JP2019082639A - Photosensitive resin composition, dry film, cured product, semiconductor element, printed wiring board, and electronic component - Google Patents

Abstract

To provide a photosensitive resin composition excellent in high heat resistance, low linear thermal expansion, sensitivity and resolution, a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, and a semiconductor element, a printed wiring board and an electronic component having the cured product.SOLUTION: The photosensitive resin composition contains: a polybenzoxazole precursor (A) which is a polyamide resin obtained by a reaction between a diamine component and a dicarboxylic acid component; and a photosensitizer (B). In a polyamide structure of the polybenzoxazole precursor (A), a proportion of a structure represented by general formula (1) is 0.1-15% and a proportion of a structure represented by general formula (2) is 85-99.9%.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition, a dry film, a cured product, a semiconductor element, a printed wiring board and an electronic component.

  Since polybenzoxazole is excellent in heat resistance and electrical insulation, it is a surface protective film of an electrical material or an interlayer insulating film, for example, a coating film of a semiconductor element, an electronic material such as a flexible printed wiring board material, a heat resistant insulating interlayer material Application to parts is in progress.

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

Japanese Examined Patent Publication No. 1-046862

  However, in the composition described in Patent Document 1, there were cases in which coexistence of the heat resistance of the cured product, and the sensitivity and resolution in photolithography was not sufficient. In addition, since the linear thermal expansion coefficient of the cured product is low (that is, low CTE) is also required because it causes cracks, warpage, and the like.

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

  As a result of intensive studies conducted by the present inventors in view of the above, by using a polyamide-based resin containing a benzooxazole structure in a specific ratio as a polybenzoxazole precursor, or a polyamide-based resin having a benzoxazole structure and polyhydroxy By using together the polybenzoxazole precursor which is an amide | amido in a specific ratio, it discovers that the said subject can be solved and came to complete this 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 comprises a photosensitive resin (B) and a polybenzoxazole precursor (A) which is a polyamide resin obtained from the reaction of a diamine component and a dicarboxylic acid component. A composition,
In the polyamide structure of the polybenzoxazole precursor (A), the ratio of the structure represented by the following general formula (1) is 0.1 to 15%, and the ratio of the structure represented by the following general formula (2) is 85 It is characterized by being -99.9%.

(In General Formula (1), P is a residue of a diamine component, and is a divalent compound having a benzoxazole structure of any one of the following General Formulas (1-1), (1-2) and (1-3) R ′ is a residue of a dicarboxylic acid component and is a divalent organic group.)

(In the general formula (1-1), R _{1 to} R _{4 each} represents a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond to a nitrogen atom in the general formula (1) R _{5 to} R ₉ each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a group represented by the general formula (1) And any one of a direct bond to the nitrogen atom and may be the same or different, provided that any one of R _{1 to} R ₄ and any one of R _{5 to} R ₉ One is a direct bond with the nitrogen atom in the general formula (1).)

(In the general formula (1-2), R _{10 to} R _{14 each} represents 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 to a nitrogen atom in the general formula (1) R _{15 to} R ₁₉ each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a group represented by the general formula (1) And any one of a direct bond to the nitrogen atom and may be the same or different, provided that 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 each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group or an amino group Yes, same or different It has.)

(In the general formula (1-3), R _{22 to} R _{26 each} represents a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond to a nitrogen atom in the general formula (1) R _{27 to} R ₃₁ each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a group represented by the general formula (1) And any one of a direct bond to the nitrogen atom, and may be the same or different, provided that any one of R _{22 to} R ₂₆ and any one of R _{27 to} R ₃₁ And R ₃₂ and R ₃₃ each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, or an amino group. Yes, same or different It has.)

(In 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。） Another photosensitive resin composition of the present invention comprises 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). And a photosensitive resin composition containing
The polyamide resin (α-1) 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),
The compounding ratio of the polyamide resin (α-1) and the polybenzoxazole precursor (α-2) is 0.1: 99.9 to 15:85 in mass conversion.

(In the general formula (3), P is a residue of a diamine component, and is a divalent compound having a benzoxazole structure of any one of the following general formulas (3-1), (3-2) and (3-3) R ′ is a residue of a 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 each} represents a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond to a nitrogen atom in the general formula (3) R _{5 to} R ₉ each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a group represented by formula (3) And any one of a direct bond to the nitrogen atom and may be the same or different, provided that any one of R _{1 to} R ₄ and any one of R _{5 to} R ₉ One is a direct bond with the nitrogen atom in the general formula (3).)

(In the general formula (3-2), R _{10 to} R _{14 each} represents a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond with a nitrogen atom in the general formula (3) R _{15 to} R ₁₉ each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a group represented by formula (3) And any one of a direct bond to the nitrogen atom and may be the same or different, provided that 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 each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group or an amino group Yes, same or different It has.)

(In the general formula (3-3), R _{22 to} R _{26 each} represents a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond to a nitrogen atom in the general formula (3) R _{27 to} R ₃₁ each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a group represented by the general formula (3) And any one of a direct bond to the nitrogen atom, and may be the same or different, provided that any one of R _{22 to} R ₂₆ and any one of R _{27 to} R ₃₁ And R ₃₂ and R ₃₃ each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, or an amino group. Yes, same or different It has.)

(In 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 Is an integer greater than or equal to

  The photosensitive resin composition of the present invention preferably further contains a crosslinking agent.

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

  The cured product of the present invention is obtained by curing the photosensitive resin composition or the resin layer of 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 being excellent in sensitivity and resolution, a dry film having a resin layer obtained from the composition, A cured product of the composition or the resin layer of the dry film, a semiconductor device 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 contains a polybenzoxazole precursor (A) which is a polyamide resin obtained from the reaction of a diamine component and a dicarboxylic acid component, and a photosensitive agent (B). Resin composition, in the polyamide structure of the polybenzoxazole precursor (A), the ratio of the structure represented by the general formula (1) is 0.1 to 15%, and the general formula (2) Or a polyamide resin (α-1) obtained by the reaction of a diamine component and a dicarboxylic acid component, and a polybenzoxazole precursor ( A photosensitive resin composition comprising α-2) and a photosensitizer (B), wherein the polyamide resin (α-1) has a structure represented by the general formula (3), and the poly Benzoxazo The precursor (α-2) has a structure represented by the general formula (4), and the blending ratio of the polyamide resin (α-1) to the polybenzoxazole precursor (α-2) is in terms of mass It is a photosensitive resin composition which is 0.1: 99.9-15: 85. Hereinafter, the component which the photosensitive resin composition of this invention contains is explained in full 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 ratio of the structure represented by the following general formula (1) in the polyamide structure of 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 General Formula (1), P is a residue of a diamine component, and is a divalent compound having a benzoxazole structure of any one of the following General Formulas (1-1), (1-2) and (1-3) R ′ is a residue of a dicarboxylic acid component and is a divalent organic group.)

(In the general formula (1-1), R _{1 to} R _{4 each} represents a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond to a nitrogen atom in the general formula (1) R _{5 to} R ₉ each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a group represented by the general formula (1) And any one of a direct bond to the nitrogen atom and may be the same or different, provided that any one of R _{1 to} R ₄ and any one of R _{5 to} R ₉ One is a direct bond with the nitrogen atom in the general formula (1).)

(In the general formula (1-2), R _{10 to} R _{14 each} represents 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 to a nitrogen atom in the general formula (1) R _{15 to} R ₁₉ each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a group represented by the general formula (1) And any one of a direct bond to the nitrogen atom and may be the same or different, provided that 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 each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group or an amino group Yes, same or different It has.)

(In the general formula (1-3), R _{22 to} R _{26 each} represents a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond to a nitrogen atom in the general formula (1) R _{27 to} R ₃₁ each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a group represented by the general formula (1) And any one of a direct bond to the nitrogen atom, and may be the same or different, provided that any one of R _{22 to} R ₂₆ and any one of R _{27 to} R ₃₁ And R ₃₂ and R ₃₃ each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, or an amino group. Yes, same or different It has.)

(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 proportion in the polyamide structure means the polybenzoxazole precursor (A) after counting as one an amide structure consisting of one diamine component and one dicarboxylic acid component as in the general formula (1). Means the proportion 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 that in the diamine component, any of the general formulas (1-1), (1-2) and (1-3) It can obtain | require with the ratio (molar conversion) of the diamine which has a benzoxazole structure (Hereafter, it is also called a "benzoxazole site | part"). The ratio may be determined by analysis by NMR or the like. 10-30 are preferable and, as for the total of the amide structure in the polyamide structure contained in a polybenzoxazole precursor (A), 15-25 are more preferable.

  When the ratio of the structure represented by the general formula (1) is less than 0.1%, the heat resistance of the cured product is lowered, and the linear thermal expansion coefficient is also increased. In addition, if the ratio exceeds 15%, the sensitivity and the resolution deteriorate. Preferably, it is 1 to 10%.

  The polyamide structure of the polybenzoxazole precursor (A) is obtained from the reaction of the diamine component and the dicarboxylic acid component. The diamine component and the dicarboxylic acid component may be those used in the synthesis of polyamide, for example, diamines as the diamine component, and dicarboxylic acids such as dicarboxylic acids, dicarboxylic esters, and carboxylic acid dichlorides as the dicarboxylic acid component. Dihalides are 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, here the number of repetitions) When is 1, it means that it does not repeat 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- R _{22 to} R ₂₆ and R _{27 to} R ₃₁ in 3) are preferably a hydrogen atom or a direct bond with 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- _R 22 _{to R} 26 in _3), as the organic group R 27 _{to R 31} can be taken, for example, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, cycloalkyl having 3 to 8 carbon atoms Groups, aryl groups having 6 to 12 carbon atoms, allyl groups, trifluoromethyl groups 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, for example, 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 which 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 take Examples of the atom include fluorine, chlorine and bromine. Among them, fluorine is preferred in view 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 alkylsulfonyl groups having 1 to 10 carbon atoms such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, octylsulfonyl group, decylsulfonyl group, and dodecylsulfonyl group.

  Examples of the diamine component represented by P in the general formula (1) include diamines having a benzooxazole structure of any of the general formulas (5), (6) and (7) described later.

  Examples of the dicarboxylic acid component represented by R ′ in the general formula (1) are isophthalic acid, terephthalic acid, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenylether, 4,4'-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2, 2- Dicarboxylic acids having an aromatic ring such as bis (p-carboxyphenyl) propane and 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, oxalic acid, malonic acid Succinic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclopropane Aliphatic dicarboxylic acids such as Tanji carboxylic acids, and their dihalide thereof. Among them, preferred is 4,4'-dicarboxydiphenyl ether and its dihalides.

  In the general formula (1), the divalent organic group represented by R ′ may be an aliphatic group or an aromatic group, but is preferably an aromatic group, and on the aromatic ring, it may be in the general formula (1) More preferably, it is bound to a carbonyl. The number of carbon atoms of the divalent aromatic group is preferably 6 to 30, and more preferably 6 to 24. Although the following groups are mentioned as a specific example of the above-mentioned bivalent aromatic group, it is not limited to these, if the well-known aromatic group contained in a polybenzoxazole precursor is chosen according to a 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。）

(Wherein, A represents a single bond, —CH ₂ —, —O—, —CO—, —S—, —SO ₂ —, —NHCO—, —C (CF ₃ ) ₂ —, —C (CH ₃ ) _2- represents a divalent group selected from the group consisting of

Among the aromatic groups, the divalent organic group is preferably the following group.

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

  As an amide structure other than the said General formula (1) which polybenzoxazole precursor (A) contains in a polyamide structure, it is an amide structure represented by 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, 1 It is more preferable that it is: 99-5: 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、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）。）

(Wherein, 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 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, more preferably 15 to 25 (however, here) If the number of repetitions is 1, it means that they are not repeated continuously.))

  Examples of dihydroxydiamines represented by X in the general formula (2) include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 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) -1,1,1 1,3,3,3-hexafluoropropane etc. are mentioned. Among them, 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 either an aliphatic group or an aromatic group, but is preferably an aromatic group, and two hydroxy groups and two amino groups are in the ortho position. More preferably, it is located on an aromatic ring. It is preferable that the carbon atom number of the said tetravalent aromatic group is 6-30, and it is more preferable that it is 6-24. Specific examples of the tetravalent aromatic group include, but are not limited to, the following groups, and a known aromatic group that may be contained in the polybenzoxazole precursor is selected according to the application. Just do it.

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

  As said dicarboxylic acid component which Y in the said General formula (2) shows, it is the same as that of the dicarboxylic acid component which R 'shows in said General formula (1).

  The number average molecular weight (Mn) of the polybenzoxazole precursor (A) is preferably 5,000 to 100,000, and more preferably 8,000 to 50,000. Here, the number average molecular weight is a value measured by gel permeation chromatography (hereinafter referred to as "GPC") and converted by standard polystyrene. Moreover, it is preferable that it is 10,000-200,000, and, as for the mass mean molecular weight (Mw) of polybenzoxazole precursor (A), it is more preferable that it is 16,000-100,000. Here, the mass average molecular weight is a 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, and more preferably 70 to 90% by mass, based on the total amount of the composition solid content.

  When the photosensitive resin composition of the present invention contains the polybenzoxazole precursor (A), a cured film having high heat resistance and a low linear thermal expansion coefficient can be formed without mixing the polymer, and the sensitivity is high. Although the resolution is excellent, the polybenzoxazole precursor (A) may be used in combination of two or more as needed. Moreover, you may use it in combination with polymers other than polybenzoxazole precursor (A) in the range which does not impair the effect of this invention.

[Polyamide-based 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 a diamine component, and is a divalent compound having a benzoxazole structure of any one of the following general formulas (3-1), (3-2) and (3-3) R ′ is a residue of a 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 each} represents a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond to a nitrogen atom in the general formula (3) R _{5 to} R ₉ each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a group represented by formula (3) And any one of a direct bond to the nitrogen atom and may be the same or different, provided that any one of R _{1 to} R ₄ and any one of R _{5 to} R ₉ One is a direct bond with the nitrogen atom in the general formula (3).)

(In the general formula (3-2), R _{10 to} R _{14 each} represents a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond with a nitrogen atom in the general formula (3) R _{15 to} R ₁₉ each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a group represented by formula (3) And any one of a direct bond to the nitrogen atom and may be the same or different, provided that 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 each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group or an amino group Yes, same or different It has.)

(In the general formula (3-3), R _{22 to} R _{26 each} represents a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond to a nitrogen atom in the general formula (3) R _{27 to} R ₃₁ each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a group represented by the general formula (3) And any one of a direct bond to the nitrogen atom, and may be the same or different, provided that any one of R _{22 to} R ₂₆ and any one of R _{27 to} R ₃₁ And R ₃₂ and R ₃₃ each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, or an amino group. Yes, same or different It has.)

  The blending ratio of the polyamide resin (α-1) and the polybenzoxazole precursor (α-2) is 0.1: 99.9 to 15:85 in mass conversion. When the said polyamide-type resin ((alpha) -1) is less than 0.1, the heat resistance of hardened | cured material will fall, and a linear thermal expansion coefficient will also become high. When the polyamide resin (α-1) exceeds 15, the sensitivity and the 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 in the synthesis of polyamide, for example, diamines as the diamine component, and dicarboxylic acids such as dicarboxylic acids, dicarboxylic esters, and carboxylic acid dichlorides as the dicarboxylic acid component. Dihalides are mentioned.

  N in the general formula (3) is preferably 1 to 20, and 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), as the diamine component represented by P, as in P in the general formula (1), benzoxazoles of any one of the general formulas (5), (6) and (7) described later The diamine which has a structure is mentioned.

  The dicarboxylic acid component represented by R 'in the general formula (3) is the same as 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). Moreover, structures other than the structure shown by General formula (3) may be included, for example, the structure shown by the said 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. As Mw / Mn, 1-5 are preferable.

  It is preferable that the compounding quantity of polyamide-type resin ((alpha) -1) is 0.1 to 15% in a resin component, and it can improve the thermo-mechanical characteristic of a cured film, without impairing 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。）

(Wherein 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. is there.)

  In the said General formula (4), m is an integer greater than or equal to 1, Preferably it is 10-50, More preferably, it is 20-40.

  As a dihydroxy diamine which X in the said General formula (4) shows, it is the same as that of the dihydroxy diamine which X in the said General formula (3) shows.

  In the said General formula (4), the tetravalent organic group which X shows is the same as the tetravalent organic group which X shows in said 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), as in R ′ in the general formula (3). .

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

  The number average molecular weight (Mn) of the polybenzoxazole precursor (α-2) is preferably 5,000 to 100,000, and 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 with higher resolution can be obtained.

  If necessary, the photosensitive resin composition of the present invention may be used in combination of two or more types of polyamide resin (α-1) and polybenzoxazole precursor (α-2). Moreover, you may use it in combination with polymers other than a polyamide-type resin ((alpha) -1) and polybenzoxazole precursor ((alpha) -2) in the range which does not impair the effect of this invention. In addition, although the polybenzoxazole precursor ((alpha) -2) may have a benzoxazole structure in the range which does not impair the effect of this invention, it is preferable that it does not have a benzoxazole structure.

[Photosensitizer (B)]
There is no restriction | limiting in particular as a photosensitive agent (B), A photo-acid generator, a photoinitiator, and a photo base generator can be used. The photoacid generator is a compound that generates an acid upon irradiation with light such as ultraviolet light or visible light, the photopolymerization initiator is a compound that generates a radical or the like upon similar light irradiation, and the photobase generator is similarly The compound is a compound whose molecular structure is changed by light irradiation or which is cleaved to generate one or more basic substances. In the present invention, a photoacid generator can be suitably used as the photosensitizer (B).

As a photoacid generator, naphthoquinone diazide compound, diaryl sulfonium salt, triaryl sulfonium salt, dialkyl phenacyl sulfonium salt, diaryliodonium salt, aryl diazonium salt, aromatic tetracarboxylic acid ester, aromatic sulfonic acid ester, nitrobenzyl ester And aromatic N-oxyimide sulfonate, aromatic sulfamide, benzoquinone diazosulfonic acid ester and the like. The photoacid generator is preferably a dissolution inhibitor. Among them, naphthoquinone diazide compounds are preferable.

  Specific examples of naphthoquinone diazide compounds include naphthoquinone diazide adducts of tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene (eg, TS533, TS567, TS583, TS593 manufactured by Sanho Chemical Laboratory Co., Ltd.). And naphthoquinone diazide adducts of tetrahydroxybenzophenone (eg, BS550, BS570, BS599 manufactured by Sanho 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, and more preferably 5 to 20% by mass, based on the total mass of the composition.

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

(Crosslinking agent having phenolic hydroxyl group)
The crosslinking 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): More preferably, they are

（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 general formula (A), R ^A1 represents a di- to deca-valent organic group. R ^A2 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. N is an integer of 2 to 10 Indicate

In the general formula (A), R ^A1 is preferably an alkylene group having 1 to 3 carbon atoms which may have a substituent.

In the general formula (A), R ^A2 is preferably a hydrogen atom.

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

Moreover, it is preferable to have a fluorine atom, and, as for the crosslinking agent which has a phenolic hydroxyl group, it is more preferable to have a trifluoromethyl group. It is preferable that the said fluorine atom or the said trifluoromethyl group has a 2-10-valent organic group which R < ^A1 > in the said General formula (A) shows, and R ^<A1> is a di (trifluoromethyl) methylene group. Is preferred. The crosslinker having a phenolic hydroxyl group preferably has a bisphenol structure, and more preferably a bisphenol AF structure.

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

  The crosslinking agent having a phenolic hydroxyl group may be used alone or in combination of two or more. The blending amount of the crosslinking agent having a phenolic hydroxyl group is preferably 1 to 20% by mass, and more preferably 3 to 10% by mass, based on the total mass of the composition. With such a blending ratio, a composition having more excellent developability and being excellent in pattern formation after curing can be obtained.

(Cross-linking agent not having phenolic hydroxyl group and having two or more methylol groups)
The crosslinking agent having no phenolic hydroxyl group and having two or more methylol groups preferably has a molecular weight of 100 or more.

  The crosslinking agent having no phenolic hydroxyl group and having two or more methylol groups 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, and when n is 1, R ^B1 represents a methylol group (that is, “—CH ₂ OH”), and when n is an integer of 2 to 10 And R ^B1 represents a divalent to ten-valent organic group, 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 Indicate

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

In the general formula (B), R ^B2 is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

It is preferable that it is the following compound as a specific example of a crosslinking agent which does not have a phenolic hydroxyl group and has two or more methylol groups.

  The crosslinking agent having no phenolic hydroxyl group and two or more methylol groups may be used alone or in combination of two or more. It is preferable that the compounding quantity of the crosslinking agent which does not have this phenolic hydroxyl group and has 2 or more of methylol groups is 1-20 mass% on a composition solid content whole quantity basis. With such a blending ratio, a composition having more excellent developability and being excellent in pattern formation 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 crosslinking agent)
The melamine crosslinking agent is not particularly limited as long as it is a crosslinking agent having a melamine structure, but is preferably a melamine crosslinking agent represented by the following general formula (C).

(Wherein, R ^C1A , R ^C2A , R ^C3A , R ^C4A , R ^C5A and R ^C6A are each independently an alkylene group having 1 to 3 carbon atoms. R ^C1B , R ^C2B , R ^C3B , R ^C4B And R ^C5B and R ^C6B are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

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

  The melamine-based crosslinking agent may be used alone or in combination of two or more. It is preferable that the compounding quantity of a melamine type crosslinking agent is 0.5-15 mass% on the basis of composition solid content whole quantity. The residual film rate of an unexposed part can be made higher as it is 0.5-15 mass%, and the undeveloped part of an exposed part can be prevented.

(Urea based crosslinking agent)
The urea crosslinking agent is not particularly limited, but is preferably a melamine crosslinking 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。）

(Wherein, R ^D1 and R ^D2 each 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。）

(Wherein, R ^E1 each independently represents a hydrogen atom or a monovalent organic group, and R ^E2 represents a divalent organic group).

  The urea-based crosslinking agent is preferably an alkylated urea resin, and more preferably has a 2-imidazolidinone ring. For example, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 4,5-dimethoxy-1,3-bis (methoxymethyl) imidazo And 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 specific compounds of the urea-based crosslinking agent, the following compounds and the like can be used.

  The urea-based crosslinking agent may be used alone or in combination of two or more. The compounding amount of the urea-based crosslinking agent is preferably 1 to 20% by mass on the basis of the total solid content of the composition. When the content 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 a thiol compound, the development residue can be reduced. The thiol compound is not particularly limited, and in addition to D, L-dithiothreitol, 2-mercaptoethanol, the following compounds and the like can be used. Among these, D, L-dithiothreitol is preferable.

  As the thiol compound, one type may be used alone, or two or more types may be used in combination. The compounding amount of the thiol compound is preferably 0.01 to 20% by mass, and more preferably 0.1 to 10% by mass, based on the total amount of the composition solid content. By setting it as the said range, generation | occurrence | production of a 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 formability can be improved. The urea compound is not particularly limited. 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 Benzoylurea, benzylurea, 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, butylurea, N, N'-diethyl-N, N'-diphenylurea and the like It is possible to have.

  The urea compounds may be used alone or in combination of two or more. The compounding amount of the urea compound is preferably 0.01 to 15% by mass, and more preferably 0.05 to 10% by mass, based on the total amount of the composition solid content. By setting the above range, the residual film rate can be improved, the developability of a thick photosensitive film on a 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 a silane coupling agent, adhesion to a silicon substrate can be improved. The silane coupling agent is preferably a silane coupling agent having an arylamino group and a silane coupling agent having two or more trialkoxysilyl groups. It is more preferable that it is a silane coupling agent which has an arylamino group from having excellent resolution.

  The silane coupling agent having an arylamino group is described. The aryl group of the arylamino group includes aromatic hydrocarbon groups such as phenyl group, tolyl group and xylyl group, fused polycyclic aromatic groups such as naphthyl group, anthracenyl group and phenanthrenyl group, aromatic groups such as thienyl group and indolyl group Group heterocyclic groups.

（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).

(Wherein, R ^{F1 to} R ^F5 each independently represent a hydrogen atom or an organic group)

In the above general formula (F), R ^{F1 to} R ^F5 are preferably hydrogen atoms.

  In the silane coupling agent having an arylamino group, it is preferable that the silicon atom and the arylamino group be 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 following compounds.

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

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

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

  A silane coupling agent may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, you may contain silane coupling agents other than the silane coupling agent which has the arylamino group mentioned above, and the silane coupling agent which has two or more trialkoxy silyl groups.

  It is preferable that the compounding quantity of a silane coupling agent is 1-15 mass% on the basis of composition solid content whole quantity. The development remainder of an exposure part can be prevented as it is 1-15 mass%.

  A solvent can be blended with 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 other optional additives. 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 it can. These may be used alone or in combination of two or more. The amount of the solvent to be used can be used in the range of 50 to 9000 parts by mass with respect to 100 parts by mass of the polybenzoxazole precursor (A) according to the applied film thickness and viscosity.

  In the photosensitive resin composition of the present invention, known sensitizers, adhesion auxiliaries and the like can be blended as long as the effects of the present invention are not impaired.

  In addition, various other organic or inorganic low molecular weight or high molecular weight compounds may be added to the photosensitive resin composition of the present invention in order to impart processing characteristics and various functions. For example, surfactants, leveling agents, plasticizers, fine particles and the like can be used. The fine particles include organic fine particles of polystyrene, polytetrafluoroethylene or the like, and inorganic fine particles of colloidal silica, carbon, layered silicate or the like. Furthermore, various coloring agents, 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 drying after applying the photosensitive resin composition of the present invention.

  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, lip coater, comma coater, film coater, etc. The resin layer can be manufactured by forming the above-mentioned resin layer, and preferably laminating a cover film (protective film) thereon. The cover film and the carrier film may be the same film material or different films.

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

  As a carrier film, thermoplastic films, such as polyester films, such as a polyethylene terephthalate of thickness of 2-150 micrometers, are used, for example.

  Although a polyethylene film, a polypropylene film, etc. can be used as a cover film, What has smaller adhesive force with a resin layer than a carrier film is good.

  100 micrometers or less are preferable and, as for the film thickness of the resin layer on the dry film of this invention, the range of 5-50 micrometers is more preferable.

  The photosensitive resin composition of the present invention is preferably positive. The pattern film which is the hardened | cured material is manufactured as follows using the photosensitive resin composition of this invention, for example. In addition, although the case where polybenzoxazole precursor (A) is included is demonstrated by the following manufacturing method, it is the same also when polyamide resin ((alpha) -1) and polybenzoxazole precursor ((alpha) -2) are included. .

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

  The substrate is not particularly limited, and can be widely applied to semiconductor substrates such as silicon wafers, wiring substrates, and substrates made of various resins, metals, and the like.

  Next, as step 2, the above-mentioned coating film is exposed through a photomask having a pattern or directly. As the exposure light beam, one having a wavelength capable of generating an acid by activating a photoacid generator as a photosensitizer (B) is used. Specifically, the exposure light beam preferably has a maximum wavelength in the range of 350 to 410 nm. As described above, the light sensitivity 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 or the like can be used.

  Subsequently, as Step 3, heating may be performed to close a part of the polybenzoxazole precursor (A) in the unexposed area. Here, the ring closure rate is about 30%. The heating time and the heating temperature are appropriately changed according to the polybenzoxazole precursor (A), the coating film thickness and the type of photoacid generator as the photosensitizer (B).

  Next, in step 4, the coated film is treated with a developer. Thereby, the exposed part in a coating film can be removed and the pattern film of the photosensitive resin composition of this invention can be formed.

  As a method used for development, any method can be selected from among known methods for developing a photoresist, such as a rotary spray method, a paddle method, and a dipping method accompanied by ultrasonic treatment. As a developing solution, inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, ammonia water, etc., organic amines such as ethylamine, diethylamine, triethylamine, triethanolamine, etc., tetramethyl ammonium hydroxide, tetrabutyl ammonium hydroxide And aqueous solutions of quaternary ammonium salts and the like. In addition, if necessary, water-soluble organic solvents such as methanol, ethanol and isopropyl alcohol and surfactants may be added in appropriate amounts. Thereafter, if necessary, the coating film is washed with a rinse solution to obtain a pattern film. As the rinse solution, distilled water, methanol, ethanol, isopropyl alcohol or the like can be used alone or in combination. Also, the above solvent may be used as a developer.

  Thereafter, in step 5, the patterned film is heated to obtain a cured coating (cured product). At this time, polybenzoxazole precursor (A) may be subjected to ring closure to obtain polybenzoxazole. The heating temperature is appropriately set so that the patterned 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 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 temperature rising oven capable of setting a temperature program. As the atmosphere (gas) at this time, air may be used, or an inert gas such as nitrogen or argon may be used.

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

  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 component imparting heat resistance and insulation as a permanent film composed of polybenzoxazole. In particular, surface protection 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 having a bump structure, interlayer insulating films for multilayer circuits, passive It can be suitably used as an insulating material for parts, a protective film of a printed wiring board such as a solder resist or a coverlay film, a liquid crystal alignment film, and the like.

  Although the manufacturing method of the photosensitive resin composition of this invention is not specifically limited, The polybenzoxazole precursor (A) which is a polyamide-type resin obtained from reaction of the said diamine component and a dicarboxylic acid component, and a photosensitive agent (B) In the case of the manufacturing method of the photosensitive resin composition to mix | blend, it manufactures suitably by using the diamine component which has a benzoxazole structure in any one of following General formula (5), (6) and (7) as said diamine. can do. A photosensitive resin composition comprising 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 photosensitive agent (B). In the case of the manufacturing method of, it can manufacture suitably by using the diamine component which has a benzooxazole structure in any one of following General formula (5), (6) and (7) as said 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 each} represents a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, or an amino group, and may be the same or different) .R ₅ to R ₉ is a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, or a amino group, may be the same or different. However, R ₁ to R Any one of ₄ and any one of R _{5 to} R ₉ is an amino group.)

(In the general formula (6), R _{10 to} R _{14 each} represents a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, or an amino group, and may be identical or different. which may .R ₁₅ to R ₁₉ is a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, or a amino group, may be the same or different. However, R ₁₀ one of to R _{14, and,} one of R 15 _{to R 19} is an amino group _{.R 20, R 21} are each a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo Group, a sulfonyl group, or an amino group, which may be the same or different)

(In the general formula (7), R _{22 to} R _{26 each} represents a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, or an amino group, and may be the same or different) .R ₂₇ to R ₃₁ is a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, or a amino group, may be the same or different. _{However, R} 22 to R _And any one of R _{27 to} R ₃₁ is an amino group, each of R ₃₂ and R ₃₃ is a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, 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 by way of examples, but the present invention is not limited to the following examples. In the following, “parts” and “%” are all based on mass unless otherwise noted.

(Synthesis of Polybenzoxazole Precursor A-1) (Benzoxazole 10%)
In a 0.5 liter flask equipped with a stirrer and a thermometer, 85 g of N-methylpyrrolidone is charged, 10.29 g (28.1 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 2- (4-) 0.70 g (3.12 mmol) of aminophenyl) -5-aminobenzoxazole was dissolved with stirring. Thereafter, the flask is immersed in an ice bath, and 10.00 g (33.9 mmol) of 4,4'-diphenyletherdicarboxylic acid chloride is added in the form of a solid over 10 minutes while keeping the inside of the flask at 0 to 5 ° C. Stir for 30 minutes. Then, stirring was continued at room temperature for 18 hours. The stirred solution was poured into 400 mL of ion exchange water (specific resistance 18.2 MΩ · cm), and the precipitate was recovered. Thereafter, the obtained solid was dissolved in 420 mL of acetone, and poured into 1 L of ion exchanged water. The precipitated solid was recovered, and then dried under reduced pressure to obtain a carboxyl group-terminated partially cyclized polybenzoxazole precursor. The weight average molecular weight determined by GPC method standard polystyrene conversion was 31,700.

(Synthesis of polybenzoxazole precursor A-2) (benzoxazole site 5%)
In a 0.5 liter flask equipped with a stirrer and a thermometer, 85 g of N-methylpyrrolidone is charged, 10.86 g (29.65 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 2- (4-) 0.7 g (1.55 mmol) of aminophenyl) -5-aminobenzoxazole was dissolved with stirring. Thereafter, the flask is immersed in an ice bath, and 10.00 g (33.9 mmol) of 4,4'-diphenyletherdicarboxylic acid chloride is added in the form of a solid over 10 minutes while keeping the inside of the flask at 0 to 5 ° C. Stir for 30 minutes. Then, stirring was continued at room temperature for 18 hours. The stirred solution was poured into 400 mL of ion exchange water (specific resistance 18.2 MΩ · cm), and the precipitate was recovered. Thereafter, the obtained solid was dissolved in 420 mL of acetone, and poured into 1 L of ion exchanged water. The precipitated solid was recovered, and then dried under reduced pressure to obtain a carboxyl group-terminated partially cyclized polybenzoxazole precursor. The weight average molecular weight determined by GPC method standard polystyrene conversion was 33,700.

(Synthesis of polybenzoxazole precursor R-1) (benzoxazole 30%)
In a 0.5 liter flask equipped with a stirrer and a thermometer, 85 g of N-methylpyrrolidone is charged, and 8.00 g (21.8 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 2- (4- Aminophenyl) -5-aminobenzoxazole g (9.32 mmol) was dissolved with stirring. Thereafter, the flask is immersed in an ice bath, and 10.00 g (33.9 mmol) of 4,4'-diphenyletherdicarboxylic acid chloride is added in the form of a solid over 10 minutes while keeping the inside of the flask at 0 to 5 ° C. Stir for 30 minutes. Then, stirring was continued at room temperature for 18 hours. The stirred solution was poured into 400 mL of ion exchange water (specific resistance 18.2 MΩ · cm), and the precipitate was recovered. Thereafter, the obtained solid was dissolved in 420 mL of acetone, and poured into 1 L of ion exchanged water. The precipitated solid was recovered, and then dried under reduced pressure to obtain a carboxyl group-terminated partially cyclized polybenzoxazole precursor. The weight average molecular weight determined by GPC method standard polystyrene conversion was 28,200.

(Synthesis of polybenzoxazole precursor R-2) (benzoxazole site 0%)
In a 0.5 liter flask equipped with a stirrer and a thermometer, 212 g of N-methylpyrrolidone was charged, and 60.52 g (165.22 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane was stirred and dissolved. Thereafter, the flask is immersed in an ice bath, and 53.02 g (179.65 mmol) of 4,4-diphenyletherdicarboxylic acid chloride is added in the form of solid 5 g each over 30 minutes while keeping the inside of the flask at 0 to 5 ° C. The solution was stirred for 30 minutes. Then, stirring was continued at room temperature for 5 hours. The stirred solution was poured into 1 L of ion exchange water (specific resistance 18.2 MΩ · cm), and the precipitate was recovered. Thereafter, the obtained solid was dissolved in 420 mL of acetone, and poured into 1 L of ion exchanged water. After the precipitated solid was recovered, it was dried under reduced pressure to obtain a polybenzoxazole (PBO) precursor (R-2) having the following repeating structure of carboxyl group terminal. 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 other amide structures. The polybenzoxazole precursor R-2 has the following other amide structure in the polyamide structure.
・ Amide structure having benzoxazole structure

・ Other amide structures

Example 1
(Evaluation of the physical properties)
After dissolving 100 parts by mass of the polybenzoxazole precursor A-1 and 10 parts by mass of the diazonaphthoquinone compound in 300 parts by mass of γ-butyrolactone, the resultant was filtered with a 0.2 μm filter to obtain a varnish of a photosensitive resin composition. 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 having a film thickness of about 30 μm. Next, the coated silicon wafer was heated at 150 ° C./30 minutes, 250 ° C./30 minutes, 320 ° C./30 minutes using an oven. The obtained cured film was peeled off from the silicon wafer, and the glass transition temperature (Tg) and the thermal expansion coefficient (CTE) were measured by TMA (thermomechanical analysis).

(Pattern preparation)
The above 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 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 1 to 30 μm pattern was drawn. After exposure, development was carried out with a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 120 seconds, followed by rinsing with water to obtain a pattern of a positive cured film.

(Evaluation of unexposed area residual film rate)
The film thickness of the cured film after development was measured, and the ratio to the film thickness before development was taken to obtain the unexposed area residual film ratio.
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”), and the size of the smallest pattern capable of patterning the exposed area without scum resolution (L (μm) / S (μm)), sensitivity at that time is sensitivity And

(Example 2)
Evaluation was performed in the same manner as in Example 1 except that the polybenzoxazole precursor was changed to A-2.

(Comparative example 1)
Evaluation was performed in the same manner as in Example 1 except that the polybenzoxazole precursor was changed to R-1.
As a result of evaluation of developability, the exposed portion was not dissolved in the developer and no pattern was obtained.

(Comparative example 2)
Evaluation was carried out in the same manner as in Example 1 except that the polybenzoxazole precursor was changed to R-2.
As a result of evaluating the developability, both the exposed area and the unexposed area were dissolved in the developer and no pattern was obtained.

(Synthesis of polybenzoxazole precursor A-3) (benzoxazole site 2%)
In a 0.5 liter flask equipped with a stirrer and a thermometer, 85 g of N-methylpyrrolidone is charged, 11.21 g (30.6 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 2- (4- 0.145 g (0.644 mmol) of aminophenyl) -5-aminobenzoxazole was dissolved with stirring. Thereafter, the flask is immersed in an ice bath, and 10.10 g (34.2 mmol) of 4,4'-diphenyletherdicarboxylic acid chloride is added in the form of a solid over 10 minutes while keeping the inside of the flask at 0 to 5 ° C. Stir for 30 minutes. Then, stirring was continued at room temperature for 18 hours. The stirred solution was poured into 400 mL of ion exchange water (specific resistance 18.2 MΩ · cm), and the precipitate was recovered. Thereafter, the obtained solid was dissolved in 420 mL of acetone, and poured into 1 L of ion exchanged water. The precipitated solid was recovered, and then dried under reduced pressure to obtain a carboxyl group-terminated partially cyclized polybenzoxazole precursor. The weight average molecular weight determined by GPC method standard polystyrene conversion was 34,500.

(Example 3)
100 parts by mass of the polybenzoxazole precursor A-2, 10 parts by mass of the diazonaphthoquinone compound and 5 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane (KBM-573) are dissolved in 300 parts by mass of γ-butyrolactone, It filtered with a 0.2 micrometer filter, and obtained the varnish of the photosensitive resin composition. 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 having a film thickness of about 30 μm. Next, the coated silicon wafer was heated at 150 ° C./30 minutes and 250 ° C./30 minutes using an oven. The obtained cured film was peeled off from the silicon wafer, and the glass transition temperature (Tg) and the thermal expansion coefficient (CTE) were measured by TMA (thermomechanical analysis).
Separately, the above varnish was coated on 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 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, development was carried out with a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 120 seconds, followed by rinsing with water to obtain a pattern of a positive cured film.

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

(Example 5)
Evaluation was performed 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 Co., Ltd.) was added.

(Example 6)
Evaluation was performed in the same manner as in Example 3 except that 5 parts by mass of TML-BPAF-MF (Honshu Kagaku) and 5 parts by mass of MW 390 (Sanwa Chemical Co., Ltd.) were added.

(Example 7)
100 parts by mass of polybenzoxazole precursor A-3, 10 parts by mass of diazonaphthoquinone compound 5 parts by mass of TML-BPAF-MF, 5 parts by mass of 1,4-benzenedimethanol, N-phenyl-3-aminopropyltrimethoxysilane ( After 5 parts by mass of KBM-573) was dissolved in 300 parts by mass of γ-butyrolactone, the resultant was filtered with a 0.2 μm filter to obtain a varnish of a photosensitive resin composition. 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 having a film thickness of about 30 μm. Next, the coated silicon wafer was heated at 150 ° C./30 minutes, 250 ° C./30 minutes, 320 ° C./30 minutes using an oven. The obtained cured film was peeled off from the silicon wafer, and the glass transition temperature (Tg) and the thermal expansion coefficient (CTE) were measured by TMA (thermomechanical analysis). Separately, the above varnish was coated on 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 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, development was carried out with a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 120 seconds, followed by rinsing 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 as additives, and TML-BPAF-MF and 1,4-benzenedimethanol were not added. Evaluation was carried out in the same manner as Example 7 except for the following.

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 linear thermal expansion coefficient, and is excellent in sensitivity and resolution.

Claims (8)

A photosensitive resin composition comprising 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),
In the polyamide structure of the polybenzoxazole precursor (A), the ratio of the structure represented by the following general formula (1) is 0.1 to 15%, and the ratio of the structure represented by the following general formula (2) is 85 The photosensitive resin composition characterized by being -99.9%.

(In General Formula (1), P is a residue of a diamine component, and is a divalent compound having a benzoxazole structure of any one of the following General Formulas (1-1), (1-2) and (1-3) R ′ is a residue of a dicarboxylic acid component and is a divalent organic group.)

(In the general formula (1-1), R _{1 to} R _{4 each} represents a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond to a nitrogen atom in the general formula (1) R _{5 to} R ₉ each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a group represented by the general formula (1) And any one of a direct bond to the nitrogen atom and may be the same or different, provided that any one of R _{1 to} R ₄ and any one of R _{5 to} R ₉ One is a direct bond with the nitrogen atom in the general formula (1).)

(In the general formula (1-2), R _{10 to} R _{14 each} represents 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 to a nitrogen atom in the general formula (1) R _{15 to} R ₁₉ each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a group represented by the general formula (1) And any one of a direct bond to the nitrogen atom and may be the same or different, provided that 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 each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group or an amino group Yes, same or different It has.)

(In the general formula (1-3), R _{22 to} R _{26 each} represents a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond to a nitrogen atom in the general formula (1) R _{27 to} R ₃₁ each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a group represented by the general formula (1) And any one of a direct bond to the nitrogen atom, and may be the same or different, provided that any one of R _{22 to} R ₂₆ and any one of R _{27 to} R ₃₁ And R ₃₂ and R ₃₃ each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, or an amino group. Yes, same or different It has.)

(In 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 comprising 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),
The polybenzoxazole precursor (α-2) has a structure represented by the following general formula (4),
A photosensitive resin composition characterized in that a compounding ratio of the polyamide resin (α-1) and the polybenzoxazole precursor (α-2) is 0.1: 99.9 to 15:85 in mass conversion. object.

(In the general formula (3), P is a residue of a diamine component, and is a divalent compound having a benzoxazole structure of any one of the following general formulas (3-1), (3-2) and (3-3) R ′ is a residue of a 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 each} represents a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond to a nitrogen atom in the general formula (3) R _{5 to} R ₉ each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a group represented by formula (3) And any one of a direct bond to the nitrogen atom and may be the same or different, provided that any one of R _{1 to} R ₄ and any one of R _{5 to} R ₉ One is a direct bond with the nitrogen atom in the general formula (3).)

(In the general formula (3-2), R _{10 to} R _{14 each} represents a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond with a nitrogen atom in the general formula (3) R _{15 to} R ₁₉ each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a group represented by formula (3) And any one of a direct bond to the nitrogen atom and may be the same or different, provided that 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 each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group or an amino group Yes, same or different It has.)

(In the general formula (3-3), R _{22 to} R _{26 each} represents a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a direct bond to a nitrogen atom in the general formula (3) R _{27 to} R ₃₁ each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a group represented by the general formula (3) And any one of a direct bond to the nitrogen atom, and may be the same or different, provided that any one of R _{22 to} R ₂₆ and any one of R _{27 to} R ₃₁ And R ₃₂ and R ₃₃ each independently represent a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, or an amino group. Yes, same or different It has.)

(In 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 Is an integer greater than or equal to   Furthermore, the crosslinking agent is included, The photosensitive resin composition of Claim 1 or 2 characterized by the above-mentioned.   It has a resin layer obtained by apply | coating and drying the photosensitive resin composition as described in any one of Claims 1-3 on a film, The dry film characterized by the above-mentioned.   A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 3 or the resin layer of a dry film according to claim 4.   A semiconductor device comprising the cured product according to claim 5.   A printed wiring board comprising the cured product according to claim 5. An electronic component comprising the cured product according to claim 5.