JP7075243B2 - Photosensitive resin compositions, dry films, cured products, and electronic components - Google Patents

Description

The present invention relates to photosensitive resin compositions, dry films, cured products, and electronic components.

The buffer coat film of semiconductor elements such as LSI and the insulating film for the rewiring layer of the wafer level package (WLP) contain a precursor of a photosensitive heat-resistant resin such as photosensitive polyimide or polybenzoxazole (PBO). Resin compositions are widely used.
As the photosensitive resin composition used for such a semiconductor element, for example, in Patent Document 1, a photosensitive resin containing an alkali-soluble resin, a diazonaphthoquinone compound, and a compound containing a —CH ₂ OH group without containing a phenolic hydroxyl group. We are proposing a composition. According to the proposed composition, it is possible to obtain a composition that can be developed without a development residue (scum) on a silicon wafer.
On the other hand, in recent years, due to the miniaturization of semiconductor elements and the increase in multi-layer wiring due to high integration, the surface protective film and the interlayer insulating film are often directly formed on the copper wiring.

Japanese Unexamined Patent Publication No. 2005-37925

According to the prior art according to the proposal of Patent Document 1, it is possible to suppress the development residue on the silicon wafer. However, this technique has a problem that a large amount of development residue is generated when developing on a copper substrate.

Therefore, an object of the present invention is a photosensitive resin composition excellent in suppressing development residue on a copper substrate, a dry film having a resin layer obtained from the composition, and curing of the composition or the resin layer of the dry film. The present invention is to provide an object and an electronic component having the cured product.

The present inventors have made diligent studies toward the realization of the above object. In this study, if the development time is lengthened to reduce the scum amount in order to reduce the development residue on the copper substrate, streaks and cracks are generated by the development, and the residual film ratio is increased. Another problem has arisen:

Therefore, as a result of further diligent studies, it was found that by using a triazole compound having a mercapto group and a melamine-based cross-linking agent in combination, it is possible to achieve both suppression of development residue and development resistance even when the development time is lengthened. , The present invention has been completed.

That is, the photosensitive resin composition of the present invention contains (A) a polybenzoxazole precursor, (B) a photoacid generator, (C) a triazole compound having a mercapto group, and (D) a melamine-based cross-linking agent. It is characterized by.

（一般式（１）中、Ｐはジアミン成分の残基であり、下記一般式（１－１）、（１－２）および（１－３）のいずれかのベンゾオキサゾール構造を有する２価の基である。Ｒ’はジカルボン酸成分の残基であり、２価の有機基である。）

（一般式（１－１）中、Ｒ_１～Ｒ_４は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、一般式（１）中の窒素原子との直接結合のいずれかであり、同一であっても異なっていてもよい。Ｒ_５～Ｒ_９は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、一般式（１）中の窒素原子との直接結合のいずれかであり、同一であっても異なっていてもよい。ただし、Ｒ_１～Ｒ_４のうちいずれか一つ、および、Ｒ_５～Ｒ_９のうちいずれか一つは、一般式（１）中の窒素原子との直接結合である。）

（一般式（１－２）中、Ｒ_１０～Ｒ_１４は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、一般式（１）中の窒素原子との直接結合のいずれかであり、同一であっても異なっていてもよい。Ｒ_１５～Ｒ_１９は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、一般式（１）中の窒素原子との直接結合のいずれかであり、同一であっても異なっていてもよい。ただし、Ｒ_１０～Ｒ_１４のうちいずれか一つ、および、Ｒ_１５～Ｒ_１９のうちいずれか一つは、一般式（１）中の窒素原子との直接結合である。Ｒ_２０、Ｒ_２１はそれぞれ水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基のいずれかであり、同一であっても異なっていてもよい。）

（一般式（１－３）中、Ｒ_２２～Ｒ_２６は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、一般式（１）中の窒素原子との直接結合のいずれかであり、同一であっても異なっていてもよい。Ｒ_２７～Ｒ_３１は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、一般式（１）中の窒素原子との直接結合のいずれかであり、同一であっても異なっていてもよい。ただし、Ｒ_２２～Ｒ_２６のうちいずれか一つ、および、Ｒ_２７～Ｒ_３１のうちいずれか一つは、一般式（１）中の窒素原子との直接結合である。Ｒ_３２、Ｒ_３３はそれぞれ水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基のいずれかであり、同一であっても異なっていてもよい。）

（一般式（２）中、Ｘはジヒドロキシジアミン類の残基であり、４価の有機基である。Ｙは、ジカルボン酸成分の残基であり、２価の有機基である。） The photosensitive resin composition of the present invention is a polyamide-based resin obtained by reacting the polybenzoxazole precursor (A) with a diamine component and a dicarboxylic acid component, and has the following general formula (1) in the polyamide structure. The proportion of the structure shown is preferably 0.1 to 15%, and the proportion of the structure represented by the following general formula (2) is preferably 85 to 99.9%.

(In the general formula (1), P is a residue of the diamine component, and is a divalent divalent having the benzoxazole structure of any one of the following general formulas (1-1), (1-2) and (1-3). Group. R'is a residue of the dicarboxylic acid component and is a divalent organic group.)

(In the general formula (1-1), R ₁ to R ₄ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, and a direct bond with a nitrogen atom in the general formula (1). R ₅ to R ₉ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, and the general formula (1). It is one of the direct bonds with the nitrogen atom of, and may be the same or different. However, any one of R ₁ to R ₄ and any one of R ₅ to R ₉ One is a direct bond with a nitrogen atom in the general formula (1).)

(In the general formula (1-2), R ₁₀ to R ₁₄ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, and a direct bond with a nitrogen atom in the general formula (1). R ₁₅ to R ₁₉ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, and the general formula (1). It is one of the direct bonds with the nitrogen atom of, and may be the same or different. However, any one of R ₁₀ to R ₁₄ and any one of R ₁₅ to R ₁₉ One is a direct bond with the nitrogen atom in the general formula (1). R ₂₀ and R ₂₁ are any of a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group and an amino group, respectively. Yes, they may be the same or different.)

(In the general formula (1-3), R ₂₂ to R ₂₆ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, and a direct bond with a nitrogen atom in the general formula (1). R ₂₇ to R ₃₁ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, and the general formula (1). It is one of the direct bonds with the nitrogen atom of, and may be the same or different. However, any one of R ₂₂ to R ₂₆ and any one of R ₂₇ to R ₃₁ . One is a direct bond with a nitrogen atom in the general formula (1). R ₃₂ and R ₃₃ are any of a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group and an amino group, respectively. Yes, they may be the same or different.)

(In the general formula (2), X is a residue of dihydroxydiamines and is a tetravalent organic group. Y is a residue of a dicarboxylic acid component and is a divalent organic group.)

In the photosensitive resin composition of the present invention, the triazole compound having the (C) mercapto group is preferably 3-mercapto-1,2,4-triazole.

The photosensitive resin composition of the present invention is preferably used for forming a cured film on a copper substrate.

The dry film of the present invention is characterized by having a resin layer obtained by applying the photosensitive resin composition to the film and drying the film.

The cured product of the present invention is characterized by being obtained by curing the resin layer of the photosensitive resin composition or the dry film.

The electronic component of the present invention is characterized by having the cured product.

According to the present invention, a photosensitive resin composition capable of achieving both suppression of development residue and development resistance even when the development time is lengthened, a dry film having a resin layer obtained from the composition, and the composition. Alternatively, it is possible to provide a cured product of the resin layer of the dry film and an electronic component having the cured product.

Hereinafter, the components contained in the photosensitive resin composition of the present invention will be described in detail.

The photosensitive resin composition of the present invention is characterized by containing (A) a polybenzoxazole precursor, (B) a photoacid generator, (C) a triazole compound having a mercapto group, and (D) a melamine-based cross-linking agent. Is to be.

According to the present invention, by using (C) a triazole compound having a mercapto group and (D) a melamine-based cross-linking agent in combination, both suppression of development residue and development resistance can be achieved even when the development time is lengthened. Can be done. The development resistance in the present invention means that the residual film ratio after development is high and there are no patterns or cracks on the surface of the cured film.

[(A) Polybenzoxazole precursor]
The photosensitive resin composition of the present invention contains (A) a polybenzoxazole precursor. (A) The method for synthesizing the polybenzoxazole precursor is not particularly limited, and the polybenzoxazole precursor may be synthesized by a known method. For example, it can be obtained by reacting a dihydroxydiamine as an amine component with a dihalide of a dicarboxylic acid such as a dicarboxylic acid dichloride as an acid component.

(A) As the polybenzoxazole precursor, the proportion of the structure represented by the following general formula (1) is 0.1 to 15% in the polyamide structure, and the proportion of the structure represented by the following general formula (2) is 85. A polyamide resin obtained from the reaction of a diamine component and a dicarboxylic acid component having an amount of about 99.9% can be preferably used, and a cured film having high heat resistance and a low coefficient of linear thermal expansion can be formed. A photosensitive resin composition having excellent resolution can be obtained.

（一般式（１）中、Ｐはジアミン成分の残基であり、下記一般式（１－１）、（１－２）および（１－３）のいずれかのベンゾオキサゾール構造を有する２価の基である。Ｒ’はジカルボン酸成分の残基であり、２価の有機基である。）

（一般式（１－１）中、Ｒ_１～Ｒ_４は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、一般式（１）中の窒素原子との直接結合のいずれかであり、同一であっても異なっていてもよい。Ｒ_５～Ｒ_９は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、一般式（１）中の窒素原子との直接結合のいずれかであり、同一であっても異なっていてもよい。ただし、Ｒ_１～Ｒ_４のうちいずれか一つ、および、Ｒ_５～Ｒ_９のうちいずれか一つは、一般式（１）中の窒素原子との直接結合である。）

（一般式（１－２）中、Ｒ_１０～Ｒ_１４は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、一般式（１）中の窒素原子との直接結合のいずれかであり、同一であっても異なっていてもよい。Ｒ_１５～Ｒ_１９は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、一般式（１）中の窒素原子との直接結合のいずれかであり、同一であっても異なっていてもよい。ただし、Ｒ_１０～Ｒ_１４のうちいずれか一つ、および、Ｒ_１５～Ｒ_１９のうちいずれか一つは、一般式（１）中の窒素原子との直接結合である。Ｒ_２０、Ｒ_２１はそれぞれ水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基のいずれかであり、同一であっても異なっていてもよい。）

（一般式（１－３）中、Ｒ_２２～Ｒ_２６は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、一般式（１）中の窒素原子との直接結合のいずれかであり、同一であっても異なっていてもよい。Ｒ_２７～Ｒ_３１は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、一般式（１）中の窒素原子との直接結合のいずれかであり、同一であっても異なっていてもよい。ただし、Ｒ_２２～Ｒ_２６のうちいずれか一つ、および、Ｒ_２７～Ｒ_３１のうちいずれか一つは、一般式（１）中の窒素原子との直接結合である。Ｒ_３２、Ｒ_３３はそれぞれ水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基のいずれかであり、同一であっても異なっていてもよい。）

（一般式（２）中、Ｘはジヒドロキシジアミン類の残基であり、４価の有機基である。Ｙは、ジカルボン酸成分の残基であり、２価の有機基である。）

(In the general formula (1), P is a residue of the diamine component, and is a divalent divalent having the benzoxazole structure of any one of the following general formulas (1-1), (1-2) and (1-3). Group. R'is a residue of the dicarboxylic acid component and is a divalent organic group.)

(In the general formula (1-1), R ₁ to R ₄ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, and a direct bond with a nitrogen atom in the general formula (1). R ₅ to R ₉ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, and the general formula (1). It is one of the direct bonds with the nitrogen atom of, and may be the same or different. However, any one of R ₁ to R ₄ and any one of R ₅ to R ₉ One is a direct bond with a nitrogen atom in the general formula (1).)

(In the general formula (1-2), R ₁₀ to R ₁₄ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, and a direct bond with a nitrogen atom in the general formula (1). R ₁₅ to R ₁₉ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, and the general formula (1). It is one of the direct bonds with the nitrogen atom of, and may be the same or different. However, any one of R ₁₀ to R ₁₄ and any one of R ₁₅ to R ₁₉ One is a direct bond with the nitrogen atom in the general formula (1). R ₂₀ and R ₂₁ are any of a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group and an amino group, respectively. Yes, they may be the same or different.)

(In the general formula (1-3), R ₂₂ to R ₂₆ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, and a direct bond with a nitrogen atom in the general formula (1). R ₂₇ to R ₃₁ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, and the general formula (1). It is one of the direct bonds with the nitrogen atom of, and may be the same or different. However, any one of R ₂₂ to R ₂₆ and any one of R ₂₇ to R ₃₁ . One is a direct bond with a nitrogen atom in the general formula (1). R ₃₂ and R ₃₃ are any of a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group and an amino group, respectively. Yes, they may be the same or different.)

(In the general formula (2), X is a residue of dihydroxydiamines and is a tetravalent organic group. Y is a residue of a dicarboxylic acid component and is a divalent organic group.)

Here, the ratio in the polyamide structure is represented by the above general formula (1) after counting the amide structure composed of one diamine component and one dicarboxylic acid component as one as in the general formula (1). It means the ratio per total number of amide structures in the polyamide structure contained in the polybenzoxazole precursor having the above-mentioned structure and the structure represented by the general formula (2). Since the reaction between the diamine component and the dicarboxylic acid component is 100% complete, the above ratio is one of the general formulas (1-1), (1-2) and (1-3) in the diamine component. It can be determined by the ratio (molar conversion) of the diamine having a benzoxazole structure (hereinafter, also referred to as “benzoxazole moiety”). The ratio may be obtained by analysis by NMR or the like. The total number of amide structures in the polyamide structure contained in the polybenzoxazole precursor having the structure represented by the general formula (1) and the structure represented by the general formula (2) is preferably 10 to 30, preferably 15 to 25. Is more preferable.

When the ratio of the structure represented by the general formula (1) is 0.1% or more, the heat resistance of the cured product is good and the coefficient of linear thermal expansion can be lowered. Further, when the above ratio is 15% or less, the sensitivity and the resolution are good. It is preferably 1 to 10%.

The polyamide structure of the polybenzoxazole precursor having the structure represented by the general formula (1) and the structure represented by the general formula (2) is obtained from the reaction of the diamine component and the dicarboxylic acid component. The diamine component and the dicarboxylic acid component may be any as long as they are used for the synthesis of polyamide. For example, the diamine component is a diamine, and the dicarboxylic acid component is a dicarboxylic acid such as a dicarboxylic acid, a dicarboxylic acid ester, or a carboxylic acid dichloride. Jihalide is mentioned.

The structure represented by the general formula (1) may be continuously repeated in a polybenzoxazole precursor having the structure represented by the general formula (1) and the structure represented by the general formula (2). It is often preferable that the number of repetitions is 1 to 5 (however, when the number of repetitions is 1, it means that the number of repetitions is not continuous).

R ₁ to R ₄ , R ₅ to R ₉ in the general formula (1-1), R ₁₀ to R ₁₄ , R ₁₅ to R ₁₉ in the general formula (1-2), and the general formula (1-). It is preferable that R ₂₂ to R ₂₆ and R ₂₇ to R ₃₁ in 3) are direct bonds with a hydrogen atom or a nitrogen atom in the general formula (1).

R ₁ to R ₄ , R ₅ to R ₉ in the general formula (1-1), R ₁₀ to R ₁₄ , R ₁₅ to R ₁₉ in the general formula (1-2), and the general formula (1-). Examples of the organic groups that R ₂₂ to R ₂₆ and R ₂₇ to R ₃₁ in 3) can take include an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a cycloalkyl group having 3 to 8 carbon atoms. Examples thereof include a group, an aryl group having 6 to 12 carbon atoms, an allyl group, a trifluoromethyl group and the like.

Examples of the organic group that can be taken by R ₂₀ and R ₂₁ in the general formula (1-2) and R ₃₂ and R ₃₃ in the general formula (1-3) include an alkyl group having 1 to 3 carbon atoms. Examples thereof include an alkoxy group having 1 to 3 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, an allyl group and a trifluoromethyl group.

Halogen that can be taken by R ₁ to R ₉ in the general formula (1-1), R ₁₀ to R ₂₁ in the general formula (1-2), and R ₂₂ to R ₃₃ in the general formula (1-3). Examples of the atom include fluorine, chlorine and bromine. Of these, fluorine is preferable because of the transmittance of the polymer.

R ₁ to R ₉ in the general formula (1-1), R ₁₀ to R ₂₁ in the general formula (1-2), and R ₂₂ to R ₃₃ in the general formula (1-3) can be taken. Examples of the sulfonyl group include an alkylsulfonyl group having 1 to 10 carbon atoms such as a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, an octylsulfonyl group, a decylsulfonyl group and a dodecylsulfonyl group.

In the general formula (1), the diamine component represented by P is a diamine corresponding to the general formulas (1-1), (1-2) and (1-3) (that is, the general formula (1-)). 1), diamines in which the two "direct bonds with nitrogen atoms in the general formula (1)" of (1-2) and (1-3) are changed to amino groups) can be mentioned.

In the general formula (1), as the dicarboxylic acid component represented by R', isophthalic acid, terephthalic acid, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, etc. 2,6-naphthalenedicarboxylic acid, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2- Bis (p-carboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) -1,1
, 1,3,3,3-hexafluoropropane and other dicarboxylic acids with aromatic rings, oxalic acid, malonic acid, succinic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3- Examples thereof include aliphatic dicarboxylic acids such as cyclopentanedicarboxylic acid and dihalides thereof. Of these, 4,4'-dicarboxydiphenyl ether and dihalide thereof are preferable.

In the general formula (1), the divalent organic group represented by R'may be an aliphatic group or an aromatic group, but it is preferably an aromatic group, and the divalent organic group represented by the general formula (1) is preferably an aromatic group. More preferably, it is bound to carbonyl. The number of carbon atoms of the divalent aromatic group is preferably 6 to 30, and more preferably 6 to 24. Specific examples of the divalent aromatic group include, but are not limited to, any known aromatic group contained in the polybenzoxazole precursor can be selected according to the intended use. good.

（式中、Ａは単結合、－ＣＨ_２－、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ_２－、－ＮＨＣＯ－、－Ｃ（ＣＦ_３）_２－、－Ｃ（ＣＨ_３）_２－からなる群から選択される２価の基を表す。）

(In the formula, A is a single bond, -CH _2- , -O-, -CO-, -S-, -SO _2- , -NHCO-, -C (CF ₃ ) _2- , -C (CH ₃ ). Represents a divalent group selected from the group consisting of _2- )

The divalent organic group is preferably the following group among the aromatic groups.

The polybenzoxazole precursor having the structure represented by the general formula (1) and the structure represented by the general formula (2) may contain two or more types of the structures represented by the general formula (1).

The ratio of the amide structure of the general formula (1) to the amide structure of the general formula (2) is preferably 0.1: 99.9 to 15:85, and preferably 1: 99 to 10:90. More preferably, it is more preferably 1:99 to 5:95.

（式中、Ｘはジヒドロキシジアミン類の残基であり、４価の有機基である。Ｙは、ジカルボン酸成分の残基であり、２価の有機基である。前記一般式（２）で示される構造は、上記一般式（１）で示される構造と一般式（２）で示される構造とを有するポリベンゾオキサゾール前駆体中に、連続して繰り返していてもよく、繰り返し数は１０～３０であることが好ましく、１５～２５であることがより好ましい（ただし、ここで繰り返し数が１の場合、連続して繰り返していないことを意味する）。）

(In the formula, X is a residue of dihydroxydiamines and is a tetravalent organic group. Y is a residue of a dicarboxylic acid component and is a divalent organic group. In the above general formula (2). The structure shown may be continuously repeated in a polybenzoxazole precursor having the structure represented by the above general formula (1) and the structure represented by the general formula (2), and the number of repetitions is 10 to 10. It is preferably 30 and more preferably 15 to 25 (however, when the number of repetitions is 1, it means that the number of repetitions is not continuous).

Examples of the dihydroxydiamines represented by X in the general formula (2) include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl and bis (3-). Amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 2, 2-Bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) -1,1, Examples thereof include 1,3,3,3-hexafluoropropane. Of these, 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane is preferable.

In the general formula (2), the tetravalent organic group represented by X may be an aliphatic group or an aromatic group, but it is preferably an aromatic group, and two hydroxy groups and two amino groups are in the ortho position. It is more preferably located on the aromatic ring. The number of carbon atoms of the tetravalent aromatic group is preferably 6 to 30, and more preferably 6 to 24. Specific examples of the tetravalent aromatic group include, but are not limited to, a known aromatic group that can be contained in the polybenzoxazole precursor, depending on the intended use. Just do it.

The tetravalent aromatic group is preferably the following group among the aromatic groups.

The dicarboxylic acid component represented by Y in the general formula (2) is the same as the dicarboxylic acid component represented by R'in the general formula (1).

Further, as the (A) polybenzoxazole precursor, a polybenzoxazole precursor having a structure represented by the following general formula (3) can be preferably used.

（式中、Ｘはジヒドロキシジアミン類の残基であり、４価の有機基である。Ｙは、ジカルボン酸成分の残基であり、２価の有機基である。ｍは１以上の整数である。）

(In the formula, X is a residue of dihydroxydiamines and is a tetravalent organic group. Y is a residue of a dicarboxylic acid component and is a divalent organic group. M is an integer of 1 or more. be.)

In the general formula (3), m is preferably 10 to 50, more preferably 20 to 40.

The dihydroxydiamines represented by X in the general formula (3) are the same as the dihydroxydiamines represented by X in the general formula (2).

The tetravalent organic group represented by X in the general formula (3) is the same as the tetravalent organic group represented by X in the general formula (2).

The dicarboxylic acid component represented by Y in the general formula (3) is the same as the dicarboxylic acid component represented by R'in the general formula (1), similar to Y in the general formula (2).

The polybenzoxazole precursor having the structure represented by the general formula (3) may contain two or more types of the structure represented by the general formula (3).

The number average molecular weight (Mn) of the (A) polybenzoxazole precursor is preferably 5,000 to 100,000, more preferably 8,000 to 50,000. Here, the number average molecular weight is a numerical value measured by gel permeation chromatography (hereinafter referred to as “GPC”) and converted into standard polystyrene. The mass average molecular weight (Mw) of the (A) polybenzoxazole precursor is preferably 10,000 to 200,000, more preferably 16,000 to 100,000. Here, the mass average molecular weight is a numerical value measured by GPC and converted into standard polystyrene. Mw / Mn is preferably 1 to 5, and more preferably 1 to 3.

The blending amount of the (A) polybenzoxazole precursor is preferably 60 to 90% by mass based on the total solid content of the composition.

[(B) Photoacid generator]
(B) Examples of the photoacid generator include naphthoquinone diazide compounds, diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, and aromatic sulfonic acid esters. Examples thereof include nitrobenzyl ester, aromatic N-oxyimide sulfonate, aromatic sulfamide, benzoquinone diazosulfonic acid ester and the like. (B) The photoacid generator is preferably a dissolution inhibitor. Of these, it is preferably a naphthoquinone diazide compound.

Specific examples of the naphthoquinone diazide compound include naphthoquinone diazide adducts of tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene (for example, TKF-520 and TKF-528 manufactured by Sanpo Chemical Research Institute). , TKF-420, TKF-428), naphthoquinone diazide adduct of tetrahydroxybenzophenone (for example, BS550, BS570, BS599 manufactured by Sanpo Chemical Research Institute) and the like can be used. Here, the addition of naphthoquinone diazide may be carried out, for example, by reacting o-quinone diazidosulfonyl chlorides with a hydroxy compound or an amino compound.

(B) As the photoacid generator, one type may be used alone, or two or more types may be used in combination. The blending amount of the photoacid generator (B) is preferably 3 to 20% by mass based on the total solid content of the composition.

[(C) Triazole compound having a mercapto group]
The photosensitive resin composition of the present invention contains (C) a triazole compound having a mercapto group. Although the detailed mechanism is not clear, the adhesion to the copper substrate can be improved and the development residue on the copper can be suppressed.

The (C) triazole compound having a mercapto group is not particularly limited as long as it is a compound having a mercapto group and having a triazole structure. For example, the triazole compound having a mercapto group (C) is 3-mercapto. -1,2,4-triazole, 3-mercapto-4-methyl-4H-1,2,4-triazole and the like can be mentioned. Of these, a compound such as the above compound in which a mercapto group is directly bonded to the triazole ring is preferable. Further, (C) the triazole compound having a mercapto group is more preferably a compound represented by the following general formula (4), and particularly preferably 3-mercapto-1,2,4-triazole.

（式（４）中、Ｒ_４１は、水素原子または炭素数１～３のアルキル基であることが好ましく、水素原子であることがより好ましい。）

(In the formula (4), R ₄₁ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.)

(C) As the triazole compound having a mercapto group, one kind may be used alone, or two or more kinds may be used in combination. (C) The blending amount of the triazole compound having a mercapto group is preferably 0.1 to 5.0% by mass, more preferably 0.5 to 2.0% by mass, based on the total solid content of the composition. preferable.

((D) Melamine-based cross-linking agent)
Since the photosensitive resin composition of the present invention contains a melamine-based cross-linking agent, not only good development resistance can be obtained, but also the strength of the cured film when cured at low temperature is increased.

The melamine-based cross-linking agent is not particularly limited as long as it is a compound having a melamine structure, but a melamine-based cross-linking agent represented by the following general formula (5) is preferable.

（式中、Ｒ^５１Ａ、Ｒ^５２Ａ、Ｒ^５３Ａ、Ｒ^５４Ａ、Ｒ^５５ＡおよびＲ^５６Ａはそれぞれ独立に炭素数１～３のアルキレン基であることが好ましい。Ｒ^５１Ｂ、Ｒ^５２Ｂ、Ｒ^５３Ｂ、Ｒ^５４Ｂ、Ｒ^５５ＢおよびＲ^５６Ｂはそれぞれ独立に水素原子、または、炭素数１～３のアルキル基であることが好ましい。）

(In the formula, it is preferable that R ^51A , R ^52A , R ^53A , R ^54A , R ^55A and R ^56A are independently alkylene groups having 1 to 3 carbon atoms, respectively. R ^51B , R ^52B , R ^53B , R ^54B . , R ^55B and R ^56B are preferably hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, respectively.)

In the above general formula (5), it is more preferable that R ^51A , R ^52A , R ^53A , R ^54A , R ^55A and R ^56A are each methylene groups. Further, it is more preferable that R ^51B , R ^52B , R ^53B , R ^54B , R ^55B and R ^56B are independently methyl groups or hydrogen atoms, respectively.

The melamine-based cross-linking agent may be used alone or in combination of two or more. The blending amount of the melamine-based cross-linking agent is preferably 1 to 40% by mass based on the total solid content of the composition.

Further, the photosensitive resin composition of the present invention may contain a cross-linking agent other than the (D) melamine-based cross-linking agent as long as the effect of the present invention is not impaired.

A solvent can be added to the photosensitive resin composition of the present invention. As the solvent, (A) a polybenzoxazole precursor, (B) a photoacid generator, (C) a triazole compound having a mercapto group, (D) a melamine-based cross-linking agent, and any other additive are dissolved. If it is a thing, it is not particularly limited. Specific examples of the solvent include N, N'-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N, N'-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl. -Γ-Butyrolactone, Tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, dimethylsulfoxide, hexamethylphosphoramide, pyridine, γ-butyrolactone, diethylene glycol monomethyl ether can be mentioned. can. These may be used alone or in combination of two or more. The amount of the solvent used can be in the range of 50 to 9000 parts by mass with respect to 100 parts by mass of the (A) polybenzoxazole precursor, depending on the coating film thickness and viscosity.

A known sensitizer, a silane coupling agent, a adhesion aid, or the like can be added to the photosensitive resin composition of the present invention as long as the effects of the present invention are not impaired.

In addition, various organic or inorganic small molecule or polymer compounds may be added to the photosensitive resin composition of the present invention in order to impart processing characteristics and various functionalities. For example, a surfactant, a leveling agent, a plasticizer, fine particles and the like can be used. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, and inorganic fine particles such as colloidal silica, carbon and layered silicate. Further, various colorants, fibers and the like may be blended in the photosensitive resin composition of the present invention.

[Dry film]
The dry film of the present invention has a resin layer obtained by applying the photosensitive resin composition of the present invention and then drying it.

The dry film of the present invention is obtained by uniformly applying the photosensitive resin composition of the present invention to a carrier film (supporting film) by an appropriate method using a blade coater, a lip coater, a comma coater, a film coater, or the like, and drying the dry film. It can be produced by forming the above-mentioned resin layer and preferably laminating a cover film (protective film) on the resin layer. The cover film and the carrier film may be the same film material or different films may be used.

In the dry film of the present invention, as the film material of the carrier film and the cover film, any known one as used for the dry film can be used.

As the carrier film, for example, a thermoplastic film such as a polyester film such as polyethylene terephthalate having a thickness of 2 to 150 μm is used.

As the cover film, a polyethylene film, a polypropylene film or the like can be used, but one having a smaller adhesive force with the resin layer than the carrier film is preferable.

The film thickness of the resin layer on the dry film of the present invention is preferably 100 μm or less, more preferably 5 to 50 μm.

The photosensitive resin composition of the present invention is preferably of a positive type. Using the photosensitive resin composition of the present invention, a patterned film as a cured product thereof is produced, for example, as follows.

First, as step 1, a photosensitive resin composition is applied onto a substrate and dried, or a resin layer is transferred (laminated) from a dry film onto a substrate to obtain a coating film. As a method of applying the photosensitive resin composition on the substrate, a method conventionally used for applying the photosensitive resin composition, for example, a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine or the like is used. A coating method, a spray coating method using a spray coater, an inkjet method, or the like can be used. As a method for drying the coating film, a method such as air drying, heat drying using an oven or a hot plate, and vacuum drying is used. Further, it is desirable that the coating film is dried under conditions that do not cause ring closure of the (A) polybenzoxazole precursor in the photosensitive resin composition. Specifically, natural drying, blast drying, or heat drying can be performed at 70 to 140 ° C. for 1 to 30 minutes. Preferably, it is dried on a hot plate for 1 to 20 minutes. Vacuum drying is also possible, and in this case, it can be performed at room temperature for 20 minutes to 1 hour.

The substrate is not particularly limited and can be widely applied to a semiconductor substrate such as a silicon wafer, a wiring substrate, and a substrate made of various resins or metals. However, the present invention is a copper substrate, that is, a substrate having copper wiring. The effect of can be obtained well.

Next, as step 2, the coating film is exposed either through a photomask having a pattern or directly. As the exposed light beam, (B) a light having a wavelength capable of activating the photoacid generator and generating an acid is used. Specifically, the exposed light beam preferably has a maximum wavelength in the range of 350 to 410 nm. As described above, the photosensitivity can be adjusted by appropriately using a sensitizer. As the exposure apparatus, a contact aligner, a mirror projection, a stepper, a laser direct exposure apparatus and the like can be used.

Subsequently, as step 3, the unexposed portion of the (A) polybenzoxazole precursor may be partially ring-closed by heating. Here, the ring closure rate is about 30%. The heating time and the heating temperature are appropriately changed depending on (A) the polybenzoxazole precursor, the coating film thickness, and (B) the type of the photoacid generator.

Then, as step 4, the coating film is treated with a developer. Thereby, the exposed portion in the coating film can be removed to form the pattern film of the photosensitive resin composition of the present invention. According to the present invention, since the development resistance is excellent, the margin of development time is wide. For example, a dry film having a film thickness of 10 to 15 μm can be developed in a development time of 60 seconds to 180 seconds, and a residual film ratio of 80% or more. Can be maintained.

As a method used for development, any method can be selected from conventionally known photoresist development methods such as a rotary spray method, a paddle method, and a dipping method accompanied by ultrasonic treatment. The developing solution includes inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate and aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine and triethanolamine, tetramethylammonium hydroxide and tetrabutylammonium hydroxide. Examples thereof include aqueous solutions of tetraammonium salts and the like. Further, if necessary, a water-soluble organic solvent such as methanol, ethanol, isopropyl alcohol or a surfactant may be added in an appropriate amount. Then, if necessary, the coating film is washed with a rinsing solution to obtain a patterned film. Distilled water, methanol, ethanol, isopropyl alcohol and the like can be used alone or in combination as the rinsing solution. Moreover, you may use the said solvent as a developer.

Then, as step 5, the pattern film is heated to obtain a cured coating film (cured product). At this time, the (A) polybenzoxazole precursor may be ring-closed to obtain polybenzoxazole. The heating temperature is appropriately set so that the pattern film of polybenzoxazole can be cured. For example, heating is carried out at 150 to 350 ° C. for about 5 to 120 minutes in an inert gas. A more preferable range of the heating temperature is 180 to 320 ° C. Heating is performed, for example, by using a hot plate, an oven, or a heating oven in which a temperature program can be set. As the atmosphere (gas) at this time, air may be used, or an inert gas such as nitrogen or argon may be used.

The use of the photosensitive resin composition of the present invention is not particularly limited, and is suitable as, for example, a paint, a printing ink, or an adhesive, or a material for forming a display device, a semiconductor device, an electronic component, an optical component, or a building material. Used. Specifically, as a material for forming a display device, a color filter, a film for a flexible display, a resist material, an alignment film, or the like can be used as a layer forming material or an image forming material. Further, as the forming material of the semiconductor device, it can be used as a resist material, a layer forming material such as a buffer coat film, or the like. Further, as a material for forming an electronic component, it can be used as a sealing material or a layer forming material for a printed wiring board, an interlayer insulating film, a wiring coating film, or the like. Furthermore, as a material for forming an optical component, as an optical material or a layer forming material, it can be used for a hologram, an optical waveguide, an optical circuit, an optical circuit component, an antireflection film, or the like. Furthermore, as a building material, it can be used as a paint, a coating agent, or the like.

The photosensitive resin composition of the present invention is mainly used as a pattern forming material, and the pattern film formed thereby functions as a permanent film made of polybenzoxazole as a component that imparts heat resistance and insulating properties. In particular, surface protective films for semiconductor devices, display devices and light emitting devices, interlayer insulating films, insulating films for rewiring, protective films for flip chip devices, protective films for devices with bump structures, interlayer insulating films for multilayer circuits, passive It can be suitably used as an insulating material for parts, a protective film for printed wiring boards such as solder resist and coverlay film, and a liquid crystal alignment film.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. In the following, "part" and "%" are all based on mass unless otherwise specified.

(Synthesis of polybenzoxazole precursor A-1)
212 g of N-methylpyrrolidone was charged in a 0.5 liter flask equipped with a stirrer and a thermometer, and 60.52 g (165.22 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved by stirring. Then, the flask is immersed in an ice bath, and 53.02 g (179.65 mmol) of 4,4-diphenyl ether dicarboxylic acid chloride is added in a solid state over 30 minutes while keeping the inside of the flask at 0 to 5 ° C., and the ice bath is added. It was stirred inside for 30 minutes. Then, stirring was continued for 5 hours at room temperature. The stirred solution was poured into 1 L of ion-exchanged water (specific resistance value 18.2 MΩ · cm), and the precipitate was recovered. Then, the obtained solid was dissolved in 420 mL of acetone and put into 1 L of ion-exchanged water. After recovering the precipitated solid, the solid was dried under reduced pressure to obtain a polybenzoxazole (PBO) precursor A-1 having the following repeating structure at the terminal of a carboxyl group. The number average molecular weight (Mn) of the polybenzoxazole precursor A-1 was 13,100, the weight average molecular weight (Mw) was 32,100, and Mw / Mn was 2.45.

(Synthesis of polybenzoxazole precursor A-2)
85 g of N-methylpyrrolidone was placed in a 0.5 liter flask equipped with a stirrer and a thermometer, and 11.21 g (30.6 mmol) and 2- (4- (4-) bis (3-amino-4-hydroxyphenyl) hexafluoropropane were charged. Aminophenyl) -5-aminobenzoxazole 0.145 g (0.644 mmol) was stirred and dissolved. Then, the flask is immersed in an ice bath, and 10.10 g (34.2 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride is added in a solid state over 10 minutes while keeping the inside of the flask at 0 to 5 ° C. Was stirred for 30 minutes. Then, stirring was continued for 18 hours at room temperature. The stirred solution was poured into 400 mL of ion-exchanged water (specific resistance value 18.2 MΩ · cm), and the precipitate was recovered. Then, the obtained solid was dissolved in 440 mL of methylpropanol and put into 1 L of ion-exchanged water. After recovering the precipitated individual, it was dried under reduced pressure to obtain a partially cyclized polybenzoxazole precursor A-2 at the terminal of a carboxyl group. The weight average molecular weight determined by GPC method standard polystyrene conversion was 34,500.

The polybenzoxazole precursor A-1 has a structure represented by the above general formula (3) and has a repeating structure having the following amide structure. The polybenzoxazole precursor A-2 has a structure represented by the above general formulas (1) and (2), and contains 98% of the following amide structure and the amide structure having the following benzoxazole structure. : Have at 2%.

(Amid structure)

(Amid structure with benzoxazole structure)

( Reference example 1)
100 parts by mass of polybenzoxazole precursor (A-1), 10 parts by mass of diazonaphthoquinone compound (B), 2 parts by mass of triazole compound (C-1) having a mercapto group, and 10 parts by mass of melamine-based cross-linking agent (D). After dissolving in 300 parts by mass of γ-butylolactone, the mixture was filtered through a 0.2 μm filter to obtain a varnish of a photosensitive resin composition.

(Example 2)
A varnish of the photosensitive resin composition of Example 2 was obtained under the same conditions as in Reference Example 1 except that the polybenzoxazole precursor (A-1) was changed to the polybenzoxazole precursor (A-2). rice field.

(Comparative Example 1)
A varnish of the photosensitive resin composition of Comparative Example 1 was obtained under the same conditions as in Reference Example 1 except that the triazole compound (C-1) having a mercapto group and the melamine-based cross-linking agent (D) were not used. rice field.

(Comparative Example 2)
A varnish of the photosensitive resin composition of Comparative Example 2 was obtained under the same conditions as in Reference Example 1 except that the melamine-based cross-linking agent (D) was not used.

(Comparative Example 3)
Comparison under the same conditions as in Reference Example 1 except that the triazole compound (C-1) having a mercapto group was changed to the triazole compound (R-1) and the melamine-based cross-linking agent (D) was not used. A varnish of the photosensitive resin composition of Example 3 was obtained.

(Comparative Example 4)
Comparison under the same conditions as in Reference Example 1 except that the triazole compound (C-1) having a mercapto group was changed to the triazole compound (R-2) and the melamine-based cross-linking agent (D) was not used. A varnish of the photosensitive resin composition of Example 4 was obtained.

(Comparative Example 5)
A varnish of the photosensitive resin composition of Comparative Example 5 was obtained under the same conditions as in Reference Example 1 except that the triazole compound (C-1) having a mercapto group was not used.

(Preparation of pattern cured film)
The varnish of the photosensitive resin composition of Reference Example 1, Example 2 and Comparative Examples 1 to 5 is applied onto a silicon wafer (Φ6 inch) subjected to copper sputtering using a spin coater, and 110 on a hot plate. It was dried at ° C. for 3 minutes to obtain a coating film having a film thickness of about 13 to 15 μm. The obtained coating film was subjected to i-line exposure of 800 mJ / cm ² through a mask on which a pattern of 10 μm was drawn. After the exposure, it was developed with a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 120 seconds and rinsed with water to obtain a pattern of a positive cured film.

(Development resistance)
The developed L / S = 10 μm / 10 μm pattern was observed with an electron microscope (SEM “JSM-6010”), and the development resistance was evaluated according to the following criteria.
⊚: The residual film ratio after development is 91% or more, and there are no patterns or cracks on the surface of the pattern cured film.
◯: The residual film ratio after development is 81% or more and less than 91%, and there are no patterns or cracks on the surface of the cured film.
X: The residual film ratio is less than 81%, or there are patterns or cracks on the surface of the cured film.

(Development residue)
The L / S = 10 μm / 10 μm pattern after development was observed with an electron microscope (SEM “JSM-6010”) to confirm the presence or absence of development residue.

Photoacid generator

Triazole compound

Melamine-based cross-linking agent

From the results shown in the above table, it can be seen that the photosensitive resin composition of the present invention can achieve both suppression of development residue and development resistance even when the development time is lengthened.

Claims (6)

A photosensitive resin composition comprising (A) a polybenzoxazole precursor, (B) a photoacid generator, (C) a triazole compound having a mercapto group, and (D) a melamine-based cross-linking agent .
The polybenzoxazole precursor (A) is a polyamide resin obtained from the reaction of a diamine component and a dicarboxylic acid component, and the proportion of the structure represented by the following general formula (1) in the polyamide structure is 0.1 to 1. The photosensitive resin composition is 15%, and the proportion of the structure represented by the following general formula (2) is 85 to 99.9% .

(In the general formula (1), P is a residue of the diamine component, and is a divalent divalent having the benzoxazole structure of any one of the following general formulas (1-1), (1-2) and (1-3). Group. R'is a residue of the dicarboxylic acid component and is a divalent organic group.)

(In the general formula (1-1), R ₁ to R ₄ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, and a direct bond with a nitrogen atom in the general formula (1). R ₅ to R ₉ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, and the general formula (1). It is one of the direct bonds with the nitrogen atom of, and may be the same or different. However, any one of R ₁ to R ₄ and any one of R 5 _to R ₉ One is a direct bond with a nitrogen atom in the general formula (1).)

(In the general formula (1-2), R ₁₀ to R ₁₄ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, and a direct bond with a nitrogen atom in the general formula (1). R ₁₅ to R ₁₉ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, and the general formula (1). It is one of the direct bonds with the nitrogen atom of, and may be the same or different. However, any one of R ₁₀ to R ₁₄ and any one of R 15 _to R ₁₉ One is a direct bond with the nitrogen atom in the general formula (1). R ₂₀ and R ₂₁ are any of a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group and an amino group, respectively. Yes, they may be the same or different.)

(In the general formula (1-3), R ₂₂ to R ₂₆ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, and a direct bond with a nitrogen atom in the general formula (1). R ₂₇ to R ₃₁ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, and the general formula (1). It is one of the direct bonds with the nitrogen atom of, and may be the same or different. However, any one of R ₂₂ to R ₂₆ and any one of R ₂₇ to R ₃₁ . One is a direct bond with a nitrogen atom in the general formula (1). R ₃₂ and R ₃₃ are any of a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group and an amino group, respectively. Yes, they may be the same or different.)

(In the general formula (2), X is a residue of dihydroxydiamines and is a tetravalent organic group. Y is a residue of a dicarboxylic acid component and is a divalent organic group.) The photosensitive resin composition according to claim 1 , wherein the (C) triazole compound having a mercapto group is 3-mercapto-1,2,4-triazole. The photosensitive resin composition according to claim 1 or 2 , which is used for forming a cured film on a copper substrate. A dry film having a resin layer obtained by applying the photosensitive resin composition according to any one of claims 1 to 3 to a film and drying the film. A cured product obtained by curing the resin layer of the photosensitive resin composition according to any one of claims 1 to 3 or the dry film according to claim 4 . An electronic component comprising the cured product according to claim 5 .