JP6929198B2 - Photosensitive resin compositions, dry films, cured products, semiconductor devices, printed wiring boards and electronic components - Google Patents

Description

The present invention relates to photosensitive resin compositions, dry films, cured products, semiconductor devices, printed wiring boards and electronic components.

Since polybenzoxazole is excellent in heat resistance and electrical insulation, electrons such as surface protective films and interlayer insulating films of electrical materials, for example, coating films of semiconductor elements, flexible printed wiring board materials, and heat insulating interlayer materials, etc. Application to parts is in progress.

Conventionally, in order to form a fine pattern of polybenzoxazole, a photosensitive resin composition containing a polybenzoxazole precursor and a photosensitizer has been used. As such a photosensitive resin composition, for example, Patent Document 1 describes a positive resist composition composed of a polybenzoxazole precursor and photosensitive diazoquinone.

Special Fair 1-046862 Gazette

However, the composition described in Patent Document 1 may not have sufficient compatibility between the heat resistance of the cured product and the sensitivity and resolution in photolithography. Further, it is also required that the linear thermal expansion coefficient of the cured product is low (that is, low CTE) because it causes cracks and warpage.

Therefore, an object of the present invention is a photosensitive resin composition capable of forming a cured film having high heat resistance and a low linear thermal expansion coefficient, and having excellent sensitivity and resolution, and a dry film having a resin layer obtained from the composition. The present invention provides a cured product of a resin layer of the composition or the dry film, a semiconductor element having the cured product, a printed wiring board, and an electronic component.

As a result of diligent studies in view of the above, the present inventors have used a polyamide resin containing a benzoxazole structure in a specific ratio as a polybenzoxazole precursor, or a polyamide resin having a benzoxazole structure and polyhydroxy. We have found that the above problems can be solved by using a polybenzoxazole precursor which is an amide in combination at a specific ratio, and have completed the present invention.

（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。） That is, the photosensitive resin composition of the present invention is a photosensitive resin containing a polybenzoxazole precursor (A), which is a polyamide resin obtained from the reaction of a diamine component and a dicarboxylic acid component, and a photosensitizer (B). It ’s a composition,
Among the polyamide structures of the polybenzoxazole precursor (A), the proportion of the structure represented by the following general formula (1) is 0.1 to 15%, and the proportion of the structure represented by the following general formula (2) is 85. It is characterized by being ~ 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 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 hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, 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 hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, 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 hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, 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 the 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.)

（一般式（３）中、Ｐはジアミン成分の残基であり、下記一般式（３−１）、（３−２）および（３−３）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。ｎは１以上の整数である。）

（一般式（３−１）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（３）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（３）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（３）中の窒素原子との直接結合である。）

（一般式（３−２）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（３）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（３）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（３）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（３−３）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（３）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（３）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（３）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（４）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。） Other photosensitive resin compositions of the present invention include a polyamide resin (α-1) obtained from the reaction of a diamine component and a dicarboxylic acid component, a polybenzoxazole precursor (α-2), and a photosensitive agent (B). A photosensitive resin composition containing
The polyamide resin (α-1) has a structure represented by the following general formula (3), and has a structure represented by the following general formula (3).
The polybenzoxazole precursor (α-2) has a structure represented by the following general formula (4) and has a structure represented by the following general formula (4).
It is characterized in that the compounding ratio of the polyamide resin (α-1) and the polybenzoxazole precursor (α-2) is 0.1: 99.9 to 15:85 in terms of mass.

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

(In the general formula (3-1), 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 (3). R _{5 to} R ₉ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the general formula (3). 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 (3).)

(In the general formula (3-2), 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 (3). R _{15 to} R ₁₉ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the general formula (3). 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 (3). 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 (3-3), 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 (3). R _{27 to} R ₃₁ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the general formula (3). 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 the nitrogen atom in the general formula (3). 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 (4), 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 1 The above integers.)

The photosensitive resin composition of the present invention preferably further contains a cross-linking agent.

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 it.

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 semiconductor device of the present invention is characterized by having the cured product.

The printed wiring board of the present invention is characterized by having the cured product.

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 forming a cured film having high heat resistance and a low linear thermal expansion coefficient and having excellent sensitivity and resolution, a dry film having a resin layer obtained from the composition, and the like. A cured product of the composition or the resin layer of the dry film, a semiconductor element having the cured product, a printed wiring board, and an electronic component can be provided.

As described above, the photosensitive resin composition of the present invention is photosensitive containing a polybenzoxazole precursor (A), which is a polyamide-based resin obtained from the reaction of a diamine component and a dicarboxylic acid component, and a photosensitizer (B). In the sex resin composition, the proportion of the structure represented by the general formula (1) in the polyamide structure of the polybenzoxazole precursor (A) is 0.1 to 15%, and the general formula (2) A photosensitive resin composition having a structure ratio of 85 to 99.9%, or a polyamide-based resin (α-1) obtained from the reaction of a diamine component and a dicarboxylic acid component, and a polybenzoxazole precursor (. A photosensitive resin composition containing α-2) and a photosensitizer (B), wherein the polyamide resin (α-1) has a structure represented by the general formula (3), and the poly The benzoxazole precursor (α-2) has a structure represented by the general formula (4), and the compounding ratio of the polyamide resin (α-1) and the polybenzoxazole precursor (α-2) is mass. It is a photosensitive resin composition having a conversion of 0.1: 99.9 to 15:85. Hereinafter, the components contained in the photosensitive resin composition of the present invention will be described in detail.

[Polybenzoxazole precursor (A)]
The polybenzoxazole precursor (A), which is a polyamide resin obtained from the reaction of the diamine component and the dicarboxylic acid component, has a polyamide structure in which the ratio of the structure represented by the following general formula (1) is 0.1 to 15%. The ratio of the structure represented by the following general formula (2) is 85 to 99.9%.

（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。）

（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 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 hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, 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 hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, 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 hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, 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 the 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 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 the polybenzoxazole precursor (A) 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. 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 (in terms of molars) of a 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 (A) is preferably 10 to 30, more preferably 15 to 25.

When the ratio of the structure represented by the general formula (1) is less than 0.1%, the heat resistance of the cured product decreases and the coefficient of linear thermal expansion also increases. Further, when the above ratio exceeds 15%, the sensitivity and the resolution deteriorate. It is preferably 1 to 10%.

The polyamide structure of the polybenzoxazole precursor (A) is obtained from the reaction of a diamine component and a dicarboxylic acid component. The diamine component and the dicarboxylic acid component may be those 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 the polybenzoxazole precursor (A), and the number of repetitions is preferably 1 to 5 (however, the number of repetitions here). If is 1, it means that it is not repeated continuously).

R _{1 to} R ₄ and R _{5 to} R _{9 in} the general formula (1-1), R _{10 to} R ₁₄ and 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 directly bonded to a hydrogen atom or a nitrogen atom in the general formula (1).

R _{1 to} R ₄ and R _{5 to} R _{9 in} the general formula (1-1), R _{10 to} R ₁₄ and 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 groups 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 alkyl groups 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), examples of the diamine component represented by P include diamines having a benzoxazole structure according to any one of the general formulas (5), (6) and (7) described later.

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- Dicarboxylic acid, oxalic acid, malonic acid having an aromatic ring such as bis (p-carboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane , Succinic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid and other aliphatic dicarboxylic acids, 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 R'is preferably an aromatic group in the general formula (1). 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, a 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 equation, A is a single bond, -CH _2- , -O-, -CO- _{, -S-, -SO 2-} , -NHCO-, -C (CF ₃ ) _2- , -C (CH ₃ ). ₂ - represents a divalent radical selected from the group consisting of).

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

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

The amide structure other than the above general formula (1) contained in the polyamide structure of the polybenzoxazole precursor (A) is an amide structure represented by the following general formula (2). The ratio of the amide structure of the general formula (1) to the amide structure of the general formula (2) is 0.1: 99.9 to 15:85, preferably 1:99 to 10:90, and 1 : 99 to 5:95 is more preferable.

（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、ポリベンゾオキサゾール前駆体（Ａ）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 the polybenzoxazole precursor (A), and the number of repetitions is preferably 10 to 30 and more preferably 15 to 25 (however, here). If the number of repetitions is 1, it means that they are not repeated continuously).

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, known aromatic groups 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).

The number average molecular weight (Mn) of the polybenzoxazole precursor (A) 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 with standard polystyrene. The mass average molecular weight (Mw) of the polybenzoxazole precursor (A) 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 with standard polystyrene. Mw / Mn is preferably 1 to 5, and more preferably 1 to 3.

The blending amount of the polybenzoxazole precursor (A) is preferably 60 to 90% by mass, more preferably 70 to 90% by mass, based on the total solid content of the composition.

When the photosensitive resin composition of the present invention contains the polybenzoxazole precursor (A), it can form a cured film having high heat resistance and a low coefficient of linear thermal expansion without mixing a polymer, and has sensitivity. Although the resolution is excellent, if necessary, two or more kinds of the polybenzoxazole precursor (A) may be used in combination. Further, it may be used in combination with a polymer other than the polybenzoxazole precursor (A) as long as the effect of the present invention is not impaired.

[Polyamide resin (α-1)]
The polyamide resin (α-1) obtained from the reaction of the diamine component and the dicarboxylic acid component has a structure represented by the following general formula (3).

（一般式（３）中、Ｐはジアミン成分の残基であり、下記一般式（３−１）、（３−２）および（３−３）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。ｎは１以上の整数である。）

（一般式（３−１）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（３）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（３）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（３）中の窒素原子との直接結合である。）

（一般式（３−２）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（３）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（３）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（３）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（３−３）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（３）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（３）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（３）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。）

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

(In the general formula (3-1), 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 (3). R _{5 to} R ₉ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the general formula (3). 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 (3).)

(In the general formula (3-2), 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 (3). R _{15 to} R ₁₉ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the general formula (3). 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 (3). 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 (3-3), 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 (3). R _{27 to} R ₃₁ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the general formula (3). 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 the nitrogen atom in the general formula (3). 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.)

The blending ratio of the polyamide resin (α-1) and the polybenzoxazole precursor (α-2) is 0.1: 99.9 to 15:85 in terms of mass. When the polyamide resin (α-1) is less than 0.1, the heat resistance of the cured product is lowered and the linear thermal expansion coefficient is also high. If the amount of the polyamide resin (α-1) exceeds 15, the sensitivity and resolution deteriorate. Preferably, it is 1:99 to 10:90.

The polyamide resin (α-1) is obtained from the reaction of a diamine component and a dicarboxylic acid component. The diamine component and the dicarboxylic acid component may be those 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.

N in the general formula (3) is preferably 1 to 20, more preferably 1 to 5.

Each R in the general formulas (3-1) to (3-3) is the same as the same R in the general formulas (1-1) to (1-3).

In the general formula (3), the diamine component represented by P is the benzoxazole of any of the general formulas (5), (6) and (7) described later, similarly to P in the general formula (1). Examples thereof include diamines having a structure.

The dicarboxylic acid component represented by R'in the general formula (3) is the same as that of R'in the general formula (1).

The polyamide resin (α-1) may contain two or more types of structures represented by the general formula (3). Further, a structure other than the structure represented by the general formula (3) may be included, and for example, a structure represented by the above general formula (2) may be included.

The number average molecular weight (Mn) of the polyamide resin (α-1) is preferably 500 to 10,000. The mass average molecular weight (Mw) of the polyamide resin (α-1) is preferably 1,500 to 25,000. Mw / Mn is preferably 1 to 5.

The blending amount of the polyamide resin (α-1) is preferably 0.1 to 15% of the resin components, and the thermomechanical properties of the cured film can be improved without deteriorating the developability.

[Polybenzoxazole precursor (α-2)]
The polybenzoxazole precursor (α-2) has a structure represented by the following general formula (4).

（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 (4), m is an integer of 1 or more, preferably 10 to 50, and more preferably 20 to 40.

The dihydroxydiamines represented by X in the general formula (4) are the same as the dihydroxydiamines represented by X in the general formula (3).

The tetravalent organic group represented by X in the general formula (4) is the same as the tetravalent organic group represented by X in the general formula (3).

The dicarboxylic acid component represented by Y in the general formula (4) is the same as the dicarboxylic acid component represented by R'in the general formula (1), similar to R'in the general formula (3). ..

The polybenzoxazole precursor (α-2) may contain two or more types of structures represented by the general formula (4).

The number average molecular weight (Mn) of the polybenzoxazole precursor (α-2) is preferably 5,000 to 100,000, more preferably 8,000 to 50,000. The mass average molecular weight (Mw) of the polybenzoxazole precursor (α-2) is preferably 10,000 to 200,000, more preferably 16,000 to 100,000. Mw / Mn is preferably 1 to 5, and more preferably 1 to 3.

The blending amount of the polybenzoxazole precursor (α-2) is preferably 85 to 99.9% in the resin component, and a pattern having a higher resolution can be obtained.

In the photosensitive resin composition of the present invention, if necessary, a polyamide resin (α-1) and a polybenzoxazole precursor (α-2) may be used in combination of two or more. Further, it may be used in combination with a polymer other than the polyamide resin (α-1) and the polybenzoxazole precursor (α-2) as long as the effect of the present invention is not impaired. The polybenzoxazole precursor (α-2) may have a benzoxazole structure as long as the effects of the present invention are not impaired, but it is preferable that the polybenzoxazole precursor (α-2) does not have a benzoxazole structure.

[Photosensitizer (B)]
The photosensitizer (B) is not particularly limited, and a photoacid generator, a photopolymerization initiator, and a photobase generator can be used. A photoacid generator is a compound that generates an acid when irradiated with light such as ultraviolet rays or visible light, a photopolymerization initiator is a compound that generates a radical or the like when irradiated with the same light, and a photobase generator is the same. It is a compound that produces one or more basic substances by changing its molecular structure or cleaving the molecule by irradiation with light. In the present invention, a photoacid generator can be preferably used as the photosensitizer (B).

Examples of the photoacid generator include naphthoquinone diazide compounds, diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, and nitrobenzyl esters. , Aromatic N-oxyimide sulfonate, aromatic sulfamide, benzoquinone diazosulfonic acid ester and the like. 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 a naphthoquinone diazide adduct of tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene (for example, TS533, TS567, TS583, TS593 manufactured by Sanpo Chemical Laboratory Co., Ltd.). ), A naphthoquinone diazide adduct of tetrahydroxybenzophenone (for example, BS550, BS570, BS599 manufactured by Sanpo Chemical Laboratory Co., Ltd.) and the like can be used.

As the photosensitizer (B), one type may be used alone, or two or more types may be used in combination. The blending amount of the photosensitizer (B) is preferably 3 to 20% by mass, more preferably 5 to 20% by mass, based on the total solid content of the composition.

(Crosslinking agent)
The photosensitive resin composition of the present invention preferably contains a cross-linking agent, and the addition of the cross-linking agent increases the strength of the cured film when it is cured at a low temperature. The cross-linking agent is not particularly limited, and may contain a known and commonly used cross-linking agent. Of these, a cross-linking agent having a phenolic hydroxyl group, a cross-linking agent having no phenolic hydroxyl group and having two or more methylol groups, a melamine-based cross-linking agent, and a urea-based cross-linking agent are preferable. Further, it is more preferable to use a cross-linking agent having a phenolic hydroxyl group and a melamine-based cross-linking agent in combination, and by combining the cross-linking agent, the developability can be adjusted and the strength of the film cured at a low temperature is increased. The mixing ratio of the cross-linking agent having a phenolic hydroxyl group and the melamine-based cross-linking agent is preferably 2: 8 to 8: 2, more preferably 3: 7 to 7: 3, and 4: 6 to 6: 4 in terms of mass. More preferred. It is more preferable to use a cross-linking agent having a phenolic hydroxyl group and a cross-linking agent having two or more methylol groups without having a phenolic hydroxyl group in combination, and the pattern rectangle at the time of development is improved and the strength of the cured film is increased. The mixing ratio of the cross-linking agent having a phenolic hydroxyl group and the cross-linking agent having two or more methylol groups without having a phenolic hydroxyl group is preferably 2: 8 to 8: 2 in terms of mass, and 3: 7 to 7: 3. Is more preferable, and 4: 6 to 6: 4 is even more preferable. The content of the cross-linking agent is preferably 1.5 to 20% by mass based on the total solid content of the composition.

(Crosslinking agent with phenolic hydroxyl group)
The cross-linking agent having a phenolic hydroxyl group is not particularly limited, but preferably has two or more hydroxyl groups (including phenolic hydroxyl groups), more preferably two or more phenolic hydroxyl groups, and is represented by the following general formula (A). It is more preferable that it is a compound.

（一般式（Ａ）中、Ｒ^Ａ１は２〜１０価の有機基を示す。Ｒ^Ａ２は、それぞれ独立に、水素原子または炭素数１〜４のアルキル基を示す。ｎは２〜１０の整数を示す。）

(In the general formula ^{(A), .R A2 R A1} is shown a 2-10 monovalent organic group, each independently, .n represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms 2-10 integer Shows.)

In the general formula (A), ^RA1 is preferably an alkylene group having 1 to 3 carbon atoms which may have a substituent.

In the general formula (A), ^RA2 is preferably a hydrogen atom.

In the general formula (A), n is preferably an integer of 2 to 4, and more preferably 2.

Further, the cross-linking agent having a phenolic hydroxyl group preferably has a fluorine atom, and more preferably has a trifluoromethyl group. The fluorine atom or the trifluoromethyl group is preferably to 2-10 monovalent organic group represented by R ^A1 in the general formula (A) has, it R ^A1 is di (trifluoromethyl) methylene group Is preferable. Further, the cross-linking agent having a phenolic hydroxyl group preferably has a bisphenol structure, and more preferably has a bisphenol AF structure.

The following compounds are preferable as specific examples of the cross-linking agent having a phenolic hydroxyl group.

As the cross-linking agent having a phenolic hydroxyl group, one type may be used alone, or two or more types may be used in combination. The blending amount of the cross-linking agent having a phenolic hydroxyl group is preferably 1 to 20% by mass, more preferably 3 to 10% by mass, based on the total solid content of the composition. With such a blending ratio, a composition having more excellent developability and more excellent pattern forming property after curing can be obtained.

(A cross-linking agent that does not have a phenolic hydroxyl group and has two or more methylol groups)
The cross-linking agent having two or more methylol groups without having a phenolic hydroxyl group preferably has a molecular weight of 100 or more.

The cross-linking agent having two or more methylol groups without having a phenolic hydroxyl group is more preferably a compound represented by the following general formula (B).

（一般式（Ｂ）中、ｎは１〜１０の整数を示し、ｎが１のとき、Ｒ^Ｂ１はメチロール基（すなわち「−ＣＨ_２ＯＨ」）を表し、ｎが２〜１０の整数のとき、Ｒ^Ｂ１は２〜１０価の有機基を示す。Ｒ^Ｂ２は、それぞれ独立に、炭素数１〜４の有機基を示す。ｍ１は１〜５の整数を示し、ｍ２は０〜４の整数を示す。）

(In the general formula (B), n represents an integer of 1 to 10, when n is 1, ^RB1 represents a methylol group (that is, "-CH ₂ OH"), and when n is an integer of 2 to 10. , R ^B1 represents an organic group having a valence of 2 ^{to 10. R B2} independently represents an organic group having 1 to 4 carbon atoms. M1 represents an integer of 1 to 5, and m2 represents an integer of 0 to 4. Shows.)

In the general formula (B), n is preferably 1.

In the general formula (B), ^RB2 is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

The following compounds are preferable as specific examples of the cross-linking agent having two or more methylol groups without having a phenolic hydroxyl group.

As the cross-linking agent which does not have a phenolic hydroxyl group and has two or more methylol groups, one type may be used alone, or two or more types may be used in combination. The blending amount of the cross-linking agent having two or more methylol groups without having a phenolic hydroxyl group is preferably 1 to 20% by mass based on the total solid content of the composition. With such a blending ratio, a composition having more excellent developability and more excellent pattern forming property after curing can be obtained.

（式中、Ｒ^Ｃ１Ａ、Ｒ^Ｃ２Ａ、Ｒ^Ｃ３Ａ、Ｒ^Ｃ４Ａ、Ｒ^Ｃ５ＡおよびＲ^Ｃ６Ａ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^Ｃ１Ｂ、Ｒ^Ｃ２Ｂ、Ｒ^Ｃ３Ｂ、Ｒ^Ｃ４Ｂ、Ｒ^Ｃ５ＢおよびＲ^Ｃ６Ｂ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。） (Melamine-based cross-linking agent)
The melamine-based cross-linking agent is not particularly limited as long as it is a cross-linking agent having a melamine structure, but a melamine-based cross-linking agent represented by the following general formula (C) is preferable.

^{(Wherein, R C1A, R C2A, R} C3A, R C4A, it is preferable ^{R C5A} and ^{R C6A} independently represents an alkylene group having 1 to 3 carbon atoms ^{.R C1B, R C2B, R C3B} , R C4B , ^RC5B and ^RC6B are preferably hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, respectively.)

In the general formula ^{(C), R C1A, R} C2A, R C3A, R C4A, and more preferably ^{R C5A} and ^{R C6A} are each methylene group. ^{Also, R C1B, R C2B, R} C3B, R C4B, and more preferably ^{R C5B} and ^{R C6B} are each independently a methyl group or a hydrogen atom.

As the melamine-based cross-linking agent, one type may be used alone, or two or more types may be used in combination. The blending amount of the melamine-based cross-linking agent is preferably 0.5 to 15% by mass based on the total solid content of the composition. When it is 0.5 to 15% by mass, the residual film ratio of the unexposed portion can be made higher, and the undeveloped residue of the exposed portion can be prevented.

(Urea-based cross-linking agent)
The urea-based cross-linking agent is not particularly limited, but is preferably a melamine-based cross-linking agent represented by the following general formula (D) or (E).

（式中、Ｒ^Ｄ１、Ｒ^Ｄ２はそれぞれ独立に水素原子または一価の有機基を示す。）

(In the formula, R ^D1 and R ^D2 independently represent a hydrogen atom or a monovalent organic group.)

（式中、Ｒ^Ｅ１はそれぞれ独立に水素原子または一価の有機基を示し、Ｒ^Ｅ２は二価の有機基を示す。）

(In the formula, ^RE1 independently represents a hydrogen atom or a monovalent organic group, and ^RE2 represents a divalent organic group.)

The urea-based cross-linking agent is preferably an alkylated urea resin, and more preferably has a 2-imidazolidinone ring. For example, 1,3,4,6-tetrakis (methoxymethyl) glycoluryl, 1,3,4,6-tetrakis (butoxymethyl) glycoluryl, 4,5-dimethoxy-1,3-bis (methoxymethyl) imidazole. Examples thereof include lysine-2-one. Examples of commercially available products include Nikalac MX-270, MX-279, MX-280 and the like manufactured by Sanwa Chemical Co., Ltd.

As a specific compound of the urea-based cross-linking agent, the following compounds and the like can be used.

One type of urea-based cross-linking agent may be used alone, or two or more types may be used in combination. The blending amount of the urea-based cross-linking agent is preferably 1 to 20% by mass based on the total solid content of the composition. When it is 1 to 20% by mass, the film strength at the time of low temperature curing can be improved without adversely affecting the development.

(Thiol compound)
The photosensitive resin composition of the present invention can contain a thiol compound. By containing the thiol compound, the development residue can be reduced. The thiol compound is not particularly limited, and D, L-dithiothreitol, 2-mercaptoethanol, and the following compounds can be used. Of these, D and L-dithiothreitol are particularly preferable.

One type of thiol compound may be used alone, or two or more types may be used in combination. The blending amount of the thiol compound is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total solid content of the composition. By setting the above range, the generation of scum can be suppressed more reliably.

(Urea compound)
The photosensitive resin composition of the present invention can contain a urea compound. By containing the urea compound, the dissolution rate of the resin can be adjusted and the pattern forming property can be improved. The urea compound is not particularly limited, and is, for example, 1,3-diphenylurea, 1,3-bis [4- (trifluoromethyl) phenyl] urea, N, N'-bis (trimethylsilyl) urea, 1-acetyl. -3-Methylurea, 1-acetyl-2-thiourea, acetylurea, 1-adamantylthiourea, 1-allyl-3- (2-hydroxyethyl) -2-thiourea, benzoylene urea, N-benzoylthiourea , Benzoyl urea, benzyl urea, 1,3-bis (tert-butoxycarbonyl) thiourea, 1,3-bis (4-chlorophenyl) urea, 1,3-bis (4-fluorophenyl) urea, 1,3- (Hydroxymethyl) urea, 1,3-bis (4-methoxyphenyl) urea, biurea, butyl urea, N, N'-diethyl-N, N'-diphenylurea and the like can be used.

One type of urea compound may be used alone, or two or more types may be used in combination. The blending amount of the urea compound is preferably 0.01 to 15% by mass, more preferably 0.05 to 10% by mass, based on the total solid content of the composition. Within the above range, the residual film ratio can be improved, the developability of the thick photosensitive film on the metal substrate can be improved, and a better pattern shape can be obtained after development.

(Silane coupling agent)
The photosensitive resin composition of the present invention can contain a silane coupling agent. By containing the silane coupling agent, the adhesion to the silicon substrate can be improved. As the silane coupling agent, a silane coupling agent having an arylamino group and a silane coupling agent having two or more trialkoxysilyl groups are preferable. A silane coupling agent having an arylamino group is more preferable because of its excellent resolution.

A silane coupling agent having an arylamino group will be described. Examples of the aryl group of the arylamino group include aromatic hydrocarbon groups such as phenyl group, trill group and xsilyl group, condensed polycyclic aromatic groups such as naphthyl group, anthracenyl group and phenanthrenyl group, and aromatic groups such as thienyl group and indolyl group. A group heterocyclic group can be mentioned.

（式中、Ｒ^Ｆ１〜Ｒ^Ｆ５はそれぞれ独立に水素原子または有機基を表す。） The silane coupling agent having an arylamino group is preferably a compound having a group represented by the following general formula (F).

(In the formula, R ^{F1 to} R ^F5 independently represent a hydrogen atom or an organic group.)

In the general formula ^(F), it is preferred that R F1 ^{to R F5} are hydrogen atoms.

In the silane coupling agent having an arylamino group, it is preferable that the silicon atom and the arylamino group are bonded by an organic group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms.

Specific examples of the silane coupling agent having an arylamino group are preferably the compounds shown below.

Next, a silane coupling agent having two or more trialkoxysilyl groups will be described. The trialkoxysilyl groups of the silane coupling agent having two or more trialkoxysilyl groups may be the same or different, and the alkoxy groups of these groups may be the same or different. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like, and among them, a methoxy group and an ethoxy group are preferable.

In a silane coupling agent having two or more trialkoxysilyl groups, it is preferable that at least two silicon atoms are bonded by an organic group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms. ..

Specific examples of the silane coupling agent having two or more trialkoxysilyl groups are preferably the following compounds.

One type of silane coupling agent may be used alone, or two or more types may be used in combination. Further, a silane coupling agent other than the above-mentioned silane coupling agent having an arylamino group and the silane coupling agent having two or more trialkoxysilyl groups may be contained.

The blending amount of the silane coupling agent is preferably 1 to 15% by mass based on the total solid content of the composition. When it is 1 to 15% by mass, it is possible to prevent the undeveloped portion of the exposed portion.

A solvent can be blended in the photosensitive resin composition of the present invention. The solvent is not particularly limited as long as it dissolves the polybenzoxazole precursor (A), the photosensitizer (B), and any other additive. 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 polybenzoxazole precursor (A), depending on the coating film thickness and viscosity.

A known sensitizer, 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, surfactants, leveling agents, plasticizers, 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 (support 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 pattern film which is a cured product thereof is produced, for example, as follows. In the following production method, the case where the polybenzoxazole precursor (A) is contained will be described, but the same applies to the case where the polyamide resin (α-1) and the polybenzoxazole precursor (α-2) are contained. ..

First, as step 1, a coating film is obtained by applying and drying the photosensitive resin composition on the substrate, or by transferring (laminating) the resin layer from the dry film onto the substrate. 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, etc. A method of coating with a spray coater, a method of spray coating with 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 polybenzoxazole precursor (A) 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 base material is not particularly limited, and can be widely applied to a semiconductor base material such as a silicon wafer, a wiring board, and a base material made of various resins or metals.

Next, as step 2, the coating film is exposed through a photomask having a pattern or directly. As the exposure light, a light having a wavelength capable of activating the photoacid generator as the photosensitizer (B) 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 photosensitizer 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, a part of the polybenzoxazole precursor (A) in the unexposed portion may be ring-closed by heating. Here, the ring closure rate is about 30%. The heating time and heating temperature are appropriately changed depending on the polybenzoxazole precursor (A), the coating film thickness, and the type of photoacid generator as the photosensitizer (B).

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.

As a method used for development, any method can be selected from conventionally known photoresist developing 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 quaternary ammonium 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 liquid to obtain a patterned film. Distilled water, methanol, ethanol, isopropyl alcohol and the like can be used alone or in combination as the rinsing liquid. 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 polybenzoxazole precursor (A) may be closed to obtain polybenzoxazole. The heating temperature is appropriately set so that the pattern film of polybenzoxazole can be cured. For example, heating is performed at 150 to 350 ° C. for about 5 to 120 minutes in an inert gas. A more preferred range of heating temperature is 180-320 ° 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, the display device can be used as a layer-forming material or an image-forming material for a color filter, a film for a flexible display, a resist material, an alignment film, or the like. Further, as a material for forming a 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 an optical component forming material, an optical material or a layer forming material can be used for holograms, optical waveguides, optical circuits, optical circuit components, antireflection films and 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.

The method for producing the photosensitive resin composition of the present invention is not particularly limited, but the polybenzoxazole precursor (A) and the photosensitive agent (B), which are polyamide-based resins obtained from the reaction of the diamine component and the dicarboxylic acid component, are used. In the case of the method for producing a photosensitive resin composition to be blended, it is suitably produced by using a diamine component having the benzoxazole structure of any of the following general formulas (5), (6) and (7) as the diamine. can do. Further, a photosensitive resin composition containing a polyamide resin (α-1) obtained from the reaction of the diamine component and the dicarboxylic acid component, a polybenzoxazole precursor (α-2), and a photosensitizer (B). In the case of the above-mentioned production method, it can be suitably produced by using the diamine component having the benzoxazole structure of any one of the following general formulas (5), (6) and (7) as the diamine.

（一般式（５）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、アミノ基である。）

（一般式（６）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、又は、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。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、アミノ基である。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（７）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、アミノ基である。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。）

(In the general formula (5), R _{1 to} R ₄ 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, and may be the same or different. R _{5 to} R ₉ 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, and may be the same or different. However, R _{1 to} R _{Any one of 4} and any one of R _{5 to} R ₉ are amino groups.)

(In the general formula (6), R _{10 to} R ₁₄ are any of a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, or an amino group, and even if they are the same, they are different. _{R 15 to} R ₁₉ may be any of a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group and an amino group, and may be the same or different. However, R _{10 may be used.} Any one of ~ R ₁₄ and any one of R ₁₅ ~ R ₁₉ are amino groups. R ₂₀ and R ₂₁ are hydrogen atom, organic group, nitro group, halogen atom and sulfo, respectively. It is any of a group, a sulfonyl group, and an amino group, and may be the same or different.)

(In the general formula (7), R _{22 to} R ₂₆ 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, and may be the same or different. R _{27 to} R ₃₁ 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, and may be the same or different. However, R _{22 to} R _{Any one of 26} and any one of R _{27 to} R ₃₁ are amino groups. R ₃₂ and R ₃₃ are hydrogen atoms, organic groups, nitro groups, halogen atoms and sulfo groups, respectively. It is either a sulfonyl group or an amino group, and may be the same or different.)

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) (Benzoxazole Site 10%)
85 g of N-methylpyrrolidone was charged in a 0.5 liter flask equipped with a stirrer and a thermometer, and 10.29 g (28.1 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 2- (4- (4-) Aminophenyl) -5-aminobenzoxazole 0.70 g (3.12 mmol) was stirred and dissolved. Then, the flask is immersed in an ice bath, and 10.00 g (33.9 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride is added as a solid over 10 minutes while keeping the temperature inside 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 420 mL of acetone and put into 1 L of ion-exchanged water. The precipitated individual was recovered and dried under reduced pressure to obtain a partially cyclized polybenzoxazole precursor at the terminal of a carboxyl group. The weight average molecular weight determined by GPC method standard polystyrene conversion was 31,700.

(Synthesis of Polybenzoxazole Precursor A-2) (Benzoxazole Site 5%)
85 g of N-methylpyrrolidone was charged in a 0.5 liter flask equipped with a stirrer and a thermometer, and 10.86 g (29.65 mmol) and 2- (4-65 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane were charged. Aminophenyl) -5-aminobenzoxazole 0.7 g (1.55 mmol) was dissolved by stirring. Then, the flask is immersed in an ice bath, and 10.00 g (33.9 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride is added as a solid over 10 minutes while keeping the temperature inside 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 420 mL of acetone and put into 1 L of ion-exchanged water. The precipitated individual was recovered and dried under reduced pressure to obtain a partially cyclized polybenzoxazole precursor at the terminal of a carboxyl group. The weight average molecular weight determined by GPC method standard polystyrene conversion was 33,700.

(Synthesis of Polybenzoxazole Precursor R-1) (Benzoxazole Site 30%)
85 g of N-methylpyrrolidone was placed in a 0.5 liter flask equipped with a stirrer and a thermometer, and 8.00 g (21.8 mmol) and 2- (4- (4-) bis (3-amino-4-hydroxyphenyl) hexafluoropropane were charged. Aminophenyl) -5-aminobenzoxazole g (9.32 mmol) was dissolved by stirring. Then, the flask is immersed in an ice bath, and 10.00 g (33.9 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride is added as a solid over 10 minutes while keeping the temperature inside 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 420 mL of acetone and put into 1 L of ion-exchanged water. The precipitated individual was recovered and dried under reduced pressure to obtain a partially cyclized polybenzoxazole precursor at the terminal of a carboxyl group. The weight average molecular weight determined by GPC method standard polystyrene conversion was 28,200.

(Synthesis of polybenzoxazole precursor R-2) (Benzoxazole site 0%)
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 as a solid over 30 minutes while keeping the temperature inside the flask at 0 to 5 ° C., and the ice bath is added. It was stirred inside for 30 minutes. Then, stirring was continued at room temperature for 5 hours. 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. The precipitated solid was recovered and dried under reduced pressure to obtain a polybenzoxazole (PBO) precursor (R-2) having the following repeating structure at the terminal of a carboxyl group. The number average molecular weight (Mn) of the polybenzoxazole precursor (R-2) was 13,100, the weight average molecular weight (Mw) was 32,100, and Mw / Mn was 2.45.

・その他のアミド構造

The polybenzoxazole precursors A-1, A-2, R-1 and A-3 described later have an amide structure having the following benzoxazole structure in the polyamide structure and another amide structure. The polybenzoxazole precursor R-2 has the following other amide structures in the polyamide structure.
・ Amide structure with benzoxazole structure

・ Other amide structures

(Example 1)
(Evaluation of the physical properties)
100 parts by mass of the polybenzoxazole precursor A-1 and 10 parts by mass of the diazonaphthoquinone compound were dissolved in 300 parts by mass of γ-butyrolactone and then filtered through a 0.2 μm filter to obtain a varnish of a photosensitive resin composition. This varnish was applied onto a 6-inch silicon wafer using a spin coater and dried on a hot plate at 120 ° C. for 30 minutes to obtain a coating film having a film thickness of about 30 μm. Next, the silicon wafer with a coating film was heated at 150 ° C./30 minutes, 250 ° C./30 minutes, and 320 ° C./30 minutes using an oven. The obtained cured film was peeled off from a silicon wafer, and the glass transition temperature (Tg) and the coefficient of thermal expansion (CTE) were measured by TMA (thermomechanical analysis).

(Pattern making)
The varnish was applied onto a 6-inch silicon wafer using a spin coater and dried on a hot plate at 120 ° C. for 3 minutes to obtain a coating film having a film thickness of about 5 μm. The obtained coating film was subjected to i-line exposure of ^{300 to 600 mJ / cm 2} through a mask on which a pattern of 1 to 30 μm was drawn. After exposure, it was developed in 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.

(Evaluation of unexposed area residual film ratio)
The film thickness of the cured film after development was measured, and the ratio with the film thickness before development was taken to determine the residual film ratio of the unexposed portion.
Residual film ratio = (film thickness after development / μm) / (film thickness before development / μm) × 100

(Evaluation of sensitivity and resolution)
The pattern after development is observed with an electron microscope (SEM "JSM-6010"), the size of the minimum pattern that can pattern the exposed part without scum is the resolution (L (μm) / S (μm)), and the exposure amount at that time is the sensitivity. And said.

(Example 2)
The evaluation was carried out in the same manner as in Example 1 except that the polybenzoxazole precursor was changed to A-2.

(Comparative Example 1)
The evaluation was carried out in the same manner as in Example 1 except that the polybenzoxazole precursor was changed to R-1.
When the developability was evaluated, the exposed part did not dissolve in the developing solution and no pattern could be obtained.

(Comparative Example 2)
The evaluation was carried out in the same manner as in Example 1 except that the polybenzoxazole precursor was changed to R-2.
When the developability was evaluated, both the exposed part and the unexposed part were dissolved in the developing solution and no pattern was obtained.

(Synthesis of Polybenzoxazole Precursor A-3) (Benzoxazole Site 2%)
85 g of N-methylpyrrolidone was charged 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 while keeping the temperature inside the flask at 0 to 5 ° C., 10.10 g (34.2 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride is added as a solid over 10 minutes, and the mixture is placed in the ice bath. 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 420 mL of acetone and put into 1 L of ion-exchanged water. The precipitated individual was recovered and dried under reduced pressure to obtain a partially cyclized polybenzoxazole precursor at the terminal of a carboxyl group. The weight average molecular weight determined by GPC method standard polystyrene conversion was 34,500.

(Example 3)
After dissolving 100 parts by mass of polybenzoxazole precursor A-2, 10 parts by mass of diazonaphthoquinone compound, and 5 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (KBM-573) in 300 parts by mass of γ-butyrolactone. The mixture was filtered through a 0.2 μm filter to obtain a varnish of a photosensitive resin composition. This varnish was applied onto a 6-inch silicon wafer using a spin coater and dried on a hot plate at 120 ° C. for 30 minutes to obtain a coating film having a film thickness of about 30 μm. Next, the silicon wafer with a coating film was heated at 150 ° C./30 minutes and 250 ° C./30 minutes using an oven. The obtained cured film was peeled off from a silicon wafer, and the glass transition temperature (Tg) and the coefficient of thermal expansion (CTE) were measured by TMA (thermomechanical analysis).
Separately, the varnish was applied onto a 6-inch silicon wafer using a spin coater, and dried on a hot plate at 120 ° C. for 30 minutes to obtain a coating film having a film thickness of about 5 μm. The obtained coating film was subjected to i-line exposure of 300 to 600 mJ / cm ^2. After exposure, it was developed in 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.

(Example 4)
Evaluation was carried out in the same manner as in Example 3 except that 10 parts by mass of TML-BPAF-MF was added.

(Example 5)
The evaluation was carried out in the same manner as in Example 3 except that the polybenzoxazole precursor was changed to A-3 and 10 parts by mass of MX270 (Sanwa Chemical) was added.

(Example 6)
Evaluation was carried out in the same manner as in Example 3 except that 5 parts by mass of TML-BPAF-MF (Honshu Chemical Industry) and 5 parts by mass of MW390 (Sanwa Chemical) were added.

(Example 7)
Polybenzoxazole precursor A-3 100 parts by mass, diazonaphthoquinone compound 10 parts by mass TML-BPAF-MF 5 parts by mass, 1,4-benzenedimethanol 5 parts by mass, N-phenyl-3-aminopropyltrimethoxysilane ( KBM-573) 5 parts by mass was dissolved in 300 parts by mass of γ-butylolactone and then filtered through a 0.2 μm filter to obtain a varnish of a photosensitive resin composition. This varnish was applied onto a 6-inch silicon wafer using a spin coater and dried on a hot plate at 120 ° C. for 30 minutes to obtain a coating film having a film thickness of about 30 μm. Next, the silicon wafer with a coating film was heated at 150 ° C./30 minutes, 250 ° C./30 minutes, and 320 ° C./30 minutes using an oven. The obtained cured film was peeled off from a silicon wafer, and the glass transition temperature (Tg) and the coefficient of thermal expansion (CTE) were measured by TMA (thermomechanical analysis). Separately, the varnish was applied onto a 6-inch silicon wafer using a spin coater, and dried on a hot plate at 120 ° C. for 30 minutes to obtain a coating film having a film thickness of about 5 μm. The obtained coating film was subjected to i-line exposure of 300 to 600 mJ / cm ^2. After the exposure, it was developed in 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.

(Example 8)
The polybenzoxazole precursor was changed to A-2, 1 part by mass of dithiothreitol and 1 part by mass of diphenylurea were added, and TML-BPAF-MF and 1,4-benzenedimethanol were not added. Other than that, the evaluation was carried out in the same manner as in Example 7.

From the results shown in the above table, it can be seen that the photosensitive resin composition of the present invention can form a cured film having high heat resistance and a low coefficient of linear thermal expansion, and is excellent in sensitivity and resolution.

Claims (8)

A photosensitive resin composition containing a polybenzoxazole precursor (A), which is a polyamide resin obtained from the reaction of a diamine component and a dicarboxylic acid component, and a photosensitizer (B).
Among the polyamide structures of the polybenzoxazole precursor (A), the proportion of the structure represented by the following general formula (1) is 0.1 to 15%, and the proportion of the structure represented by the following general formula (2) is 85. A photosensitive resin composition characterized by being ~ 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 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 hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, 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 hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, 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 hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, 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 the 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.) A photosensitive resin composition containing a polyamide resin (α-1) obtained from the reaction of a diamine component and a dicarboxylic acid component, a polybenzoxazole precursor (α-2), and a photosensitizer (B). ,
The polyamide resin (α-1) has a structure represented by the following general formula (3), and has a structure represented by the following general formula (3).
The polybenzoxazole precursor (α-2) has a structure represented by the following general formula (4) and has a structure represented by the following general formula (4).
A photosensitive resin composition characterized in that the compounding ratio of the polyamide resin (α-1) and the polybenzoxazole precursor (α-2) is 0.1: 99.9 to 15:85 in terms of mass. thing.

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

(In the general formula (3-1), 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 (3). R _{5 to} R ₉ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the general formula (3). 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 (3).)

(In the general formula (3-2), 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 (3). R _{15 to} R ₁₉ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the general formula (3). 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 (3). 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 (3-3), 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 (3). R _{27 to} R ₃₁ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the general formula (3). 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 the nitrogen atom in the general formula (3). 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 (4), 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 1 The above integers.) The photosensitive resin composition according to claim 1 or 2, further comprising a cross-linking agent. 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. A semiconductor device having the cured product according to claim 5. A printed wiring board having the cured product according to claim 5. An electronic component having the cured product according to claim 5.