylbutyl) thiourea, 1,3-bis (3-methylbutyl) urea, 1,3-bis (3-methylbutyl) thiourea, 1,3-bis (1-ethylpropyl) Urea, 1,3-bis (1-ethylpropyl) thiourea, 1,3-dicyclohexylurea, 1,3-dicyclohexylthiourea, 1,3-diphenylurea, 1,3-diphenylthiourea, 1,3- Dihydroxyethylurea, 1,3-dihydroxyethylthiourea, 1,3-di (4-pyridyl) urea, 1,3-di (4-pyridyl) thiourea, 1,3-di (3-pyridyl) urea, 1,3-di ( -Pyridyl) thiourea, 1,3-di (2-pyridyl) urea, 1,3-di (2-pyridyl) thiourea, 1-adamantyl-3-phenylurea, 1-adamantyl-3-phenylthiourea, , 3-di (o-tolyl) urea, 1,3-di (o-tolyl) thiourea, 1,3-di (p-tolyl) urea, 1,3-di (p-tolyl) thiourea, -Methyl-3-ethylurea, 1-methyl-3-ethylthiourea, 1-methyl-3-n-propylurea, 1-methyl-3-n-propylthiourea, 1-methyl-3-isopropylurea, 1- Methyl-3-isopropylthiourea, 1-methyl-3- (2-methylbutyl) urea, 1-methyl-3- (2-methylbutyl) thiourea, 1-methyl-3- (1-methylbutyl) urea, 1- Methyl-3- (1-methylbutyl) thio 1-methyl-3-n-pentylurea, 1-methyl-3-n-pentylthiourea, 1-methyl-3-n-butylurea, 1-methyl-3-n-butylthiourea, 1-methyl- 3-n-hexylurea, 1-methyl-3-n-hexylthiourea, 1-methyl-3-cyclohexylurea, 1-methyl-3-cyclohexylthiourea, 1,3-bis (3,5-dimethylphenyl) Urea, 1,3-bis (3,5-dimethylphenyl) thiourea, 1,3-bis (3-methoxypropyl) urea, 1,3-bis (3-methoxypropyl) thiourea, 1-methyl-3 -Benzylurea, 1-methyl-3-benzylthiourea, 1,3-dibenzylurea, 1,3-dibenzylthiourea, 1-ethyl-3-n-propylurea, 1-ethyl-3-n-propylthiourea, -Ethyl-3-isopropylurea, 1-ethyl-3-isopropylthiourea, 1-ethyl-3- (2-methylbutyl) urea, 1-ethyl-3- (2-methylbutyl) thiourea, 1-ethyl-3 -(1-methylbutyl) urea, 1-ethyl-3- (1-methylbutyl) thiourea, 1-ethyl-3-n-pentylurea, 1-ethyl-3-n-pentylthiourea, 1-ethyl-3- n-butylurea, 1-ethyl-3-n-butylthiourea, 1-ethyl-3-n-hexylurea, 1-ethyl-3-n-hexylthiourea, 1-ethyl-3-cyclohexylurea, 1-ethyl -3-cyclohexylthiourea, 1-methyl-3- (3,5-dimethylphenyl) urea, 1-methyl-3- (3,5-dimethylphenyl) thiourea, 1-ethyl-3- (3,5 -Jimee Ruphenyl) urea, 1-ethyl-3- (3,5-dimethylphenyl) thiourea, 1-methyl-3-acetylurea, 1-methyl-3-acetylthiourea, and urea compound represented by formula (23) , Or a polymer thereof, and N-methoxymethylated nylon and methoxymethylated urea resin (manufactured by Sanwa Chemical Co., Ltd., trade name: Nikalac, product number MX-290, polymerization degree 1.8, and Nippon Cytec Industries, Ltd., Trade name UFR65, degree of polymerization 2.5) is preferred, but is not limited thereto. Moreover, in using these, it may be individual or a mixture of 2 or more types.

  (C) The addition amount of a component is 0.1-30 mass parts with respect to 100 mass parts of (A) polyimide precursor. If the addition amount of component (C) to 100 parts by mass of (A) polyimide precursor is 0.1 parts by mass or more, the stability of the photosensitive resin composition of the present invention is improved, while the amount is 30 parts by mass or less. If there is, for example, when the photosensitive resin composition of the present invention is formed on copper or a copper alloy, a good relief pattern can be obtained. The amount of component (C) added is preferably 0.1 to 20 parts by mass from the viewpoint of photosensitivity characteristics, and 0.1 to 4 from the viewpoint of excellent elongation of the cured relief pattern and suppression of discoloration of copper or copper alloy. More preferably, 8 parts by mass.

  Among the components (C) described above, the compound represented by the following general formula (5) or general formula (6) or a polymer thereof is preferably used, and these are used in the photosensitive resin composition of the present invention. In this case, the effect can be further improved in suppressing discoloration of copper or copper alloy. Furthermore, for example, a urea compound represented by the following general formula (7) such as 1,3-dimethylurea is suitably used for the resin composition. In this case, a relief pattern forming ability with higher sensitivity can be obtained. Furthermore, particularly in terms of photosensitivity, 1,3-dimethoxymethylurea and its polymer, 1,3-dimethylolurea and its polymer are more preferable.

｛式中、Ｒ₁₃及びＲ₁₄は、それぞれ独立に、炭素数１〜１０の直鎖若しくは分岐のアルキル基、ヒドロキシ基で置換された直鎖若しくは分岐のアルキル基、炭素数６〜１５の芳香族基、又はアルコキシ基で置換された炭素数６〜１５の芳香族基である。Ｒ₁₅及びＲ₁₆は、それぞれ独立に、水素原子、炭素数１〜１０の直鎖若しくは分岐のアルキル基、アルコキシ基若しくはヒドロキシ基で置換された直鎖若しくは分岐のアルキル基、炭素数６〜１５の芳香族基、又はアルコキシ基で置換された炭素数６〜１５の芳香族基である。｝で表される化合物、若しくはその重合体；
一般式（６）：

｛式中、Ｒ₁₇及びＲ₁₈は、それぞれ独立に、炭素数１〜１０の直鎖若しくは分岐のアルキル基、アルコキシ基若しくはヒドロキシ基で置換された直鎖若しくは分岐のアルキル基、炭素数６〜１５の芳香族基、又はアルコキシ基で置換された炭素数６〜１５の芳香族基である。Ｒ₁₉は、炭素数１〜１０のアルキル基若しくは芳香族基、若しくはアルキルエーテル基、又は、アルコキシ基で置換された炭素数１〜１０のアルキル基である。｝；
一般式（７）：

｛式中、Ｒ₂₀は、炭素数１〜１０の直鎖若しくは分岐のアルキル基、ヒドロキシ基で置換された直鎖若しくは分岐のアルキル基、炭素数６〜１５の芳香族基、又はアルコキシ基で置換された炭素数６〜１５の芳香族基である。Ｒ₂₁は、炭素数１〜１０の直鎖若しくは分岐のアルキル基、ヒドロキシ基で置換された直鎖若しくは分岐のアルキル基である。Ｒ₂₀、Ｒ₂₁は、互いに異なっていても同じであってもよい。Ｒ₂₂及びＲ₂₃は、それぞれ独立に、水素原子、炭素数１〜１０の直鎖若しくは分岐のアルキル基、アルコキシ基若しくはヒドロキシ基で置換された直鎖若しくは分岐のアルキル基、炭素数６〜１５の芳香族基、又はアルコキシ基で置換された炭素数６〜１５の芳香族基である。｝。 General formula (5):

{In the formula, each of R ₁₃ and R ₁₄ independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkyl group substituted with a hydroxy group, or an aromatic group having 6 to 15 carbon atoms. Or an aromatic group having 6 to 15 carbon atoms substituted with an alkoxy group or an alkoxy group. R ₁₅ and R ₁₆ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkyl group substituted with an alkoxy group or a hydroxy group, or 6 to 15 carbon atoms. Or an aromatic group having 6 to 15 carbon atoms substituted with an alkoxy group. } Or a polymer thereof;
General formula (6):

{In the formula, R ₁₇ and R ₁₈ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkyl group substituted with an alkoxy group or a hydroxy group, and 6 to 6 carbon atoms. It is a C6-C15 aromatic group substituted by 15 aromatic groups or an alkoxy group. R ₁₉ is an alkyl group having 1 to 10 carbon atoms, an aromatic group, an alkyl ether group, or an alkyl group having 1 to 10 carbon atoms substituted with an alkoxy group. };
General formula (7):

{In the formula, R ₂₀ represents a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkyl group substituted with a hydroxy group, an aromatic group having 6 to 15 carbon atoms, or an alkoxy group. It is a substituted aromatic group having 6 to 15 carbon atoms. R ₂₁ is a linear or branched alkyl group having 1 to 10 carbon atoms or a linear or branched alkyl group substituted with a hydroxy group. R ₂₀ and R ₂₁ may be different from each other or the same. R ₂₂ and R ₂₃ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkyl group substituted with an alkoxy group or a hydroxy group, or 6 to 15 carbon atoms. Or an aromatic group having 6 to 15 carbon atoms substituted with an alkoxy group. }.

｛式中、Ｒ₂₄及びＲ₂₅、それぞれ独立に、水素原子、炭素数１〜４０の直鎖若しくは分岐のアルキル基、又はカルボキシル基、ヒドロキシ基、アミノ基若しくはニトロ基で置換された炭素数１〜４０のアルキル基若しくは芳香族基である。Ｒ₂₆は、水素原子、フェニル基、アミノ基若しくはシリル基で置換された炭素数１〜４０のアルキル基若しくは芳香族基である。｝及び下記一般式（９）：

｛式中、Ｒ₂₇は、水素原子、カルボキシル基、ヒドロキシ基、アミノ基、ニトロ基、炭素数１〜４０の直鎖若しくは分岐のアルキル基、又はカルボキシル基、ヒドロキシ基、アミノ基若しくはニトロ基で置換された炭素数１〜４０のアルキル基若しくは芳香族基であり、Ｒ₂₈は、水素原子、フェニル基、アミノ基若しくはシリル基で置換された炭素数１〜４０のアルキル基若しくは芳香族基である。｝及び下記一般式（１０）：

｛式中、Ｒ₂₉は、水素原子、炭素数１〜４０の直鎖若しくは分岐のアルキル基、又はカルボキシル基、ヒドロキシ基、アミノ基若しくはニトロ基で置換された炭素数１〜４０のアルキル基若しくは芳香族基であり、Ｒ₃₀は、水素原子、フェニル基、アミノ基若しくはシリル基で置換された炭素数１〜４０のアルキル基若しくは芳香族基である。｝ (D) Azole compound The photosensitive resin composition of the present invention comprises (D) the following general formula (8), the following general formula (9), and the following general formula (9) as components other than the above components (A) to (C). The azole compound represented by 10) may be contained. (D) An azole compound has the effect | action which prevents discoloration of copper or a copper alloy, when forming the photosensitive resin composition of this invention, for example on copper or a copper alloy.
General formula (8):

{In the formula, R ₂₄ and R ₂₅ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, or a carbon number 1 substituted with a carboxyl group, a hydroxy group, an amino group, or a nitro group. ˜40 alkyl groups or aromatic groups. R ₂₆ is a C 1-40 alkyl group or aromatic group substituted with a hydrogen atom, a phenyl group, an amino group or a silyl group. } And the following general formula (9):

{In the formula, R ₂₇ represents a hydrogen atom, a carboxyl group, a hydroxy group, an amino group, a nitro group, a linear or branched alkyl group having 1 to 40 carbon atoms, or a carboxyl group, a hydroxy group, an amino group, or a nitro group. A substituted or unsubstituted alkyl group or aromatic group having 1 to 40 carbon atoms, and R ₂₈ is a substituted or unsubstituted alkyl group or aromatic group having 1 to 40 carbon atoms substituted with a hydrogen atom, phenyl group, amino group or silyl group. is there. } And the following general formula (10):

{In the formula, R ₂₉ represents a hydrogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, or an alkyl group having 1 to 40 carbon atoms substituted with a carboxyl group, a hydroxy group, an amino group, or a nitro group; It is an aromatic group, and R ₃₀ is an alkyl group having 1 to 40 carbon atoms or an aromatic group substituted with a hydrogen atom, a phenyl group, an amino group or a silyl group. }

(D) The azole compound has the general formula (8) as 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl- 1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1- (2-dimethylaminoethyl) triazole 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole,
As the general formula (9), 1H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl ] -Benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -benzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl- 1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzo Riazor, 5-carboxy -1H- benzotriazole,
Examples of the general formula (10) include 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, and 1-methyl-1H-tetrazole. It is not limited to this. Among these, from the viewpoint of suppressing discoloration of copper or a copper alloy, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole and the like are particularly preferable. These azole compounds may be used alone or in a mixture of two or more.

  (D) The addition amount of an azole compound is 0.1-20 mass parts with respect to 100 mass parts of (A) polyimide precursor, and 0.5-5 mass parts is preferable from a viewpoint of a photosensitivity characteristic. (D) If the addition amount of azole compound to 100 parts by mass of (A) polyimide precursor is 0.1 parts by mass or more, when the photosensitive resin composition of the present invention is formed on copper or a copper alloy, On the other hand, when the photosensitive resin composition of the present invention is formed on copper or a copper alloy as long as it is 20 parts by mass or less, a good relief pattern is obtained.

(E) Hindered phenol compound The photosensitive resin composition of the present invention is, for example, a compound having an action of preventing discoloration of copper or a copper alloy when formed on copper or a copper alloy. A phenol compound may be contained. Here, the hindered phenol compound has a structure represented by the following general formula (11), general formula (12), general formula (16), general formula (17) or general formula (18) in the molecule. (E) hindered phenol compound, which is a compound and a component of the photosensitive resin composition of the present invention, has the following general formula (11), general formula (12), general formula (16), general formula (17), And at least one phenol compound selected from the group consisting of compounds represented by formula (18).

｛式中、Ｒ₃₁は、t-ブチル基であり、Ｒ₃₂及びＲ₃₄は、それぞれ独立に、水素原子又はアルキル基であり、Ｒ₃₃は、水素原子、アルキル基、アルコキシ基、ヒドロキシアルキル基、ジアルキルアミノアルキル基、ヒドロキシ基、又はカルボキシル基で置換されたアルキル基であり、そしてＲ₃₅は、水素原子又はアルキル基である。｝；
一般式（１２）：

｛式中、Ｒ₃₆は、t-ブチル基であり、Ｒ₃₇、Ｒ₃₈及びＲ₃₉は、それぞれ独立に、水素原子、又はアルキル基であり、Ｒ₄₀は、アルキレン基、硫黄原子、ジメチレンチオエーテル基、又は下記一般式（１３）：

（式中、Ｒ₄₁は、炭素数１〜６のアルキル基、ジエチレンチオエーテル基、又は下記式（１４）：

で表される基である。）若しくは下記式（１５）：

で表される基である。｝；
一般式（１６）：

｛式中、Ｒ₄₂は、t-ブチル基、シクロヘキシル基、又はメチルシクロヘキシル基であり、Ｒ₄₃、Ｒ₄₄、及びＲ₄₅は、それぞれ独立に、水素原子、又はアルキル基であり、そしてＲ₄₆は、アルキレン基、硫黄原子、又はテレフタル酸エステルである。｝；
一般式（１７）：

｛式中、Ｒ₄₇は、t-ブチル基であり、Ｒ₄₈、Ｒ₄₉及びＲ₅₀は、それぞれ独立に、水素原子、又はアルキル基であり、そしてＲ₅₁は、アルキル基、フェニル基、イソシアヌレート基又はプロピオネート基である。｝；
一般式（１８）：

｛式中、Ｒ₅₂及びＲ₅₃は、それぞれ独立に、水素原子又は炭素数１〜６の１価の有機基であり、Ｒ₅₅は、アルキル基、フェニル基、イソシアヌレート基又はプロピオネート基であり、Ｒ₅₄は、下記一般式（１９）：

（式中、Ｒ₅₆、Ｒ₅₇及びＲ₅₈は、それぞれ独立に、水素原子、又は炭素数１〜６の１価の有機基である。但し、Ｒ₅₆、Ｒ₅₇及びＲ₅₈のうち少なくとも２つは炭素数１〜６の１価の有機基である。）で表される基、又はフェニル基である。｝。 General formula (11):

{Wherein R ₃₁ represents a t-butyl group, R ₃₂ and R ₃₄ each independently represent a hydrogen atom or an alkyl group, and R ₃₃ represents a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyalkyl group. , A dialkylaminoalkyl group, a hydroxy group, or an alkyl group substituted with a carboxyl group, and R ₃₅ is a hydrogen atom or an alkyl group. };
Formula (12):

{In the formula, R ₃₆ represents a t-butyl group; R ₃₇ , R ₃₈ and R ₃₉ each independently represents a hydrogen atom or an alkyl group; and R ₄₀ represents an alkylene group, a sulfur atom, or dimethylene. Thioether group or the following general formula (13):

(In the formula, R ₄₁ represents an alkyl group having 1 to 6 carbon atoms, a diethylenethioether group, or the following formula (14):

It is group represented by these. ) Or the following formula (15):

It is group represented by these. };
Formula (16):

{Wherein R ₄₂ is a t-butyl group, a cyclohexyl group, or a methylcyclohexyl group, R ₄₃ , R ₄₄ , and R ₄₅ are each independently a hydrogen atom or an alkyl group, and R ₄₆ Is an alkylene group, a sulfur atom, or a terephthalic acid ester. };
Formula (17):

{In the formula, R ₄₇ is a t-butyl group; R ₄₈ , R ₄₉ and R ₅₀ are each independently a hydrogen atom or an alkyl group; and R ₅₁ is an alkyl group, a phenyl group, an isocyanate group. It is a nurate group or a propionate group. };
General formula (18):

{Wherein R ₅₂ and R ₅₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, and R ₅₅ is an alkyl group, a phenyl group, an isocyanurate group or a propionate group. , R ₅₄ is represented by the following general formula (19):

(In the formula, R ₅₆ , R ₅₇ and R ₅₈ are each independently a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, provided that at least 2 of R ₅₆ , R ₅₇ and R ₅₈ are present. Is a monovalent organic group having 1 to 6 carbon atoms.) Or a phenyl group. }.

  (E) A hindered phenol compound has the effect | action which prevents discoloration of copper or a copper alloy, when forming the photosensitive resin composition of this invention on copper or a copper alloy, for example. In the present invention, specific phenol compounds among the phenol compounds, that is, the phenol compounds represented by the above general formula (11), general formula (12), general formula (16), general formula (17), and general formula (18) By using, there is an advantage that a high-resolution polyimide can be obtained without causing discoloration or corrosion even on copper or a copper alloy.

  (E) The hindered phenol compound has, for example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3 as the general formula (11). -(3,5-di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, etc. Examples of (12) include 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-thio-bis (3-methyl-6-tert-butylphenol), 4,4 ′. -Butylidene-bis (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6 Hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionate], N, N ′ hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide) and the like, and the general formula (16) includes, for example, 2 , 2′-methylene-bis (4-methyl-6-tert-butylphenol), 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) and the like, For example, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], tris- (3,5-di-t-butyl-4-hydroxybenzyl) ) -Isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and the like, Is, for example, 1,3,5-tris (3-hydroxy-2,6-dimethyl-4-isopropylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H)- Trione, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H)- Trione, 1,3,5-tris (4-s-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H)- Trione, 1,3,5-tris [4- (1-ethylpropyl) -3- Droxy-2,6-dimethylbenzyl] -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris [4-triethylmethyl-3-hydroxy -2,6-dimethylbenzyl] -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (3-hydroxy-2,6-dimethyl -4-phenylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-3-hydroxy-2 , 5,6-trimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-5-ethyl) -3-hydroxy-2,6-dimethylbenzyl) -1,3,5-tria Din-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl) -1,3 5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)- 1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-5,6-diethyl-3-hydroxy-2- Methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-3-hydroxy-2-methylbenzyl) ) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, , 3,5-tris (4-t-butyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, , 3,5-tris (4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione However, it is not limited to this. Among these, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H ) -Trione and the like are particularly preferred.

  (E) The addition amount of a hindered phenol compound is 0.1-20 mass parts with respect to 100 mass parts of (A) polyimide precursor, and 0.5-10 mass parts is preferable from a viewpoint of a photosensitivity characteristic. (E) If the addition amount with respect to 100 mass parts of (A) polyimide precursor of a hindered phenol compound is 0.1 mass part or more, the photosensitive resin composition of this invention was formed, for example on copper or a copper alloy. In this case, discoloration / corrosion of copper or copper alloy is prevented, and on the other hand, if it is 20 parts by mass or less, the photosensitivity is excellent.

(F) Organic Titanium Compound The photosensitive resin composition of the present invention may contain (F) an organic titanium compound as a compound that improves chemical resistance. The organic titanium compound that can be used as the component (F) is not particularly limited as long as the organic chemical substance is bonded to the titanium atom via a covalent bond or an ionic bond.

Specific examples of (F) organic titanium compounds are shown in the following I) to VII):
I) Titanium chelate compound: Among them, a titanium chelate having two or more alkoxy groups is more preferable because it provides a stable composition and a good pattern. Specifically, titanium bis (triethanolamine) diisopro Poxide, Titanium di (n-butoxide) bis (2,4-pentanedionate, Titanium diisopropoxide bis (2,4-pentanedionate), Titanium diisopropoxide bis (tetramethylheptanedionate), Titanium diisopropoxide bis (ethylacetoacetate) and the like.

  II) Tetraalkoxytitanium compounds: for example, titanium tetra (n-butoxide), titanium tetraethoxide, titanium tetra (2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide , Titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra (n-nonyloxide), titanium tetra (n-propoxide), titanium tetrastearyloxide, titanium tetrakis [bis {2,2- (allyloxymethyl) Butoxide}] and the like.

III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis (η ⁵ -2,4-cyclopentadien-1-yl) bis (2,6-difluorophenyl) titanium, bis (η ⁵ − 2,4-cyclopentadien-1-yl) bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium and the like.

  IV) Monoalkoxytitanium compounds: for example, titanium tris (dioctyl phosphate) isopropoxide, titanium tris (dodecylbenzenesulfonate) isopropoxide, and the like.

  V) Titanium oxide compound: For example, titanium oxide bis (pentanedionate), titanium oxide bis (tetramethylheptanedionate), phthalocyanine titanium oxide, and the like.

  VI) Titanium tetraacetylacetonate compound: For example, titanium tetraacetylacetonate.

VII) Titanate coupling agent: For example, isopropyltridodecylbenzenesulfonyl titanate.
Among these, at least one compound selected from the group consisting of I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanocene compound is preferable from the viewpoint of more chemical resistance.

  The addition amount of these organic titanium compounds is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the (A) polyimide precursor. When the addition amount is 0.05 parts by weight or more, desired heat resistance or chemical resistance is exhibited, while when it is 10 parts by weight or less, the storage stability is excellent.

(G) Other components The photosensitive resin composition of this invention may contain components other than the said (A)-(F) component.
In the photosensitive resin composition of the present invention, each component of the photosensitive resin composition is dissolved in a solvent to form a varnish, which is used as a negative photosensitive resin composition solution. Can do. As the solvent, it is preferable to use a polar organic solvent from the viewpoint of solubility of the component (A) in the polyimide precursor. Specifically, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α -Acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone and the like can be mentioned, and these can be used alone or in combination of two or more.

The said solvent can be used in 30-1500 mass parts with respect to 100 mass parts of polyimide precursors according to the desired coating film thickness and viscosity of the photosensitive resin composition.
Furthermore, in order to improve the storage stability of the photosensitive resin composition, a solvent containing alcohols is preferable.

  Alcohols that can be used are typically alcohols having an alcoholic hydroxyl group in the molecule and no olefinic double bond. Specific examples include methyl alcohol, ethyl alcohol, and n-propyl. Alcohols such as alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, lactic esters such as ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol- Propylene glycol monoalkyl ethers such as 1-ethyl ether, propylene glycol-2-ethyl ether, propylene glycol-1- (n-propyl) ether, propylene glycol-2- (n-propyl) ether Ethylene glycol methyl ether, ethylene glycol ethyl ether, mono-alcohols such as ethylene glycol -n- propyl ether, 2-hydroxyisobutyric acid esters, ethylene glycol, di alcohols such as propylene glycol, and the like. Among these, lactic acid esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyric acid esters, and ethyl alcohol are preferable. Particularly, ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, propylene Glycol-1- (n-propyl) ether is more preferred.

  The content of the alcohol having no olefinic double bond in all the solvents is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. When the content of alcohol having no olefinic double bond is 5% by mass or more, the storage stability of the photosensitive resin composition is good, and when it is 50% by mass or less, the solubility of the polyimide precursor is good. become.

Further, a sensitizer can be optionally added to improve the photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzal) cyclopentane, and 2,6-bis (4′-diethylaminobenzal). ) Cyclohexanone, 2,6-bis (4′-diethylaminobenzal) -4-methylcyclohexanone, 4,4′-bis (dimethylamino) chalcone, 4,4′-bis (diethylamino) chalcone, p-dimethylaminocinna Millidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) Isonaphthothiazole, 1,3-bis (4′-dimethyl) Aminobenzal) acetone, 1,3-bis (4′-diethylaminobenzal) acetone, 3,3′-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7 -Dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N- Phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-fur Nyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p-dimethylaminostyryl) naphtho (1, 2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene and the like. These can be used alone or in combination of, for example, 2 to 5 kinds.
The sensitizer for improving the photosensitivity is preferably used in an amount of 0.1 to 25 parts by mass with respect to 100 parts by mass of the polyimide precursor.

  In order to improve the resolution of the relief pattern, a monomer having a photopolymerizable unsaturated bond can be optionally added. Such a monomer is preferably a (meth) acryl compound that undergoes a radical polymerization reaction with a photopolymerization initiator, and is not particularly limited to the following, but includes ethylene glycol such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate. Polyethylene glycol mono or diacrylate and methacrylate, propylene glycol or polypropylene glycol mono or diacrylate and methacrylate, glycerol mono, di or triacrylate and methacrylate, cyclohexane diacrylate and dimethacrylate, 1,4-butanediol di Acrylate and dimethacrylate, 1,6-hexanediol diacrylate and dimethacrylate, neopentyl glycol Acrylate and dimethacrylate, mono or diacrylate and methacrylate of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and derivatives thereof, methacrylamide and derivatives thereof, trimethylolpropane triacrylate and methacrylate, di or tri of glycerol Mention may be made of compounds such as acrylates and methacrylates, di, tri, or tetraacrylates and methacrylates of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds.

  It is preferable that 1-50 mass parts is used for the monomer which has said photopolymerizable unsaturated bond for improving the resolution of a relief pattern with respect to 100 mass parts of (A) component polyimide precursor.

  In addition, an adhesion aid can be optionally added to improve the adhesion between the film formed using the photosensitive resin composition of the present invention and the substrate. Adhesion aids include γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3- Methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) succinimide N- [3- (triethoxysilyl) propyl] phthalamic acid, benzophenone-3,3′-bis (N- [3-triethoxysilyl] propylamide) -4,4′-dicarboxylic acid, benzene-1, 4-bis (N- [3-trie Toxisilyl] propylamide) -2,5-dicarboxylic acid, 3- (triethoxysilyl) propyl succinic anhydride, silane coupling agents such as N-phenylaminopropyltrimethoxysilane, and aluminum tris (ethyl acetoacetate), Examples thereof include aluminum adhesion assistants such as aluminum tris (acetylacetonate) and ethyl acetoacetate aluminum diisopropylate.

  In these, it is more preferable to use a silane coupling agent from the point of adhesive force. The addition amount of the adhesion assistant is preferably in the range of 0.5 to 25 parts by mass with respect to 100 parts by mass of the component (A) polyimide precursor.

In addition, a thermal polymerization inhibitor can be optionally added to improve the viscosity of the photosensitive resin composition solution during storage and the stability of photosensitivity. Examples of thermal 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-phenylhydroxylamine ammonium salt, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt and the like are used.
As a quantity of the thermal-polymerization inhibitor added to the photosensitive resin composition, the range of 0.005-12 mass parts is preferable with respect to 100 mass parts of polyimide precursors.

  Further, as a crosslinking agent, when the relief pattern is heat-cured, a polyimide precursor can be crosslinked, or a crosslinking agent that can form a crosslinked network by itself is added to further enhance heat resistance and chemical resistance. be able to. As the crosslinking agent, an amino resin or a derivative thereof is preferably used, and among them, a glycol urea resin, a hydroxyethylene urea resin, a melamine resin, a benzoguanamine resin, or a derivative thereof is preferably used. Particularly preferred is an alkoxymethylated melamine compound, and hexamethoxymethylmelamine is mentioned as an example.

  In consideration of various performances other than heat resistance and chemical resistance, the addition amount of the crosslinking agent is preferably 2 to 40 parts by mass, more preferably 100 parts by mass of the polyimide precursor of the component (A). 5 to 30 parts by mass. When the addition amount is 2 parts by mass or more, good heat resistance and chemical resistance are exhibited, and when it is 40 parts by mass or less, the storage stability is excellent.

<Pattern Forming Method, Semiconductor Device, and Manufacturing Method Thereof>
Hereinafter, a pattern forming / manufacturing method for forming a cured relief pattern using the above-described photosensitive resin composition of the present invention, a semiconductor device using the pattern forming method, and a manufacturing method thereof will be described.

The pattern forming method of the present invention comprises:
(1) forming a photosensitive resin layer comprising the photosensitive resin composition on a substrate;
(2) exposing the photosensitive resin layer;
(3) removing the unexposed portion after the exposure to form a relief pattern;
(4) heat-treating the relief pattern;
including.

  As a method for coating the photosensitive resin composition used in the present invention on a substrate, methods conventionally used for coating a photosensitive resin composition, for example, spin coater, bar coater, blade coater, curtain coater A method of applying with a screen printer or the like, a method of applying with a spray coater, or the like can be used.

As a method for drying the coating film, methods such as air drying, heat drying with an oven or hot plate, and vacuum drying are used. Moreover, it is desirable that the coating film be dried under conditions such that imidation of the polyamic acid ester in the photosensitive resin composition does not occur. Specifically, when performing air drying or heat drying, it can be performed at 20 ° C. to 140 ° C. for 1 minute to 1 hour.
The coating film thus obtained is exposed with a UV light source or the like through a photomask or reticle having a pattern, using an exposure apparatus such as a contact aligner, a mirror projection, or a stepper.

  Thereafter, post-exposure baking (PEB) or a pre-development baking by any combination of temperature and time may be performed as necessary for the purpose of improving photosensitivity. The range of the baking conditions is preferably 40 to 120 ° C. and the time of 10 to 240 seconds, but is not limited to this range as long as the various characteristics of the photosensitive resin composition of the present invention are not impaired.

As a developing method, an arbitrary method can be selected and used from conventionally known photoresist developing methods such as a rotary spray method, a paddle method, and an immersion method involving ultrasonic treatment. Further, after development, for the purpose of adjusting the shape of the relief pattern, post-development baking at any combination of temperature and time may be performed as necessary.
The developer used for development is preferably a good solvent for the photosensitive resin composition or a combination of the good solvent and the poor solvent. As the good solvent, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. are preferable and poor. As the solvent, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water and the like are preferable. When mixing and using a good solvent and a poor solvent, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the photosensitive resin composition. Moreover, several types of solvents can be used in combination.

  The polyimide precursor pattern is converted into a cured relief pattern made of polyimide by heating to disperse the photosensitive component and imidization. Various methods such as a method using a hot plate, a method using an oven, and a method using a temperature rising oven capable of setting a temperature program can be selected as the method for heat curing. Heating can be performed at 200 ° C. to 400 ° C. for 30 minutes to 5 hours. Air may be used as the atmospheric gas for heat curing, and an inert gas such as nitrogen or argon may be used.

The present invention also provides a semiconductor device having a base material which is a semiconductor element and a polyimide pattern formed on the base material by the pattern forming method described above. The present invention also provides a method for manufacturing a semiconductor device using a semiconductor element as a base material and including the above-described pattern forming method as part of the process. The semiconductor device of the present invention protects a cured relief pattern formed by the above pattern forming method using a surface protective film, an interlayer insulating film, a rewiring insulating film, a flip chip device protective film, or a semiconductor device having a bump structure. As a film | membrane, it can manufacture by combining with the manufacturing method of a well-known semiconductor device.
The photosensitive resin composition of the present invention is useful not only for application to semiconductor devices as described above but also for applications such as interlayer insulation of multilayer circuits, cover coating of flexible copper-clad plates, solder resist films, or liquid crystal alignment films. It is.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
In Examples, Comparative Examples, and Reference Examples, physical properties of the photosensitive resin composition were measured and evaluated according to the following methods.

(1) Weight average molecular weight The weight average molecular weight (Mw) of each polyimide precursor was measured by the gel permeation chromatography method (standard polystyrene conversion). The column used for the measurement is a trade name Shodex 805M / 806M series manufactured by Showa Denko KK, the standard monodisperse polystyrene is Shodex STANDARD SM-105 manufactured by Showa Denko KK, and the developing solvent is N-methyl-2-pyrrolidone The detector used was a trade name Shodex RI-930 manufactured by Showa Denko.

(2) Identification of urea compound The synthesized urea compound was identified by gel permeation chromatography measurement and FT-IR spectrum measurement. The column used for the gel permeation chromatography measurement was trade name Shodex 801/802 in series, the developing solvent was tetrahydrofuran, and the detector used was Showa Denko trade name Shodex RI2031 Plus. The FT-IR spectrum measurement was performed using a brand name Centaurus manufactured by Thermo Spectra-Tech USA.

(3) Evaluation of patterning characteristics of polyimide pattern A photosensitive resin composition was spin-coated on a 6-inch silicon wafer or a copper substrate and dried to form a 10 μm thick coating film. The coating using a test pattern with the reticle to i-line stepper NSR1755i7B (Japan, manufactured by Nikon Corporation), the irradiated energy at 25 mJ / cm ² step from 50 mJ / cm ² to 300 mJ / cm ^2. Subsequently, the coating film formed on the wafer is spray-developed with a developing machine (D-SPIN636 type, manufactured by Dainippon Screen Mfg. Co., Ltd.) using cyclopentanone, rinsed with propylene glycol methyl ether acetate, and polyamide An acid ester pattern was obtained.

  The wafer on which the pattern is formed is heat-treated in a nitrogen atmosphere at 200 ° C. for 1 hour and then at 350 ° C. for 2 hours using a temperature-programmed cure furnace (VF-2000 type, manufactured by Koyo Lindberg, Japan). Thus, a polyimide pattern having a thickness of 5 μm was obtained on the silicon wafer. The film thickness was measured using a Tencor P-15 type step gauge (manufactured by KLA Tencor). About each obtained pattern, the width | variety of the pattern shape and the pattern part was observed under the optical microscope, and the resolution was calculated | required. Regarding the resolution, a pattern having a plurality of openings with different areas is formed by the above method by exposing through a reticle with a test pattern, and the area of the obtained pattern opening is equal to the corresponding pattern mask opening area. If it is 1/2 or more, it is considered that it has been resolved, and the length of the opening side of the mask corresponding to the resolved opening having the smallest area is taken as the resolution. The resolution is good if it is 10 μm or less, that is, if the aspect ratio (film thickness after coating and drying / resolution) is 1 or more, and the minimum exposure for resolving the aspect ratio 1 was determined.

(4) Accuracy evaluation of polyimide pattern Based on the following criteria, the accuracy of the polyimide pattern formed in (3) above was evaluated:
“Good”: The pattern cross-section does not slide, undercut, swelling, or bridging does not occur, the aspect ratio is 1 or more, and the pattern shape does not change during heat curing. . Furthermore, in the case of copper substrates, there is no copper discoloration / corrosion;
“Bad”: Those that do not satisfy at least one of the above conditions.

(5) Discoloration / corrosion evaluation of copper substrate The polyimide pattern formed on the copper substrate in (3) above was evaluated based on the following criteria:
“Good”: No discoloration or corrosion of the copper substrate even when observed with a 200 × optical microscope;
“Slightly good”: Discoloration / corrosion of the copper substrate is slightly observed when observed with a 200 × optical microscope;
“Slightly bad”: The copper substrate is slightly discolored or corroded visually;
“Bad”: The copper substrate clearly shows discoloration and corrosion.

(6) Stability evaluation of photosensitive resin composition The photosensitive resin composition was spin-coated on a 6-inch silicon wafer and dried to form a 10 μm-thick coating film. Next, the coating film formed on the wafer is spray-developed with a developing machine (D-SPIN636 type, manufactured by Dainippon Screen Mfg. Co., Ltd.) using cyclopentanone, and rinsed with propylene glycol methyl ether acetate. The time required for the coating film to completely dissolve was determined (initial dissolution time). Thereafter, the photosensitive resin composition was allowed to stand at 23 ° C. for 1 month, and the same evaluation was carried out after the standing. When the coating film dissolution time after one month was within 150% of the initial dissolution time, it was judged as “good”, and when it exceeded 150%, it was judged as “bad”.

(7) Chemical resistance test After a polyamic acid ester pattern was formed on a 6-inch nitride silicon wafer (manufactured by Kyodo International Co., Ltd.) in the same manner as in (3) above, a temperature rising programmed curing furnace (VF-2000) 7 μm-thick polyimide pattern was obtained by heat treatment at 200 ° C. for 1 hour and then at 250 ° C. for 2 hours in a nitrogen atmosphere using a mold, manufactured by Koyo Lindberg Co., Japan. The obtained polyimide pattern was immersed in a solution consisting of 1 wt% potassium hydroxide, 39 wt% 3-methoxy-3-methyl-1-butanol and 60 wt% dimethyl sulfoxide at 110 ° C. for 1 hour. After washing with water and air drying, the film thickness was measured and observed under an optical microscope to evaluate the polyimide coating. “Poor” when the film thickness fluctuation is within ± 3% and no cracks occur, and “Poor” when the film thickness fluctuation exceeds ± 3% or cracks occur ".

(8) Elongation of cured relief pattern (polyimide coating film) The photosensitive resin composition was spin-coated and dried on a 6-inch silicon wafer or copper substrate so that the film thickness after curing was about 10 μm, and then the temperature was raised. Using a programmed curing furnace (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd., Japan) under a nitrogen atmosphere, heating at 200 ° C. for 1 hour and 350 ° C. for 2 hours to cure a relief pattern (coating with heat-cured polyimide) Membrane). The obtained polyimide coating film was cut into a 3 mm width strip using a dicing saw (DAD3350 type, manufactured by DISCO), and then a 46% hydrofluoric acid was used from a silicon wafer or a ferric chloride aqueous solution. It was peeled off from the copper substrate and used as a polyimide tape on Si and Cu, respectively. The elongation of the obtained polyimide tape was measured according to ASTM D882-09 using a tensile tester (UTM-II-20 type, manufactured by Orientec Corp.). The elongation was considered good if it was 20% or more, and good if it was 30% or more.

<Reference Example 1> (Synthesis of polyimide precursor A)
Place 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) in a 2 liter separable flask, add 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone and stir at room temperature. While stirring, 81.5 g of pyridine was added to obtain a reaction mixture. After completion of the exothermic reaction, the mixture was allowed to cool to room temperature and left for 16 hours.

  Next, under ice cooling, a solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 4,4′-diaminodiphenyl ether (DADPE). A suspension of 93.0 g in γ-butyrolactone 350 ml was added over 60 minutes with stirring. After further stirring for 2 hours at room temperature, 30 ml of ethyl alcohol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.

  The obtained reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was separated by filtration and dissolved in 1.5 liter of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate a polymer, and the resulting precipitate was filtered off and then vacuum dried to obtain a powdery polymer (polyimide precursor A). When the molecular weight of the polyimide precursor A was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20000.

Reference Example 2 (Synthesis of polyimide precursor B)
The above Reference Example except that 147.1 g of 3,3′4,4′-biphenyltetracarboxylic dianhydride was used in place of 155.1 g of 4,4′-oxydiphthalic dianhydride of Reference Example 1. Reaction was performed in the same manner as described in 1 to obtain a polyimide precursor B. When the molecular weight of the polyimide precursor B was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 22,000.

Reference Example 3 (Synthesis of urea compound U5)
80 g of tetrahydrofuran was placed in a 200 ml three-necked flask, 7.7 g of 2-methoxyethylamine was added and stirred at room temperature, and 12.3 g of phenyl isocyanate was added dropwise with stirring. After completion of the exothermic reaction, the mixture was allowed to cool to room temperature and left for 16 hours. When the reaction solution was measured by gel permeation chromatography, it was confirmed that the peak area of the raw material decreased and a new product peak appeared. When the reaction rate was calculated from the peak area ratio between the raw material and the product, the reaction rate was 99% or more. Thereafter, the reaction solution was reprecipitated in hexane, and the obtained product was collected by filtration and dried under reduced pressure. The FT-IR spectrum of the product was measured and confirmed to be urea compound U5 (3337 cm ⁻¹ : N—H stretching vibration, 1629 cm ⁻¹ : C═O stretching vibration, 1567 cm ⁻¹ : NH deformation angle. Vibration, 1120 cm ⁻¹ : C—O—C reverse symmetrical stretching vibration, 1098 cm ⁻¹ , 763 cm ⁻¹ , 693 cm ⁻¹ : mono-substituted benzene C—H in-plane bending vibration).

Reference Example 4 (Synthesis of urea compound U6)
As described in Reference Example 3 above, except that 11.4 g of n-butyl isocyanate was used instead of 12.3 g of phenyl isocyanate of Reference Example 3, and 8.6 g of 2-methoxyethylamine was used instead of 7.7 g. The reaction is carried out in the same manner as in the method, and it is confirmed by gel permeation chromatography that the reaction rate is 99% or more, the product is recovered by reprecipitation, and after drying under reduced pressure, the product is subjected to FT-IR measurement. The formation of urea compound U6 was confirmed (3333 cm ⁻¹ : N—H stretching vibration, 2959 cm ⁻¹ , 2871 cm ⁻¹ : methyl group C—H stretching vibration, 2934 cm ⁻¹ : methylene group C—H stretching vibration, 1622 cm < ^-1 >: C = O stretching vibration, 1574 cm < ^-1 >: N-H bending vibration, 1120 cm < ^-1 >: C-O-C reverse symmetrical stretching vibration).

Reference Example 5 (Synthesis of urea compound U7)
As described in Reference Example 3, except that 9.4 g of aminoacetaldehyde dimethyl acetal was used instead of 7.7 g of 2-methoxyethylamine in Reference Example 3 and 10.6 g of phenyl isocyanate was used instead of 12.3 g. The reaction is carried out in the same manner as in the method, and it is confirmed by gel permeation chromatography that the reaction rate is 99% or more, the product is recovered by reprecipitation, and after drying under reduced pressure, the product is subjected to FT-IR measurement. The formation of urea compound U7 was confirmed (3374 cm ⁻¹ : N—H stretching vibration, 2934 cm ⁻¹ : methoxy group C—H stretching vibration, 1644 cm ⁻¹ : C═O stretching vibration, 1556 cm ⁻¹ : N— H bending vibration, 1123 cm ⁻¹ : C—O—C reverse symmetrical stretching vibration, 1065 cm ⁻¹ , 745 cm ⁻¹ , 696 cm ^−1. : Mono-substituted benzene C—H in-plane bending vibration).

Reference Example 6 (Synthesis of urea compound U8)
The above-mentioned reference, except that 10.3 g of aminoacetaldehyde dimethyl acetal was used instead of 7.7 g of 2-methoxyethylamine in Reference Example 3 and 9.7 g of n-butyl isocyanate was used instead of 12.3 g of phenyl isocyanate. The reaction was conducted in the same manner as described in Example 3, and the reaction rate was confirmed to be 99% or more by gel permeation chromatography measurement. The reaction solution was reprecipitated in hexane, and the resulting product was filtered. After drying under reduced pressure, the product was subjected to FT-IR measurement to confirm the formation of urea compound U8 (3335 cm ⁻¹ : N—H stretching vibration, 2931 cm ⁻¹ : methylene group C—H stretching vibration, 2832 cm ^−1. : Methoxy group C—H stretching vibration, 1624 cm ⁻¹ : C═O stretching vibration, 1575 cm ⁻¹ : N—H bending vibration, 11 25cm ^-1: C-O-C antisymmetric stretching ^vibration, 1052cm -1: C-N stretching vibration).

Reference Example 7 (Synthesis of urea compound U9)
20 g of the tetrahydrofuran of Reference Example 3 was used instead of 80 g, 2.8 g of 3,5-dimethoxyaniline was used instead of 7.7 g of 2-methoxyethylamine, and 2.2 g of phenyl isocyanate was used instead of 12.3 g. Except for the above, the reaction is carried out in the same manner as described in Reference Example 3, and it is confirmed by gel permeation chromatography that the reaction rate is 99% or more, and the product is recovered by reprecipitation, After drying under reduced pressure, the product was subjected to FT-IR measurement to confirm the formation of urea compound U9 (3317 cm ⁻¹ : N—H stretching vibration, 2883 cm ⁻¹ : methyl group C—H stretching vibration, 1635 cm ⁻¹ : C. = O stretching ^vibration, 1562cm -1: N-H deformation ^{vibration, 1141cm -1: C-O-} C antisymmetric stretching vibration, ^{1090 cm} -1, 75 cm ^-1, 691cm ^-1: mono-substituted benzene C-H in-plane bending ^vibration, 732 cm -1: 1,3,5-trisubstituted benzene C-H out-of-plane deformation vibration).

Reference Example 8 (Synthesis of urea compound U10)
Except for using 7.9 g of 1,2-bis (2-aminoethoxy) ethane instead of 7.7 g of 2-methoxyethylamine in Reference Example 3, and using 12.7 g of phenylisocyanate instead of 12.3 g, Reaction was performed in the same manner as described in Reference Example 3 above, and the reaction rate was confirmed to be 99% or more by gel permeation chromatography measurement, and the reaction solution was reprecipitated in hexane, and obtained. The product was filtered, and after drying under reduced pressure, the product was subjected to FT-IR measurement to confirm the formation of urea compound U10 (3316 cm ⁻¹ : N—H stretching vibration, 1633 cm ⁻¹ : C═O stretching vibration, 1562 cm. ^-1: N-H deformation ^{vibration, 1141cm -1: C-O-} C antisymmetric stretching ^{vibration, 1090cm -1, 759cm -1, 691cm} -1: mono-substituted benzene -H plane bending vibration).

Reference Example 9 (Synthesis of urea compound U11)
As described in Reference Example 3 above, except that 11.1 g of m-xylylene diisocyanate was used instead of 12.3 g of phenyl isocyanate of Reference Example 3, and 8.9 g of 2-methoxyethylamine was used instead of 7.7 g. The reaction is carried out in the same manner as described above, and it is confirmed by gel permeation chromatography that the reaction rate is 99% or more, the reaction solution is re-precipitated in hexane, the resulting product is filtered, and the pressure is reduced. After drying, the product was subjected to FT-IR measurement to confirm the formation of urea compound U11 (3322 cm ⁻¹ : N—H stretching vibration, 2888 cm ⁻¹ : methyl group C—H stretching vibration, 1620 cm ⁻¹ : C = O stretching ^vibration, 1573cm -1: N-H deformation ^{vibration, 1118cm -1: C-O-} C antisymmetric stretching ^{vibration, 784cm -1, 698cm} -1: m Disubstituted benzene C-H out-of-plane deformation vibration).

<Reference Example 10> (Synthesis of urea compound U12)
32 g of tetrahydrofuran in Reference Example 3 was used instead of 80 g, 5.0 g of 3,5-dimethoxyaniline was used instead of 7.7 g of 2-methoxyethylamine, and m-xylylene diisocyanate 3 was used instead of 12.3 g of phenyl isocyanate. The reaction was conducted in the same manner as described in Reference Example 3 except that 0.1 g was used, and the reaction rate was confirmed to be 99% or more by gel permeation chromatography measurement. The product obtained by filtration was filtered, and after drying under reduced pressure, the product was subjected to FT-IR measurement to confirm the formation of urea compound U12 (3317 cm ⁻¹ : NH stretching vibration, 2882 cm ^−1. : methyl group C-H stretching ^vibration, 1632cm -1: C = O stretching ^vibration, 1563cm -1: N-H deformation vibration, 1119Cm ^1: C-O-C antisymmetric stretching ^{vibration, 759cm -1, 691cm} -1: m- disubstituted benzene C-H out-of-plane deformation ^{vibration, 731cm} -1: 1,3,5- trisubstituted benzene C-H Out-of-plane bending vibration).

<Example 1>
Using the polyimide precursor A, a photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. 100 g of polyimide precursor A which is a polyamic acid ester, 6 g of 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime (photoinitiator), 1,3-dimethylolurea (urea compound U1) 1 g, 1 g of tolyltriazole (benzotriazole compound), 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6 -(1H, 3H, 5H) -trione (hindered phenol compound) 1 g, N-phenyldiethanolamine 10 g, 7-diethylamino-3-ethoxycarbonylcoumarin 0.05 g, tetraethylene glycol dimethacrylate 8 g, N- [3- ( Triethoxysilyl) propyl] phthalamic acid 1.5 g and 2-nitroso-1- Shift - with Le 0.05 g, (in the following referred to NMP) N-methyl-2-pyrrolidone was dissolved in a mixed solvent consisting of 80g ethyl lactate 20g. The viscosity of the resulting solution was adjusted to about 35 poise by further adding a small amount of the mixed solvent to obtain a photosensitive resin composition.

The minimum exposure amount satisfying an aspect ratio of 1 or more of the polyimide coating film obtained by coating, drying, exposing, developing and heat-treating the composition on a silicon wafer and a copper substrate according to the above-described method is as high as 100 mJ / cm ^2. In addition, the pattern accuracy was good, and no discoloration or corrosion was observed even on the copper substrate, and the elongation of the coating film dissolution time after standing at 23 ° C. for 1 month was 100%.

<Examples 2 to 13 and Reference Examples 14 to 23 >
The polyimide precursor A, 1,3-dimethylol urea (U1), tolyltriazole, 1,3,5-tris (4- t-Butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione has the composition shown in Table 1 below. Instead, a photosensitive resin composition was prepared (see Table 1 remarks column for U2 to U4, and the following for U5 to U12), and the same evaluation as in Example 1 was performed. In any case, the minimum exposure amount satisfying an aspect ratio of 1 or more of a polyimide coating film obtained by coating, drying, exposing, developing and heat-treating on a silicon wafer and a copper substrate according to the above-mentioned method is as high as 200 mJ / cm ² or less. In addition, the pattern accuracy was good, the discoloration and corrosion were not observed even on the copper substrate, which was good or slightly good, and the elongation of the coating film dissolution time after standing at 23 ° C. for 1 month was also good.

<Example 24>
A photosensitive resin composition similar to that of Example 2 was prepared except that 0.5 g of titanium diisopropoxide bis (ethylacetoacetate) was further added to the composition of Example 2. As a result of chemical resistance evaluation, the film thickness variation was within ± 3%, and no cracks were observed, which was good. The other evaluation results were the same as in Example 2.

<Example 25>
A photosensitive resin composition similar to that of Example 2 was prepared except that 0.5 g of titanium tetra (n-butoxide) was further added to the composition of Example 2. As a result of chemical resistance evaluation, the film thickness variation was within ± 3%, and no cracks were observed, which was good. The other evaluation results were the same as in Example 2.

<Example 26>
To the composition of Example 2, 0.5 g of bis (η ⁵ -2,4-cyclopentadien-1-yl) bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium was added. A photosensitive resin composition similar to that of Example 2 was prepared except that: As a result of chemical resistance evaluation, the film thickness variation was within ± 3%, and no cracks were observed, which was good. The other evaluation results were the same as in Example 2.

<Examples 27 to 33>
Each photosensitive resin composition of Examples 2, 6, and 8-12 was made into a polyimide tape according to the above-mentioned method, and the elongation of the cured relief pattern was measured. The results are shown in Table 2 below. In Examples 27-31, both elongation on Si and Cu were good showing 30% or more, and in Examples 32 and 33, it was good showing elongation of 30% or more on Si, and good on Cu. The above elongation was slightly good.

<Comparative Example 1>
From the composition of Example 2, 1,3-dimethylolurea (U1), tolyltriazole, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5 -The photosensitive resin composition similar to Example 2 was prepared except having extracted triazine-2,4,6- (1H, 3H, 5H) -trione, and the same evaluation as Example 1 was performed. The polyimide coating film obtained by applying, drying, exposing, developing, and heat-treating on a silicon wafer and a copper substrate according to the above-described method has a good pattern accuracy, but does not contain the component (C) and satisfies an aspect ratio of 1 or more. The minimum exposure amount was 250 mJ / cm ² and the sensitivity was slightly lowered, and discoloration was visually observed on the copper substrate. Furthermore, the elongation of the coating film dissolution time after standing at 23 ° C. for 1 month was poor at 160%.

<Comparative example 2>
A photosensitive resin composition similar to that of Example 2 was prepared except that 1,3-dimethylolurea (U1) was omitted from the composition of Example 2, and evaluation similar to that of Example 1 was performed. The polyimide coating film obtained by applying, drying, exposing, developing, and heat-treating on a silicon wafer and a copper substrate according to the above-described method has a good pattern accuracy, but does not contain the component (C) and satisfies an aspect ratio of 1 or more. The minimum exposure amount was 250 mJ / cm ^2, and the sensitivity was slightly lowered. Furthermore, the elongation of the coating film dissolution time after standing at 23 ° C. for 1 month was as poor as 160%. On the other hand, no discoloration on the copper substrate was observed.

<Comparative Example 3>
From the composition of Example 3, 1 g of 1,3-dimethylolurea (U1) was changed to 40 g of methoxymethylated urea resin (manufactured by Sanwa Chemical Co., Ltd., trade name: Nicalak, product number MX-290, polymerization degree 1.8) (U2). A photosensitive resin composition similar to that in Example 3 was prepared, and the same evaluation as in Example 1 was performed. The polyimide coating film obtained by coating, drying, exposing, developing and heat-treating on a silicon wafer and a copper substrate according to the above-mentioned method has good pattern accuracy, and the minimum exposure amount satisfying an aspect ratio of 1 or more is 200 mJ / cm ^2. However, discoloration was visually observed on the copper substrate, which was defective.

<Comparative Example 4>
Photosensitivity similar to Example 9 except that the composition of Example 9 was changed to 40 g of 1 g of methoxymethylated urea resin (manufactured by Sanwa Chemical Co., Ltd., trade name: Nikalac, product number MX-290, polymerization degree 1.8) (U2) The same evaluation as in Example 1 was performed. The polyimide coating film obtained by coating, drying, exposing, developing and heat-treating on a silicon wafer and a copper substrate according to the above-mentioned method has good pattern accuracy, and the minimum exposure amount satisfying an aspect ratio of 1 or more is 200 mJ / cm ^2. However, discoloration was observed with an optical microscope on the copper substrate, which was somewhat poor.

  The photosensitive resin composition of the present invention can be suitably used in the field of photosensitive materials useful for the production of electrical / electronic materials such as semiconductor devices and multilayer wiring boards. More specifically, the composition of the present invention can be suitably used as a photosensitive resin composition on copper or a copper alloy.

Claims (12)

below:
(A) The following general formula (1):

{Wherein X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n is an integer of _{2 to} 150, and R ₁ and R ₂ are each independently Hydrogen atom or the following general formula (2):

Wherein R ₃ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is It is an integer of 2-10.) The monovalent organic group represented by this, or a C1-C4 saturated aliphatic group. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. } Polyimide precursor having a structural unit represented by: 100 parts by mass,
(B) Photopolymerization initiator: 1 to 20 parts by mass, and (C) the following general formula (3):

{Wherein, A is an oxygen atom or a sulfur atom, R ₆ and R ₇ are each independently a linear or branched alkyl group substituted with an alkoxy group or a hydroxy group. R ₈ and R ₉ are each independently a hydrogen atom, a linear or branched alkyl group, or an alkoxy group or a linear or branched alkyl group substituted with hydroxy group having 1 to 10 carbon atoms. } Or a polymer thereof and the following general formula (4):

{Wherein, A is an oxygen atom or a sulfur atom, R ₁₀ and R ₁₁ are each independently a linear or branched alkyl group substituted with an alkoxy group or a hydroxy group. R ₁₂ is an alkylene or alkylene ether group, or an alkylene group having 1 to 10 carbon atoms substituted with an alkoxy group. }, Or at least one compound selected from the group consisting of polymers thereof, or polymers thereof: 0.1 to 30 parts by mass,
A negative photosensitive resin composition comprising: The compound (C) or a polymer thereof is represented by the following general formula (5):

{Wherein, R ₁₃ and R ₁₄ are each independently a linear or branched alkyl group substituted with human Dorokishi group. R ₁₅ and R ₁₆ are independently a hydrogen atom, a linear or branched alkyl group, or an alkoxy group or a linear or branched alkyl group substituted with hydroxy group having 1 to 10 carbon atoms. } Or a polymer thereof and the following general formula (6):

{Wherein, R ₁₇ and R ₁₈ are each independently a linear or branched alkyl group substituted with an alkoxy group or a hydroxy group. R ₁₉ is an alkylene or alkylene ether group having 1 to 10 carbon atoms, or a substituted alkylene group having 1 to 10 carbon atoms in the alkoxy group. } The negative photosensitive resin composition of Claim 1 selected from the group which consists of a compound represented by these, or its polymer. The compound (C) or a polymer thereof is represented by the following general formula (7):

{Wherein, R ₂₀ and R ₂₁ is a linear or branched alkyl group substituted with human Dorokishi group. R ₂₀ and R ₂₁ may be different from each other or the same. R ₂₂ and R ₂₃ are each independently a hydrogen atom, a linear or branched alkyl group, or an alkoxy group or a linear or branched alkyl group substituted with hydroxy group having 1 to 10 carbon atoms. } The negative photosensitive resin composition of Claim 1 represented by these.   The negative photosensitive resin composition of Claim 1 whose said (C) compound or its polymer is 1, 3- dimethylol urea or its polymer. The negative photosensitive resin composition is (D) the following general formula (8):

{Wherein R ₂₄ and R ₂₅ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, or a carbon number substituted with a carboxyl group, a hydroxy group, an amino group or a nitro group. 1 to 40 alkyl groups or aromatic groups. R ₂₆ is a C 1-40 alkyl group or aromatic group substituted with a hydrogen atom, a phenyl group, an amino group or a silyl group. } And the following general formula (9):

{In the formula, R ₂₇ represents a hydrogen atom, a carboxyl group, a hydroxy group, an amino group, a nitro group, a linear or branched alkyl group having 1 to 40 carbon atoms, or a carboxyl group, a hydroxy group, an amino group, or a nitro group. A substituted or unsubstituted alkyl group or aromatic group having 1 to 40 carbon atoms, and R ₂₈ is a substituted or unsubstituted alkyl group or aromatic group having 1 to 40 carbon atoms substituted with a hydrogen atom, phenyl group, amino group or silyl group. is there. } And the following general formula (10):

{In the formula, R ₂₉ represents a hydrogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, or an alkyl group having 1 to 40 carbon atoms substituted with a carboxyl group, a hydroxy group, an amino group, or a nitro group; It is an aromatic group, and R ₃₀ is an alkyl group having 1 to 40 carbon atoms or an aromatic group substituted with a hydrogen atom, a phenyl group, an amino group or a silyl group. } The negative photosensitive resin composition of any one of Claims 1-4 which further contains 0.1-20 mass parts of azole compounds represented by these.   The negative photosensitive resin composition of any one of Claims 1-5 in which the said negative photosensitive resin composition further contains 0.1-20 mass parts of (E) hindered phenol compounds. (E) The hindered phenol compound is represented by the following general formula (11):

{Wherein R ₃₁ is a t-butyl group, R ₃₂ and R ₃₄ are each independently a hydrogen atom or an alkyl group, and R ₃₃ is a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyalkyl group. Group, a dialkylaminoalkyl group, a hydroxy group, or an alkyl group substituted with a carboxyl group, and R ₃₅ is a hydrogen atom or an alkyl group. } A compound represented by
The following general formula (12):

{In the formula, R ₃₆ represents a t-butyl group; R ₃₇ , R ₃₈ and R ₃₉ each independently represents a hydrogen atom or an alkyl group; and R ₄₀ represents an alkylene group, a sulfur atom, or dimethylene. Thioether group or the following general formula (13):

(In the formula, R ₄₁ represents an alkyl group having 1 to 6 carbon atoms, a diethylenethioether group, or the following formula (14):

It is group represented by these. ) Or the following formula (15):

It is group represented by these. } A compound represented by
The following general formula (16):

{Wherein R ₄₂ is a t-butyl group, a cyclohexyl group, or a methylcyclohexyl group, R ₄₃ , R ₄₄ , and R ₄₅ are each independently a hydrogen atom or an alkyl group, and R ₄₆ Is an alkylene group, a sulfur atom, or a terephthalic acid ester. } A compound represented by
The following general formula (17):

{In the formula, R ₄₇ is a t-butyl group; R ₄₈ , R ₄₉ and R ₅₀ are each independently a hydrogen atom or an alkyl group; and R ₅₁ is an alkyl group, a phenyl group, an isocyanate group. It is a nurate group or a propionate group. }; And the following general formula (18):

{Wherein R ₅₂ and R ₅₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, and R ₅₅ is an alkyl group, a phenyl group, an isocyanurate group or a propionate group. , R ₅₄ is represented by the following general formula (19):

(In the formula, R ₅₆ , R ₅₇ and R ₅₈ are each independently a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, provided that at least 2 of R ₅₆ , R ₅₇ and R ₅₈ are present. Is a monovalent organic group having 1 to 6 carbon atoms.) Or a phenyl group. } The negative photosensitive resin composition of Claim 6 chosen from the group which consists of a compound represented by these.   The negative photosensitive resin composition of any one of Claims 1-7 in which the said negative photosensitive resin composition further contains 0.05-10 mass parts of (F) organic titanium compounds.   The negative photosensitive resin composition according to claim 8, wherein the organic titanium compound is at least one selected from the group consisting of a titanium chelate compound, a tetraalkoxytitanium compound, and a titanocene compound. The following steps:
(1) Applying the negative photosensitive resin composition according to any one of claims 1 to 9 to a substrate,
(2) irradiating the negative photosensitive resin composition with actinic rays,
(3) The negative photosensitive resin composition after the irradiation is developed to form a relief pattern, and (4) The relief pattern is heated.
A method for forming a cured relief pattern. below:
(1) forming a photosensitive resin layer comprising the photosensitive resin composition according to any one of claims 1 to 9 on a substrate;
(2) exposing the photosensitive resin layer;
(3) removing the unexposed portion after the exposure to form a relief pattern;
(4) A method for producing a cured relief pattern, comprising a step of heat-treating the relief pattern.   A semiconductor device having a cured relief pattern obtained by the manufacturing method according to claim 11.