TWI781220B - Photosensitive resin compositions, dry films, cured products, semiconductor elements, printed wiring boards, and electronic parts - Google Patents

Abstract

The object of the present invention is to provide a photosensitive resin composition capable of forming a cured film with high heat resistance and low linear thermal expansion coefficient, and excellent in sensitivity and resolution, a dry film having a resin layer obtained from the composition, and the composition Or a cured product of the resin layer of the dry film, a semiconductor element, a printed wiring board, and an electronic component having the cured product. The solution of the present invention is a photosensitive resin composition, etc., which contains a polyamide-based resin obtained by reacting a diamine component and a dicarboxylic acid component, that is, a polybenzoxazole precursor (A), and a photosensitive agent. (B) The photosensitive resin composition is characterized in that 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%. The proportion of the structure represented by the general formula (2) is 85-99.9%.

Description

Photosensitive resin composition, dry film, cured product, semiconductor element, printed wiring board and electronic parts

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

Due to its excellent heat resistance and electrical insulation, polybenzoxazole is being used as a surface protective film or interlayer insulating film for electrical materials, such as a coating film for semiconductor devices, or for flexible printed wiring board materials, heat-resistant insulation The application of electronic parts such as interlayer materials.

Conventionally, in order to form fine patterns of polybenzoxazole, a photosensitive resin composition in which a polybenzoxazole precursor and a photosensitive agent are blended 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. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 1-046862

[Problem to be solved by the invention]

However, in the composition described in Patent Document 1, the heat resistance of the cured product and the combination of sensitivity and resolution in photolithography may not be sufficient. In addition, due to cracks, warping, etc., the cured product has a low coefficient of linear thermal expansion (that is, a low CTE).

Therefore, the object of the present invention is to provide a cured film capable of forming a cured film with high heat resistance and low linear thermal expansion coefficient, a photosensitive resin composition with excellent sensitivity and resolution, a dry film having a resin layer obtained from the composition, and the composition or cured products of the resin layer of the dry film, semiconductor elements, printed wiring boards and electronic parts having the cured products.

The inventors of the present invention have found that by including the benzoxazole structure in a specific ratio, the polyamide-based resin is used as a polybenzoxazole precursor, or by adding a polyamide resin having a benzoxazole The polyamide-based resin with an oxazole structure and the polyhydroxyamide, ie, the polybenzoxazole precursor, are used together in a specific ratio to solve the above-mentioned problems and finally complete the present invention.

(一般式(1)中，P為二胺成分之殘基，為具有下述一般式(1-1)、(1-2)及(1-3)中任一種苯并噁唑構造的2價之基；R’為二羧酸成分之殘基，為2價之有機基)。

(一般式(1-1)中，R₁ ～R₄ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基、與一般式(1)中之氮原子的直接鍵結之任一個，可為相同亦可為相異；R₅ ～R₉ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基、與一般式(1)中之氮原子的直接鍵結之任一個，可為相同亦可為相異；惟，R₁ ～R₄ 當中之任一個及R₅ ～R₉ 當中之任一個為與一般式(1)中之氮原子的直接鍵結)。

(一般式(1-2)中，R₁₀ ～R₁₄ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基、與一般式(1)中之氮原子的直接鍵結之任一個，可為相同亦可為相異；R₁₅ ～R₁₉ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基、與一般式(1)中之氮原子的直接鍵結之任一個，可為相同亦可為相異；惟，R₁₀ ～R₁₄ 當中之任一個及R₁₅ ～R₁₉ 當中之任一個為與一般式(1)中之氮原子的直接鍵結；R₂₀ 、R₂₁ 分別為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基之任一個，可為相同亦可為相異)。

(一般式(1-3)中，R₂₂ ～R₂₆ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基、與一般式(1)中之氮原子的直接鍵結之任一個，可為相同亦可為相異；R₂₇ ～R₃₁ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基、與一般式(1)中之氮原子的直接鍵結之任一個，可為相同亦可為相異；惟，R₂₂ ～R₂₆ 當中之任一個及R₂₇ ～R₃₁ 當中之任一個為與一般式(1)中之氮原子的直接鍵結；R₃₂ 、R₃₃ 分別為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基之任一個，可為相同亦可為相異)。

(一般式(2)中，X為二羥基二胺類之殘基，為4價之有機基；Y為二羧酸成分之殘基，為2價之有機基)。That is, the photosensitive resin composition of the present invention contains a polyamide-based resin obtained by reacting a diamine component and a dicarboxylic acid component, that is, a polybenzoxazole precursor (A), and a photosensitive agent (B ) photosensitive resin composition, characterized in that in the polyamide structure of the aforementioned polybenzoxazole precursor (A), the ratio of the structure represented by the following general formula (1) is 0.1 to 15%, and the following general The ratio of the structure represented by formula (2) is 85 to 99.9%.

(In the general formula (1), P is the residue of the diamine component, which is 2 with any one of the benzoxazole structures in the following general formulas (1-1), (1-2) and (1-3). Valence base; R' is the residue of a dicarboxylic acid component, which is a divalent organic group).

(In general formula (1-1), R ₁ to R ₄ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the direct connection between nitrogen atoms in general formula (1) Any one of the bonds can be the same or different; R ₅ ~ R ₉ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the general formula (1) Any one of the direct bonds of the nitrogen atom in , may be the same or different; however, any one of R ₁ to R ₄ and any one of R ₅ to R ₉ is the same as that in the general formula (1). direct bond to the nitrogen atom).

(In general formula (1-2), R ₁₀ to R ₁₄ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the direct connection between nitrogen atoms in general formula (1) Any one of the bonds may be the same or different; 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) Any one of the direct bonds of the nitrogen atom in can be the same or different; however, any one of R ₁₀ to R ₁₄ and any one of R ₁₅ to R ₁₉ is the same as that in general formula (1). direct bonding of nitrogen atom; R ₂₀ and R ₂₁ are respectively any one of hydrogen atom, organic group, nitro group, halogen atom, sulfo group, sulfonyl group and amino group, which may be the same or different).

(In general formula (1-3), R ₂₂ to R ₂₆ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the direct connection between nitrogen atoms in general formula (1) Any one of the bonds can be the same or different; R ₂₇ ~ R ₃₁ are hydrogen atom, organic group, nitro group, halogen atom, sulfo group, sulfonyl group, amino group, and the general formula (1) Any one of the direct bonds of the nitrogen atom in , may be the same or different; however, any one of R ₂₂ to R ₂₆ and any one of R ₂₇ to R ₃₁ is the same as that in general formula (1). direct bonding of nitrogen atom; R ₃₂ and R ₃₃ are respectively any one of hydrogen atom, organic group, nitro group, halogen atom, sulfo group, sulfonyl group and amino group, which may be the same or different).

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

(一般式(3)中，P為二胺成分之殘基，為具有下述一般式(3-1)、(3-2)及(3-3)中任一種苯并噁唑構造的2價之基；R’為二羧酸成分之殘基，為2價之有機基；n為1以上之整數)。

(一般式(3-1)中，R₁ ～R₄ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基、與一般式(3)中之氮原子的直接鍵結之任一個，可為相同亦可為相異；R₅ ～R₉ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基、與一般式(3)中之氮原子的直接鍵結之任一個，可為相同亦可為相異；惟，R₁ ～R₄ 當中之任一個及R₅ ～R₉ 當中之任一個為與一般式(3)中之氮原子的直接鍵結)。

(一般式(3-2)中，R₁₀ ～R₁₄ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基、與一般式(3)中之氮原子的直接鍵結之任一個，可為相同亦可為相異；R₁₅ ～R₁₉ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基、與一般式(3)中之氮原子的直接鍵結之任一個，可為相同亦可為相異；惟，R₁₀ ～R₁₄ 當中之任一個及R₁₅ ～R₁₉ 當中之任一個為與一般式(3)中之氮原子的直接鍵結；R₂₀ 、R₂₁ 分別為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基之任一個，可為相同亦可為相異)。

(一般式(3-3)中，R₂₂ ～R₂₆ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基、與一般式(3)中之氮原子的直接鍵結之任一個，可為相同亦可為相異；R₂₇ ～R₃₁ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基、與一般式(3)中之氮原子的直接鍵結之任一個，可為相同亦可為相異；惟，R₂₂ ～R₂₆ 當中之任一個及R₂₇ ～R₃₁ 當中之任一個為與一般式(3)中之氮原子的直接鍵結；R₃₂ 、R₃₃ 分別為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基之任一個，可為相同亦可為相異)。

(一般式(4)中，X為二羥基二胺類之殘基，為4價之有機基；Y為二羧酸成分之殘基，為2價之有機基；m為1以上之整數)。Another photosensitive resin composition of the present invention, which contains a polyamide-based resin (α-1) obtained by the reaction of a diamine component and a dicarboxylic acid component, and a polybenzoxazole precursor (α-2) . A photosensitive resin composition with a photosensitive agent (B), characterized in that the aforementioned polyamide-based resin (α-1) has a structure represented by the following general formula (3), and the aforementioned polybenzoxazole precursor (α -2) has a structure represented by the following general formula (4), the blending ratio of the aforementioned polyamide-based resin (α-1) to the aforementioned polybenzoxazole precursor (α-2) is 0.1 in terms of mass: 99.9～15:85.

(In the general formula (3), P is the residue of the diamine component, which is 2 with any one of the benzoxazole structures in the following general formulas (3-1), (3-2) and (3-3). valent group; R' is the residue of a dicarboxylic acid component, which is a divalent organic group; n is an integer of 1 or more).

(In general formula (3-1), R ₁ ~ R ₄ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the direct connection between nitrogen atoms in general formula (3) Any one of the bonds can be the same or different; R ₅ ~ R ₉ are hydrogen atom, organic group, nitro group, halogen atom, sulfo group, sulfonyl group, amino group, and in the general formula (3) Any one of the direct bonds of the nitrogen atom in , may be the same or different; however, any one of R ₁ to R ₄ and any one of R ₅ to R ₉ is the same as that in the general formula (3). direct bond to the nitrogen atom).

(In general formula (3-2), R ₁₀ to R ₁₄ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the direct connection between nitrogen atoms in general formula (3) Any one of the bonds may be the same or different; 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) Any one of the direct bonds of the nitrogen atom in can be the same or different; however, any one of R ₁₀ to R ₁₄ and any one of R ₁₅ to R ₁₉ is the same as that in general formula (3). direct bonding of nitrogen atom; R ₂₀ and R ₂₁ are respectively any one of hydrogen atom, organic group, nitro group, halogen atom, sulfo group, sulfonyl group and amino group, which may be the same or different).

(In general formula (3-3), R ₂₂ to R ₂₆ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the direct connection between nitrogen atoms in general formula (3) Any of the bonds can be the same or different; 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) Any one of the direct bonds of the nitrogen atom in , may be the same or different; however, any one of R ₂₂ to R ₂₆ and any one of R ₂₇ to R ₃₁ is the same as that in general formula (3). direct bonding of nitrogen atom; R ₃₂ and R ₃₃ are respectively any one of hydrogen atom, organic group, nitro group, halogen atom, sulfo group, sulfonyl group and amino group, which may be the same or different).

(In general formula (4), X is the residue of dihydroxydiamine, which is a tetravalent organic group; Y is the residue of a dicarboxylic acid component, which is a divalent organic group; m is an integer of 1 or more) .

The photosensitive resin composition of the present invention preferably further contains a crosslinking agent. Furthermore, the photosensitive resin composition of the present invention preferably contains a triazole compound having a mercapto group, and preferably uses a triazole compound having a mercapto group and a melamine-based crosslinking agent in combination. In the photosensitive resin composition of the present invention, preferably, the triazole compound having a mercapto group is 3-mercapto-1,2,4-triazole.

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

The cured product of the present invention is characterized in that it is obtained by curing the above-mentioned photosensitive resin composition or the resin layer of the above-mentioned dry film.

The semiconductor device of the present invention is characterized by having the above-mentioned cured product.

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

The electronic component of the present invention is characterized by having the aforementioned hardened product. [Effect of the invention]

According to the present invention, it is possible to provide a photosensitive resin composition capable of forming a cured film with high heat resistance and low coefficient of linear thermal expansion, and excellent in sensitivity and resolution, a dry film having a resin layer obtained from the composition, and the composition Or a cured product of the resin layer of the dry film, a semiconductor element, a printed wiring board, and an electronic component having the cured product.

The photosensitive resin composition of the present invention is as described above, and it contains a polyamide-based resin obtained by reacting a diamine component and a dicarboxylic acid component, that is, a polybenzoxazole precursor (A), and a photosensitive agent (B). In the photosensitive resin composition, in the polyamide structure of the aforementioned polybenzoxazole precursor (A), the ratio of the structure represented by the aforementioned general formula (1) is 0.1 to 15%, and the ratio of the aforementioned general formula (2) A photosensitive resin composition with a structure ratio of 85 to 99.9%, or a polyamide-based resin (α-1) obtained by the reaction of a diamine component and a dicarboxylic acid component, and a polybenzoxazole precursor The photosensitive resin composition of the substance (α-2) and the photosensitizer (B), the aforementioned polyamide-based resin (α-1) has the structure represented by the aforementioned general formula (3), the aforementioned polybenzoxazole precursor (α-2) has a structure represented by the aforementioned general formula (4), and the blending ratio of the aforementioned polyamide-based resin (α-1) to the aforementioned polybenzoxazole precursor (α-2) is 0.1 in terms of mass :99.9～15:85 photosensitive resin composition. Hereinafter, the components containing the photosensitive resin composition of the present invention will be described in detail.

[Polybenzoxazole precursor (A)] The polyamide-based resin obtained by the reaction of the diamine component and the dicarboxylic acid component, that is, the polybenzoxazole precursor (A), is a polyamide structure, 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 to 99.9%.

(一般式(1)中，P為二胺成分之殘基，為具有下述一般式(1-1)、(1-2)及(1-3)中任一種苯并噁唑構造的2價之基；R’為二羧酸成分之殘基，為2價之有機基)。

(一般式(1-1)中，R₁ ～R₄ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基、與一般式(1)中之氮原子的直接鍵結之任一個，可為相同亦可為相異；R₅ ～R₉ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基、與一般式(1)中之氮原子的直接鍵結之任一個，可為相同亦可為相異；惟，R₁ ～R₄ 當中之任一個及R₅ ～R₉ 當中之任一個為與一般式(1)中之氮原子的直接鍵結)。

(一般式(1-2)中，R₁₀ ～R₁₄ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基、與一般式(1)中之氮原子的直接鍵結之任一個，可為相同亦可為相異；R₁₅ ～R₁₉ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基、與一般式(1)中之氮原子的直接鍵結之任一個，可為相同亦可為相異；惟，R₁₀ ～R₁₄ 當中之任一個及R₁₅ ～R₁₉ 當中之任一個為與一般式(1)中之氮原子的直接鍵結；R₂₀ 、R₂₁ 分別為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基之任一個，可為相同亦可為相異)。

(一般式(1-3)中，R₂₂ ～R₂₆ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基、與一般式(1)中之氮原子的直接鍵結之任一個，可為相同亦可為相異；R₂₇ ～R₃₁ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基、與一般式(1)中之氮原子的直接鍵結之任一個，可為相同亦可為相異；惟，R₂₂ ～R₂₆ 當中之任一個及R₂₇ ～R₃₁ 當中之任一個為與一般式(1)中之氮原子的直接鍵結；R₃₂ 、R₃₃ 分別為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基之任一個，可為相同亦可為相異)。

(式(2)中，X為二羥基二胺類之殘基，為4價之有機基；Y為二羧酸成分之殘基，為2價之有機基)。

(In the general formula (1), P is the residue of the diamine component, which is 2 with any one of the benzoxazole structures in the following general formulas (1-1), (1-2) and (1-3). Valence base; R' is the residue of a dicarboxylic acid component, which is a divalent organic group).

(In general formula (1-1), R ₁ to R ₄ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the direct connection between nitrogen atoms in general formula (1) Any one of the bonds can be the same or different; R ₅ ~ R ₉ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the general formula (1) Any one of the direct bonds of the nitrogen atom in , may be the same or different; however, any one of R ₁ to R ₄ and any one of R ₅ to R ₉ is the same as that in the general formula (1). direct bond to the nitrogen atom).

(In general formula (1-2), R ₁₀ to R ₁₄ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the direct connection between nitrogen atoms in general formula (1) Any one of the bonds may be the same or different; 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) Any one of the direct bonds of the nitrogen atom in can be the same or different; however, any one of R ₁₀ to R ₁₄ and any one of R ₁₅ to R ₁₉ is the same as that in general formula (1). direct bonding of nitrogen atom; R ₂₀ and R ₂₁ are respectively any one of hydrogen atom, organic group, nitro group, halogen atom, sulfo group, sulfonyl group and amino group, which may be the same or different).

(In general formula (1-3), R ₂₂ to R ₂₆ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the direct connection between nitrogen atoms in general formula (1) Any one of the bonds can be the same or different; R ₂₇ ~ R ₃₁ are hydrogen atom, organic group, nitro group, halogen atom, sulfo group, sulfonyl group, amino group, and the general formula (1) Any one of the direct bonds of the nitrogen atom in , may be the same or different; however, any one of R ₂₂ to R ₂₆ and any one of R ₂₇ to R ₃₁ is the same as that in general formula (1). direct bonding of nitrogen atom; R ₃₂ and R ₃₃ are respectively any one of hydrogen atom, organic group, nitro group, halogen atom, sulfo group, sulfonyl group and amino group, which may be the same or different).

(In formula (2), X is a residue of dihydroxydiamine, which is a tetravalent organic group; Y is a residue of a dicarboxylic acid component, which is a divalent organic group).

Here, the so-called ratio in the structure of polyamide, except that the amide structure composed of a diamine component and a dicarboxylic acid component is taken as a calculation as in the general formula (1), means that it is equivalent to polyphenylene The ratio of the total number of amide structures in the polyamide structure contained in the oxazole precursor (A). After the 100% reaction of the diamine component and the dicarboxylic acid component is completed, the above-mentioned ratio can be any one of the general formula (1-1), (1-2) and (1-3) in the diamine component The ratio (mole conversion) of the diamine in the benzoxazole structure (hereinafter also referred to as "benzoxazole moiety") was determined. This ratio can be determined by analysis such as NMR. The total number of amide structures in the polyamide structures contained in the polybenzoxazole precursor (A) is preferably 10-30, more preferably 15-25.

When the proportion 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. Also, if the ratio exceeds 15%, the sensitivity and resolution will deteriorate. Preferably it is 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 used in the synthesis of polyamides. For example, the diamine component includes diamines, and the dicarboxylic acid component includes dicarboxylic acid, dicarboxylic acid ester, Dihalides of dicarboxylic acids such as carboxylic acid dichloride.

The structure represented by the aforementioned general formula (1) is preferably able to be repeated continuously in the polybenzoxazole precursor (A), and the number of repetitions is 1 to 5 (however, when the number of repetitions is 1, it means not repeated consecutively).

R ₁ to R ₄ , R ₅ to R ₉ in the aforementioned general formula (1-1), R ₁₀ to R ₁₄ , R ₁₅ to R ₁₉ in the aforementioned general formula (1-2), and R 15 to R 19 in the aforementioned general formula (1-1) R ₂₂ to R ₂₆ and R ₂₇ to R ₃₁ in -3) are preferably directly bonded to a hydrogen atom or a nitrogen atom in the general formula (1).

As R ₁ to R ₄ , R ₅ to R ₉ in the aforementioned general formula (1-1), R ₁₀ to R ₁₄ , R ₁₅ to R ₁₉ in the aforementioned general formula (1-2), and R 15 to R 19 in the aforementioned general formula The organic groups of R ₂₂ to R ₂₆ and R ₂₇ to R ₃₁ in formula (1-3) include, for example, alkyl groups with 1 to 3 carbons, alkoxy groups with 1 to 3 carbons, and alkoxy groups with 3 to 8 carbons. Cycloalkyl, aryl with 6 to 12 carbons, allyl, trifluoromethyl, etc.

Examples of organic groups that can be used as R ₂₀ and R ₂₁ in the general formula (1-2) and R ₃₂ and R ₃₃ in the general formula (1-3) above include alkyl groups having 1 to 3 carbon atoms, Alkoxy with 1 to 3 carbons, cycloalkyl with 3 to 8 carbons, aryl with 6 to 12 carbons, allyl, trifluoromethyl, etc.

As R ₁ to R ₉ in the aforementioned general formula (1-1), R ₁₀ to R ₂₁ in the aforementioned general formula (1-2), and R ₂₂ to R ₃₃ in the aforementioned general formula (1-3) The halogen atoms include fluorine, chlorine and bromine. Among them, fluorine is preferable in view of the relationship between the transmittance of the polymer.

As R ₁ to R ₉ in the aforementioned general formula (1-1), R ₁₀ to R ₂₁ in the aforementioned general formula (1-2), and R ₂₂ to R ₃₃ in the aforementioned general formula (1-3) The sulfonyl group includes methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, octylsulfonyl, decylsulfonyl, dodecylsulfonyl and other alkylsulfonyl groups with 1 to 10 carbon atoms.

In the above-mentioned general formula (1), as the diamine component represented by P, diamines having any one of the benzoxazole structures in the general formulas (5), (6) and (7) described later can be mentioned.

In the aforementioned general formula (1), examples of the dicarboxylic acid component represented by R' include isophthalic acid, terephthalic acid, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4 '-Dicarboxytetraphenylsilane, bis(4-carboxyphenyl) phenylene, 2,2-bis(p-carboxyphenyl)propane, 2,2-bis(4-carboxyphenyl)-1,1, Dicarboxylic acids with aromatic rings such as 1,3,3,3-hexafluoropropane, oxalic acid, malonic acid, succinic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid Acids, aliphatic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid, and their dihalides. Among them, 4,4'-dicarboxydiphenyl ether and its dihalides are preferred.

In the above-mentioned general formula (1), although the divalent organic group represented by R' can be an aliphatic group or an aromatic group, it is preferably an aromatic group, and it is more preferably on the aromatic ring and the above-mentioned general The carbonyl group in formula (1) is bonded. The number of carbon atoms in the divalent aromatic group is preferably 6-30, more preferably 6-24. Specific examples of the aforementioned divalent aromatic groups include the following groups, but are not limited thereto, and the known aromatic genes included in the polybenzoxazole precursor may be selected for the application. .

(式中，A表示選自由單鍵、-CH₂ -、-O-、-CO-、-S-、 -SO₂ -、-NHCO-、-C(CF₃ )₂ -、-C(CH₃ )₂ -所構成之群組中之2價基)。

(In the formula, A represents the group selected from single bond, -CH ₂ -, -O-, -CO-, -S-, -SO ₂ -, -NHCO-, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ - the 2-valent base in the group formed).

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

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

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

(式中，X為二羥基二胺類之殘基，為4價之有機基；Y為二羧酸成分之殘基，為2價之有機基；前述一般式(2)表示之構造可於聚苯并噁唑前驅物(A)中連續進行重複，較佳為重複數為10～30，更佳為15～25(惟，於此重複數為1時，係意指未連續進行重複))。

(wherein, X is the residue of dihydroxydiamines, which is a 4-valent organic group; Y is the residue of a dicarboxylic acid component, which is a 2-valent organic group; the structure represented by the aforementioned general formula (2) can be expressed in The polybenzoxazole precursor (A) is repeated continuously, preferably the number of repetitions is 10-30, more preferably 15-25 (however, when the number of repetitions is 1, it means that the number of repetitions is not continuously repeated) ).

Examples of dihydroxydiamines represented by X in the aforementioned 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) base) phenyl, bis(4-amino-3-hydroxyphenyl) phenyl, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexa Fluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, etc. Among them, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane is preferred.

In the aforementioned general formula (2), although the 4-valent organic group represented by X can be an aliphatic group or an aromatic group, it is preferably an aromatic group, more preferably two hydroxyl groups and two amine based groups. The ortho position is placed on the aromatic ring. The number of carbon atoms in the tetravalent aromatic group is preferably 6-30, more preferably 6-24. Specific examples of the aforementioned tetravalent aromatic group include the following groups, but are not limited thereto. Known aromatic genes included in the polybenzoxazole precursor can be selected for the application, namely Can.

The above-mentioned tetravalent aromatic group is preferably the following group among the above-mentioned 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 5,000-100,000, more preferably 8,000-50,000. Here, the number average molecular weight is measured by gel permeation chromatography (Gel Permeation chromatography; hereinafter referred to as "GPC"), and is a value converted to standard polystyrene. Also, the mass average molecular weight (Mw) of the polybenzoxazole precursor (A) is preferably 10,000-200,000, more preferably 16,000-100,000. Here, the mass average molecular weight is measured by GPC and is a value converted to standard polystyrene. Mw/Mn is preferably 1-5, more preferably 1-3.

The blending amount of the polybenzoxazole precursor (A) is preferably 60-90% by mass, more preferably 70-90% 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), even if no polymer is mixed, it can form a cured film with high heat resistance and low linear thermal expansion coefficient, and although the sensitivity and resolution are excellent, However, if necessary, two or more polybenzoxazole precursors (A) can be used in combination. Moreover, in the range which does not impair the effect of this invention, it can use together with polymers other than a polybenzoxazole precursor (A).

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

(一般式(3)中，P為二胺成分之殘基，為具有下述一般式(3-1)、(3-2)及(3-3)中之任一個苯并噁唑構造之2價基；R’為二羧酸成分之殘基，為2價之有機基；n為1以上之整數)。

(一般式(3-1)中，R₁ ～R₄ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基、與一般式(3)中之氮原子的直接鍵結之任一個，可為相同亦可為相異；R₅ ～R₉ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基、與一般式(3)中之氮原子的直接鍵結之任一個，可為相同亦可為相異；惟，R₁ ～R₄ 當中之任一個及R₅ ～R₉ 當中之任一個為與一般式(3)中之氮原子的直接鍵結)。

(一般式(3-2)中，R₁₀ ～R₁₄ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基、與一般式(3)中之氮原子的直接鍵結之任一個，可為相同亦可為相異；R₁₅ ～R₁₉ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基、與一般式(3)中之氮原子的直接鍵結之任一個，可為相同亦可為相異；惟，R₁₀ ～R₁₄ 當中之任一個及R₁₅ ～R₁₉ 當中之任一個為與一般式(3)中之氮原子的直接鍵結；R₂₀ 、R₂₁ 分別為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基之任一個，可為相同亦可為相異)。

(一般式(3-3)中，R₂₂ ～R₂₆ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基、與一般式(3)中之氮原子的直接鍵結之任一個，可為相同亦可為相異；R₂₇ ～R₃₁ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基、與一般式(3)中之氮原子的直接鍵結之任一個，可為相同亦可為相異；惟，R₂₂ ～R₂₆ 當中之任一個及R₂₇ ～R₃₁ 當中之任一個為與一般式(3)中之氮原子的直接鍵結；R₃₂ 、R₃₃ 分別為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基之任一個，可為相同亦可為相異)。

(In the general formula (3), P is the residue of the diamine component, which has any one of the benzoxazole structures in the following general formulas (3-1), (3-2) and (3-3) Divalent group; R' is the residue of a dicarboxylic acid component, which is a divalent organic group; n is an integer of 1 or more).

(In general formula (3-1), R ₁ ~ R ₄ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the direct connection between nitrogen atoms in general formula (3) Any one of the bonds can be the same or different; R ₅ ~ R ₉ are hydrogen atom, organic group, nitro group, halogen atom, sulfo group, sulfonyl group, amino group, and in the general formula (3) Any one of the direct bonds of the nitrogen atom in , may be the same or different; however, any one of R ₁ to R ₄ and any one of R ₅ to R ₉ is the same as that in the general formula (3). direct bond to the nitrogen atom).

(In general formula (3-2), R ₁₀ to R ₁₄ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the direct connection between nitrogen atoms in general formula (3) Any one of the bonds may be the same or different; 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) Any one of the direct bonds of the nitrogen atom in can be the same or different; however, any one of R ₁₀ to R ₁₄ and any one of R ₁₅ to R ₁₉ is the same as that in general formula (3). direct bonding of nitrogen atom; R ₂₀ and R ₂₁ are respectively any one of hydrogen atom, organic group, nitro group, halogen atom, sulfo group, sulfonyl group and amino group, which may be the same or different).

(In general formula (3-3), R ₂₂ to R ₂₆ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the direct connection between nitrogen atoms in general formula (3) Any of the bonds can be the same or different; 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) Any one of the direct bonds of the nitrogen atom in , may be the same or different; however, any one of R ₂₂ to R ₂₆ and any one of R ₂₇ to R ₃₁ is the same as that in general formula (3). direct bonding of nitrogen atom; R ₃₂ and R ₃₃ are respectively any one of hydrogen atom, organic group, nitro group, halogen atom, sulfo group, sulfonyl group and amino group, which may be the same or different).

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

The polyamide-based resin (α-1) is obtained by reacting a diamine component and a dicarboxylic acid component. The diamine component and the dicarboxylic acid component may be used as long as they are synthesized in polyamide. For example, as the diamine component, there are diamines, and as the dicarboxylic acid component, there are dicarboxylic acid, dicarboxylic acid ester, Dihalides of dicarboxylic acids such as carboxylic acid dichloride.

n in the aforementioned general formula (3) is preferably 1-20, more preferably 1-5.

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

In the aforementioned general formula (3), the diamine component represented by P is the same as P in the aforementioned general formula (1), and can include those having the following general formulas (5), (6) and (7). Diamines of any benzoxazole structure.

In the aforementioned general formula (3), the dicarboxylic acid component represented by R' is the same as R' in the aforementioned general formula (1).

The polyamide-based resin (α-1) may contain two or more structures represented by the general formula (3). Moreover, the structure other than the structure represented by general formula (3) may be included, For example, the structure represented by the said general formula (2) may be contained.

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

The blending amount of the polyamide-based resin (α-1) is preferably 0.1-15% in the resin component, without reducing the developability, and can improve the thermomechanical properties of the cured film.

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

(式中，X為二羥基二胺類之殘基，為4價之有機基；Y為二羧酸成分之殘基，為2價之有機基；m為1以上之整數)。

(In the formula, X is a residue of dihydroxydiamine, which is a tetravalent organic group; Y is a residue of a dicarboxylic acid component, which is a divalent organic group; m is an integer of 1 or more).

In the aforementioned general formula (4), m is an integer of 1 or more, preferably 10-50, more preferably 20-40.

The dihydroxydiamines represented by X in the general formula (4) are the same as the dihydroxydiamines represented by X in the general formula (2).

In the aforementioned general formula (4), the tetravalent organic group represented by X is the same as the tetravalent organic group represented by X in the aforementioned general formula (2).

As the aforementioned dicarboxylic acid component represented by Y in the aforementioned general formula (4), it is the same as R' in the aforementioned general formula (3), and is the same as that represented by R' in the aforementioned general formula (1). The carboxylic acid composition is the same.

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

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

The blending amount of the polybenzoxazole precursor (α-2) is preferably 85-99.9% in the resin component, so as to obtain a pattern with higher resolution.

The photosensitive resin composition of the present invention can be used in combination of two or more polyamide resins (α-1) and polybenzoxazole precursors (α-2) if necessary. In addition, it can be used in combination with polymers other than the polyamide-based resin (α-1) and the polybenzoxazole precursor (α-2) within the range that does not impair the effect of the present invention. Furthermore, the polybenzoxazole precursor (α-2) may have a benzoxazole structure within the range that does not impair the effect of the present invention, but preferably does not have a benzoxazole structure.

[Sensitizer (B)] The sensitizer (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 free radicals when irradiated with the same light. A photobase generator is a compound that generates free radicals by the same A compound in which one or more basic substances are produced by changing the molecular structure or cleavage of the molecule by light irradiation. In this invention, a photoacid generator can be used suitably as a photosensitizer (B).

Examples of photoacid generators include naphthoquinone diazide compounds, diaryl percited salts, triaryl percited salts, dialkylphenacyl percited salts, diaryl iodonium salts, aryl heavy Nitrogenium (Diazonium) salt, aromatic tetracarboxylic acid ester, aromatic sulfonate, nitrobenzyl ester, aromatic N-oxyimide sulfonate, aromatic sulfonamide, benzoquinonediazosulfonate Etc. The photoacid generator is preferably a dissolution inhibitor. Among them, naphthoquinone diazide compounds are preferred.

As the naphthoquinone diazide compound, specifically, the naphthoquinone diazide adduct of ginseng (4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (for example, Sanbao Chemical Research Institute TS533, TS567, TS583, TS593 manufactured by the company), or naphthoquinone diazide adducts of tetrahydroxybenzophenone (such as BS550, BS570, BS599 manufactured by Sanbo Chemical Research Institute, etc.).

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

(Crosslinking agent) The photosensitive resin composition of the present invention preferably contains a crosslinking agent, and by adding the crosslinking agent, the strength of the cured film during low temperature curing is increased. The crosslinking agent is not particularly limited, and known and commonly used crosslinking agents may be contained. Among them, a crosslinking agent having a phenolic hydroxyl group, a crosslinking agent having two or more methylol groups not having a phenolic hydroxyl group, a melamine-based crosslinking agent, and a urea-based crosslinking agent are preferred. Also, it is more preferable to use a crosslinking agent having a phenolic hydroxyl group in combination with a melamine-based crosslinking agent. By combining the crosslinking agent, the developability can be adjusted, and the strength of the film cured at low temperature can be improved. The blending ratio of the cross-linking agent with phenolic hydroxyl group to the melamine-based cross-linking agent is preferably 2:8-8:2 in terms of mass, more preferably 3:7-7:3, and even more preferably 4: 6~6:4. It is more preferable to use a combination of a crosslinking agent with phenolic hydroxyl groups and a crosslinking agent with two or more methylol groups without phenolic hydroxyl groups. The pattern rectangle becomes better during development and the strength of the cured film is improved. The mixing ratio of the crosslinking agent having phenolic hydroxyl groups to the crosslinking agent having two or more methylol groups without phenolic hydroxyl groups is preferably 2:8 to 8:2 in terms of mass, more preferably 3: 7-7:3, more preferably 4:6-6:4. The content of the crosslinking agent is preferably 1.5-20% by mass based on the total solid content of the composition.

(Crosslinking agent having a 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 has two or more phenolic hydroxyl groups , and more preferably a compound represented by the following general formula (A).

(一般式(A)中，R^A1 表示2～10價之有機基；R^A2 分別獨立表示氫原子或碳數1～4之烷基；n表示2～10之整數)。

(In the general formula (A), R ^A1 represents an organic group with a valence of 2 to 10; R ^A2 independently represents a hydrogen atom or an alkyl group with 1 to 4 carbons; n represents an integer of 2 to 10).

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

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

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

Also, the crosslinking agent having a phenolic hydroxyl group preferably has a fluorine atom, and more preferably has a trifluoromethyl group. The aforementioned fluorine atom or the aforementioned trifluoromethyl group is preferably an organic group having a valence of 2 to 10 represented by R ^A1 in the aforementioned general formula (A), and R ^A1 is preferably bis(trifluoromethyl)methylene . Also, the crosslinking agent having a phenolic hydroxyl group preferably has a bisphenol structure, more preferably has a bisphenol AF structure.

As a specific example of the crosslinking agent which has a phenolic hydroxyl group, the following compounds are preferable.

The crosslinking agent which has a phenolic hydroxyl group may be used individually by 1 type, and may use it in combination of 2 or more types. The blending amount of the crosslinking agent having a phenolic hydroxyl group is preferably 1-20% by mass, more preferably 3-10% by mass, based on the total solid content of the composition. With such a blending ratio, a composition with more excellent developability and pattern formation after curing can be obtained.

(Crosslinking agent having two or more methylol groups not having phenolic hydroxyl groups) The crosslinking agent having two or more methylol groups not having phenolic hydroxyl groups preferably has a molecular weight of 100 or more.

The crosslinking agent having two or more methylol groups that do not have a phenolic hydroxyl group is more preferably a compound represented by the following general formula (B).

(一般式(B)中，n表示1～10之整數，n為1時，R^B1 表示羥甲基(亦即「-CH₂ OH」)，n為2～10之整數時，R^B1 表示2～10價之有機基；R^B2 分別獨立表示碳數1～4之有機基；m1表示1～5之整數；m2表示0～4之整數)。

(In general formula (B), n represents an integer of 1 to 10, when n is 1, R ^B1 represents a hydroxymethyl group (that is, "-CH ₂ OH"), and when n is an integer of 2 to 10, R ^B1 represents 2-10 valent organic groups; R ^B2 each independently represent an organic group with 1-4 carbon atoms; m1 represents an integer of 1-5; m2 represents an integer of 0-4).

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

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

Specific examples of the crosslinking agent having two or more methylol groups that do not have a phenolic hydroxyl group are preferably the following compounds.

The crosslinking agent having two or more methylol groups that do not have a phenolic hydroxyl group may be used alone or in combination of two or more. The blending amount of the crosslinking agent having two or more methylol groups without phenolic hydroxyl groups is preferably 1 to 20% by mass based on the total solid content of the composition. With such a blending ratio, a composition with more excellent developability and pattern formation after curing can be obtained.

(式中，以R^C1A 、R^C2A 、R^C3A 、R^C4A 、R^C5A 及R^C6A 分別獨立為碳數1～3之伸烷基較佳；以R^C1B 、R^C2B 、R^C3B 、R^C4B 、R^C5B 及R^C6B 分別獨立為氫原子或碳數1～3之烷基較佳)。(Melamine-Based Crosslinking Agent) The melamine-based crosslinking agent is not particularly limited if it has a melamine structure, but is preferably a melamine-based crosslinking agent represented by the following general formula (C).

(In the formula, R ^C1A , R ^C2A , R ^C3A , R ^C4A , R ^C5A and R ^C6A are each independently an alkylene group with 1 to 3 carbons; R ^C1B , R ^C2B , R ^C3B , R ^C4B , R ^C5B and R ^C6B are each independently a hydrogen atom or an alkyl group with 1 to 3 carbons (preferably).

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

The melamine-based crosslinking agent may be used alone or in combination of two or more. The blending amount of the melamine-based crosslinking 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 rate of the unexposed part can be further increased, and the development residue of the exposed part can be prevented.

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

(式中，R^D1 、R^D2 分別獨立表示氫原子或一價有機基)。

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

(式中，R^E1 分別獨立表示氫原子或一價之有機基，R^E2 表示二價之有機基)。

(In the formula, R ^E1 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. Examples include 1,3,4,6-tetra(methoxymethyl)glycoluril, 1,3,4,6-tetra(butoxymethyl)glycoluril, 4,5-dimethyl Oxy-1,3-bis(methoxymethyl)imidazolidin-2-one, etc. As a commercial item, Nikalack MX-270, MX-279, MX-280 etc. manufactured by Sanwa Chemical Co., Ltd. are mentioned, for example.

As a specific compound of a urea type crosslinking agent, the compound etc. which are shown below can be used.

The urea crosslinking agent may be used alone or in combination of two or more. The blending amount of the urea-based crosslinking 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 development.

(Thiol compound) The photosensitive resin composition of this invention may 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-dithiohalitol and 2-mercaptoethanol, the following compounds and the like can be used. Among them, D,L-dithiohalitol is preferred.

(式(5)中，R₄₁ 較佳為氫原子或碳數1～3之烷基，更佳為氫原子)。 　　具有巰基之三唑化合物可單獨1種使用，亦可組合2種以上使用。具有巰基之三唑化合物的摻合量以組成物固體成分全量基準，較佳為0.1～5.0質量%，更佳為0.5～2.0質量%。 　　又，根據本發明，藉由併用具有巰基之三唑化合物與三聚氰胺系交聯劑，即使增長顯影時間的情況下，亦可兼具顯影殘渣的抑制與耐顯影性。尚，所謂在本發明之耐顯影性，係指顯影後之殘膜率高，且於硬化膜表面無圖案或裂紋。A thiol compound may be used individually by 1 type, and may use it in combination of 2 or more types. The blending amount of the thiol compound is preferably 0.01-20% by mass, more preferably 0.1-10% by mass, based on the total solid content of the composition. By setting it as the said range, generation|occurrence|production of scum can be suppressed more reliably. The photosensitive resin composition of the present invention preferably contains a triazole compound having a mercapto group. Although the detailed mechanism is not yet clear, it improves the adhesion to the copper substrate and can further suppress the development residue on the copper. The triazole compound having a mercapto group is not particularly limited as long as it has a mercapto group and has a triazole structure, but examples of the triazole compound having a mercapto group include 3-mercapto-1,2,4-triazole azole, 3-mercapto-4-methyl-4H-1,2,4-triazole, etc. Among them, a compound in which a mercapto group is directly bonded to a triazole ring such as the above-mentioned compounds is preferable. Furthermore, the triazole compound having a mercapto group is more preferably a compound represented by the following general formula (5), particularly preferably 3-mercapto-1,2,4-triazole.

(In formula (5), R ₄₁ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbons, more preferably a hydrogen atom). The triazole compound having a mercapto group may be used alone or in combination of two or more. The blending amount of the triazole compound having a mercapto group is preferably 0.1-5.0% by mass, more preferably 0.5-2.0% by mass, based on the total solid content of the composition. Also, according to the present invention, by using a triazole compound having a mercapto group and a melamine-based crosslinking agent in combination, suppression of development residue and development resistance can be achieved simultaneously even when the development time is prolonged. Furthermore, the so-called development resistance in the present invention means that the residual film rate after development is high, and there are no patterns or cracks on the surface of the cured film.

(Urea Compound) The photosensitive resin composition of the present invention may contain a urea compound. By containing the urea compound, the dissolution rate of the resin can be adjusted, and the pattern formation property can be improved. The urea compound is not particularly limited, and for example, 1,3-diphenylurea, 1,3-bis[4-(trifluoromethyl)phenyl]urea, N,N'-bis(trimethyl)urea, silyl)urea, 1-acetyl-3-methylurea, 1-acetyl-2-thiourea, acetylurea, 1-adamantylthiourea, 1-allyl-3-( 2-Hydroxyethyl)-2-thiourea, benzoylurea, 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-methoxy phenyl)urea, biurea, butylurea, N,N'-diethyl-N,N'-diphenylurea, etc.

A urea compound may be used individually by 1 type, and may use it in combination of 2 or more types. The blending amount of the urea compound is preferably 0.01-15% by mass, more preferably 0.05-10% by mass, based on the total solid content of the composition. By making it into the above-mentioned range, the remaining film ratio is improved, and the developability of the thick photosensitive film on the metal substrate is improved, and a better pattern shape can be obtained after development.

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

The silane coupling agent with arylamine group will be explained. Examples of the aryl group of the arylamino group include aromatic hydrocarbon groups such as phenyl, tolyl, and xylyl, condensed polycyclic aromatic groups such as naphthyl, anthracenyl, and phenanthrenyl, and thienyl. , Indolyl and other aromatic heterocyclic groups.

(式中，R^F1 ～R^F5 分別獨立表示氫原子或有機基)。The silane coupling agent having an arylamine 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.

For the silane coupling agent with arylamine group, the silicon atom and the arylamine group are preferably organic groups with 1 to 10 carbons, preferably alkylene groups with 1 to 10 carbons.

As a specific example of the silane coupling agent which has an arylamino group, the compound shown below is preferable.

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

For the silane coupling agent having two or more trialkoxysilyl groups, at least two silicon atoms are bonded by an organic group with 1 to 10 carbons, preferably an alkylene group with 1 to 10 carbons.

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

Silane coupling agents may be used alone or in combination of two or more. In addition, a silane coupling agent other than the silane coupling agent having the above-mentioned arylamine 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 image residue on the exposed portion.

A solvent may 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 other arbitrary additives. Specific examples of solvents include N,N'-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N,N'-dimethylacetamide, diethylene glycol Alcohol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-ring Hexyl-2-pyrrolidone, dimethylsulfoxide, hexamethylphosphoramide, pyridine, γ-butyrolactone, diethylene glycol monomethyl ether. 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) depending on the coating film thickness or viscosity.

In the photosensitive resin composition of the present invention, known sensitizers, adhesion aids, etc. may be blended within the range that does not impair the effects of the present invention.

In addition, various other organic or inorganic low-molecular or high-molecular compounds may be blended in the photosensitive resin composition of the present invention in order to impart processability or various functionalities. For example, surfactants, leveling agents, plasticizers, fine particles, etc. can be used. Microparticles include organic microparticles such as polystyrene and polytetrafluoroethylene, and inorganic microparticles such as colloidal silica, carbon, and layered silicate. Furthermore, various coloring agents, fibers, etc. can be blended in the photosensitive resin composition of this invention.

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

The dry film of the present invention can be formed by applying the photosensitive resin composition of the present invention to a carrier film (support film) by using a knife coater, a lip coater, a chip coater, a film coater, etc. An appropriate method is to uniformly apply and dry to form the aforementioned resin layer, preferably by laminating a cover film (protective film) thereon. The cover film and the carrier film can be made of the same film material, or different films can be used.

In the dry film of the present invention, the film materials of the carrier film and the cover film are used as the dry film, and known ones 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, etc. can be used, but those with smaller adhesion to the resin layer than the carrier film are preferable.

The film thickness of the resin layer on the dry film of the present invention is preferably less than 100 μm, more preferably in the range of 5-50 μm.

The photosensitive resin composition of the present invention is preferably positive type. Using the photosensitive resin composition of the present invention, a patterned film of its cured product is produced, for example, as follows. Furthermore, in the following production method, although the polybenzoxazole precursor (A) is included, the polyamide-based resin (α-1) and the polybenzoxazole precursor (α- 2) is also the same.

First, as step 1, a coating film is obtained by applying a photosensitive resin composition on a base material and drying it, or by transferring (laminating) a resin layer from a dry film onto a base material. As a method of coating the photosensitive resin composition on the base material, methods that have been used in the past for coating photosensitive resin compositions can be used, such as spin coater, bar coater, knife coater, curtain coater, etc. Coating methods such as type coater, screen printing machine, etc., spray coating method with spraying machine, and inkjet method etc. can also be used. As a drying method of the coating film, methods such as air drying, heat drying in an oven or a hot plate, vacuum drying, and the like are used. In addition, drying of the coating film is desirably performed under conditions that do not cause ring closure of the polybenzoxazole precursor (A) in the photosensitive resin composition. Specifically, natural drying, ventilation drying, or heat drying can be performed at 70 to 140° C. for 1 to 30 minutes. Drying is preferably carried out on a hot plate for 1 to 20 minutes. Moreover, vacuum drying is also possible, and in this case, it can carry out at room temperature on conditions of 20 minutes - 1 hour.

The base material is not particularly limited, and can be widely applied to base materials composed of semiconductor base materials such as silicon wafers, wiring boards, various resins, or metals.

Next, as step 2, the above-mentioned coating film is passed through a photomask with a pattern, or directly exposed. Exposure light is used to activate the photoacid generator as the photosensitizer (B) to generate an acid. Specifically, the exposure light is preferably within the range of a maximum wavelength of 350 to 410 nm. As mentioned above, the photosensitivity can be adjusted by using an appropriate sensitizer. As the exposure apparatus, a contact aligner, a mirror projection, a stepper, a laser direct exposure apparatus, etc. can be used.

Next, as step 3, heating may be performed to ring-close a part of the polybenzoxazole precursor (A) in the unexposed portion. Here, the closed-loop rate is about 30%. The heating time and heating temperature are appropriately changed depending on the type of the polybenzoxazole precursor (A), the coating film thickness, and the photoacid generator as the photosensitizer (B).

Next, as Step 4, the coating film is treated with a developing solution. Thereby, the exposed part in the coating film can be removed, and the patterned film of the photosensitive resin composition of the present invention can be formed.

As the method used for development, conventionally known photoresist development methods can be selected, for example, any method can be selected from the rotary spray method, the paddle method, the method accompanied by immersion ultrasonic treatment, and the like. Examples of the developer include inorganic bases such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia, organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, tetramethylhydrogen Aqueous solutions of quaternary ammonium salts such as ammonium oxide and tetrabutylammonium hydroxide. Also, if necessary, water-soluble organic solvents such as methanol, ethanol, and isopropyl alcohol, or surfactants can be added in an appropriate amount. Then, if necessary, the coated film is washed with a cleaning solution to obtain a patterned film. As a cleaning solution, distilled water, methanol, ethanol, isopropyl alcohol, etc. can be used alone or in combination. Moreover, as a developing solution, the above-mentioned solvent can be used.

Then, as step 5, the patterned film is heated to obtain a cured coating film (cured product). In this case, the polybenzoxazole precursor (A) may be ring-closed 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 180-320°C. Heating can be performed, for example, by using a hot plate, an oven, or a temperature-programmable heating oven. As the atmosphere (gas) at this time, air may be used, and inert gases such as nitrogen and argon may be used.

The application of the photosensitive resin composition of the present invention is not particularly limited. For example, it can be suitably used as a paint, printing ink, or adhesive agent, or a forming material for display devices, semiconductor devices, electronic parts, optical parts, or building materials. Specifically, as a display device forming material, as a layer forming material or an image forming material, it can be used in a color filter, a flexible display film, a resist material, an alignment film, and the like. In addition, as a material for forming a semiconductor device, for example, a resist material, a material for forming a layer of a buffer coating film, and the like can be used. Furthermore, as a forming material of electronic parts, as a sealing material or a layer forming material, it can be used in a printed wiring board, an interlayer insulating film, a wiring covering film, and the like. Furthermore, as a forming material of optical parts, as an optical material or a layer forming material, it can be used for a hologram, an optical waveguide, an optical circuit, an optical circuit part, an antireflection 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 patterned film formed thereby is used as a permanent film composed of polybenzoxazole, because it is used as a component for imparting heat resistance or insulation, In particular, it is suitable as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, a protective film for a device with a concave-convex structure, and an interlayer insulation of a multilayer circuit for semiconductor devices, display devices, and light-emitting devices. Films, insulating materials for passive parts, protective films for printed wiring boards such as solder resists or cladding films, and liquid crystal alignment films.

Although the method for producing the photosensitive resin composition of the present invention is not particularly limited, the aforementioned polyamide-based resin obtained by the reaction of the diamine component and the dicarboxylic acid component, that is, the polybenzoxazole precursor (A) is blended In the production method of the photosensitive resin composition with the photosensitizer (B), as the aforementioned diamine, by using any one of the following general formulas (5), (6) and (7) with a benzoxazole structure Diamine components can be properly produced. In addition, the photosensitive resin containing the polyamide-based resin (α-1) obtained by the reaction of the diamine component and the dicarboxylic acid component, the polybenzoxazole precursor (α-2), and the photosensitive agent (B) In the production method of the permanent resin composition, as the above-mentioned diamine, by using a diamine component having any one of the benzoxazole structures in the following general formulas (5), (6) and (7), it can be appropriately produced .

(一般式(5)中，R₁ ～R₄ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基之任一個，可為相同亦可為相異；R₅ ～R₉ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基之任一個，可為相同亦可為相異；惟，R₁ ～R₄ 當中之任一個及R₅ ～R₉ 當中之任一個為胺基)。

(一般式(6)中，R₁₀ ～R₁₄ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基或胺基之任一個，可為相同亦可為相異。R₁₅ ～R₁₉ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基之任一個，可為相同亦可為相異；惟，R₁₀ ～R₁₄ 當中之任一個及R₁₅ ～R₁₉ 當中之任一個為胺基；R₂₀ 、R₂₁ 分別為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基之任一個，可為相同亦可為相異)。

(一般式(7)中，R₂₂ ～R₂₆ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基之任一個，可為相同亦可為相異；R₂₇ ～R₃₁ 為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基之任一個，可為相同亦可為相異；惟，R₂₂ ～R₂₆ 當中之任一個及R₂₇ ～R₃₁ 當中之任一個為胺基；R₃₂ 、R₃₃ 分別為氫原子、有機基、硝基、鹵素原子、磺基、磺醯基、胺基之任一個，可為相同亦可為相異)。 [實施例]

(In the general formula (5), R ₁ to R ₄ are any one 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 ~ _R9 is any one 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, any _one of R1~R4 and Any one of R ₅ to R ₉ is an amino group).

(In general formula (6), R ₁₀ to R ₁₄ are any one of hydrogen atom, organic group, nitro group, halogen atom, sulfo group, sulfonyl group or amino group, which may be the same or different. R ₁₅ ~ _R19 is any one 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, any _one of R10 ~ _R14 and Any one of R ₁₅ to R ₁₉ is an amino group; R ₂₀ and 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 can be the same or can be is different).

(In general formula (7), R ₂₂ to R ₂₆ are any one of hydrogen atom, organic group, nitro group, halogen atom, sulfo group, sulfonyl group, and amino group, which may be the same or different; R ₂₇ ~ _R31 is any one 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, any one of _R22 ~ _R26 and Any one of R ₂₇ to R ₃₁ is an amino group; R ₃₂ and R ₃₃ 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 is different). [Example]

Hereinafter, although the present invention will be described in more detail using examples, the present invention is not limited to the following examples. Also, the so-called "parts" and "%" in the following are all quality standards unless otherwise specified.

(Synthesis of polybenzoxazole precursor A-1) (10% benzoxazole part) In a 0.5-liter flask equipped with a stirrer and a thermometer, place 85 g of N-methylpyrrolidone and stir to dissolve bis(3-amine 10.29 g (28.1 mmol) of 4-hydroxyphenyl)hexafluoropropane and 0.70 g (3.12 mmol) of 2-(4-aminophenyl)-5-aminobenzoxazole. Then, the flask was immersed in an ice bath, and 10.00 g (33.9 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride was directly added as a solid over 10 minutes while keeping the inside of the flask at 0 to 5° C. Stir in ice bath for 30 minutes. Stirring was then continued for 18 hours at room temperature. Pour the stirred solution into 400mL of ion-exchanged water (specific resistance value 18.2MΩ･cm), and recover the precipitate. Then, the obtained solid was dissolved in 420 mL of acetone, and 1 L of ion-exchanged water was added. After recovering the separated body, it is dried under reduced pressure to obtain a partially cyclized polybenzoxazole precursor at the carboxyl end. The weight-average molecular weight calculated in terms of standard polystyrene by the GPC method was 31,700.

(Synthesis of polybenzoxazole precursor A-2) (5% benzoxazole part) In a 0.5-liter flask equipped with a stirrer and a thermometer, place 85 g of N-methylpyrrolidone and stir to dissolve bis(3-amine 10.86 g (29.65 mmol) of 4-hydroxyphenyl)hexafluoropropane and 0.7 g (1.55 mmol) of 2-(4-aminophenyl)-5-aminobenzoxazole. Then, 10.00 g (33.9 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride was directly added as a solid over 10 minutes while the flask was immersed in an ice bath, and the inside of the flask was kept at 0 to 5°C. Stir in ice bath for 30 minutes. Stirring was then continued for 18 hours at room temperature. Pour the stirred solution into 400mL of ion-exchanged water (specific resistance value 18.2MΩ･cm), and recover the precipitate. Then, the obtained solid was dissolved in 420 mL of acetone, and 1 L of ion-exchanged water was added. After recovering the separated body, it is dried under reduced pressure to obtain a partially cyclized polybenzoxazole precursor at the carboxyl end. The weight-average molecular weight calculated in terms of standard polystyrene by the GPC method was 33,700.

(Synthesis of polybenzoxazole precursor R-1) (30% benzoxazole part) In a 0.5-liter flask equipped with a stirrer and a thermometer, place 85 g of N-methylpyrrolidone and stir to dissolve bis(3-amine 8.00 g (21.8 mmol) of 4-hydroxyphenyl)hexafluoropropane and 2.09 g (9.32 mmol) of 2-(4-aminophenyl)-5-aminobenzoxazole. Then, 10.00 g (33.9 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride was directly added as a solid over 10 minutes while the flask was immersed in an ice bath, and the inside of the flask was kept at 0 to 5°C. Stir in ice bath for 30 minutes. Stirring was then continued for 18 hours at room temperature. Pour the stirred solution into 400mL of ion-exchanged water (specific resistance value 18.2MΩ･cm), and recover the precipitate. Then, the obtained solid was dissolved in 420 mL of acetone, and 1 L of ion-exchanged water was added. After recovering the separated body, it is dried under reduced pressure to obtain a partially cyclized polybenzoxazole precursor at the carboxyl end. The weight-average molecular weight calculated in terms of standard polystyrene by the GPC method was 28,200.

(Synthesis of polybenzoxazole precursor R-2) (0% benzoxazole part) In a 0.5-liter flask equipped with a stirrer and a thermometer, place 212 g of N-methylpyrrolidone and stir to dissolve bis(3-amine 60.52 g (165.22 mmol) of 4-hydroxyphenyl) hexafluoropropane. Then, the flask was immersed in an ice bath, and 53.02 g (179.65 mmol) of 4,4-diphenylether dicarboxylic acid chloride was directly added as a solid per 5 g over 30 minutes while keeping the inside of the flask at 0 to 5°C. Stir in ice bath for 30 minutes. Then, stirring was continued at room temperature for 5 hours. Put the stirred solution into 1L of ion-exchanged water (specific resistance value 18.2MΩ･cm), and recover the precipitate. Then, the obtained solid was dissolved in 420 mL of acetone, and 1 L of ion-exchanged water was added. After recovering the separated body, it was dried under reduced pressure to obtain a polybenzoxazole (PBO) precursor (R-2) having the following repeating structure at the carboxyl end. 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 the Mw/Mn was 2.45.

･其他醯胺構造

The polybenzoxazole precursors A-1, A-2, R-1 and A-3 described later are in the polyamide structure and have: the amide structure with the following benzoxazole structure and others 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 physical properties) After dissolving 100 parts by mass of polybenzoxazole precursor A-1 and 10 parts by mass of azonaphthoquinone compound in 300 parts by mass of γ-butyrolactone, filter through a 0.2 μm filter , to obtain the varnish of the photosensitive resin composition. This 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 film with a film thickness of about 30 μm. Next, use an oven to heat the coated silicon wafer at 150°C/30 minutes, 250°C/30 minutes, and 320°C/30 minutes. The obtained cured film was peeled off from the silicon wafer, and the glass transition temperature (Tg) and thermal expansion coefficient (CTE) were measured by TMA (thermomechanical analysis).

(Pattern making) The above-mentioned varnish was coated on 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 with 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 for drawing a pattern of 1 to 30 μm. After exposure, it was developed in 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 120 seconds, and washed with water to obtain a positive-type cured film pattern.

(Evaluation of remaining film rate in unexposed areas) The film thickness was measured from the cured film after development, and was determined as a ratio to the film thickness before development, and the remaining film rates in unexposed areas were obtained respectively. Residual film rate=(film thickness after development/μm)/(film thickness before development/μm)×100

(Evaluation of Sensitivity and Resolution) Observe the pattern after development with an electron microscope (SEM "JSM-6010"), and determine the resolution (L( μm)/S(μm)), the exposure at this time is defined as the sensitivity.

(Example 2) Except changing the polybenzoxazole precursor to A-2, it carried out similarly to Example 1, and evaluated.

(Comparative Example 1) Evaluation was performed in the same manner as in Example 1 except that the polybenzoxazole precursor was changed to R-1. When evaluating developability, the exposed part is not dissolved in the developer solution and no pattern can be obtained.

(Comparative Example 2) Evaluation was performed in the same manner as in Example 1 except that the polybenzoxazole precursor was changed to R-2. When evaluating developability, the exposed part and the unexposed part were all dissolved in the developer solution, and a pattern could not be obtained.

(Synthesis of polybenzoxazole precursor A-3) (2% benzoxazole part) In a 0.5-liter flask equipped with a stirrer and a thermometer, place 85 g of N-methylpyrrolidone and stir to dissolve bis(3-amine 11.21 g (30.6 mmol) of 4-hydroxyphenyl)hexafluoropropane and 0.145 g (0.644 mmol) of 2-(4-aminophenyl)-5-aminobenzoxazole. Then, 10.10 g (34.2 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride was directly added as a solid over 10 minutes while the flask was immersed in an ice bath, and the inside of the flask was kept at 0 to 5°C. Stir in ice bath for 30 minutes. Stirring was then continued for 18 hours at room temperature. Pour the stirred solution into 400mL of ion-exchanged water (specific resistance value 18.2MΩ･cm), and recover the precipitate. Then, the obtained solid was dissolved in 420 mL of acetone, and 1 L of ion-exchanged water was added. After recovering the separated body, it is dried under reduced pressure to obtain a partially cyclized polybenzoxazole precursor at the carboxyl end. The weight-average molecular weight calculated in terms of standard polystyrene by the GPC method was 34,500.

(Example 3) 100 parts by mass of polybenzoxazole precursor A-2, 10 parts by mass of azonaphthoquinone compound, N-phenyl-3-aminopropyltrimethoxysilane (KBM-573) 5 Parts by mass were dissolved in 300 parts by mass of γ-butyrolactone, and filtered through a 0.2 μm filter to obtain a varnish of a photosensitive resin composition. This 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 film with a film thickness of about 30 μm. Next, use an oven to heat the coated silicon wafer at 150°C/30 minutes and 250°C/30 minutes. The obtained cured film was peeled off from the silicon wafer, and the glass transition temperature (Tg) and thermal expansion coefficient (CTE) were measured by TMA (thermomechanical analysis). In addition, the above-mentioned 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 film with a film thickness of about 5 μm. The i-line exposure of 300-600mJ/cm< ² > was implemented with respect to the obtained coating film. After exposure, it was developed in 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 120 seconds, and washed with water to obtain a positive-type cured film pattern.

(Example 4) Except adding 10 mass parts of TML-BPAF-MF, it carried out similarly to Example 3, and evaluated.

(Example 5) The 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 Industry) was added.

(Example 6) Except adding 5 parts by mass of TML-BPAF-MF (Honshu Chemical) and 5 parts by mass of MW390 (Sanwa Chemical), it was evaluated in the same manner as in Example 3.

(Example 7) 100 parts by mass of polybenzoxazole precursor A-3, 10 parts by mass of azonaphthoquinone compound, 5 parts by mass of TML-BPAF-MF, 5 parts by mass of 1,4-benzenedimethanol, N -5 parts by mass of phenyl-3-aminopropyltrimethoxysilane (KBM-573) was dissolved in 300 parts by mass of γ-butyrolactone, and filtered through a 0.2 μm filter to obtain a varnish of photosensitive resin composition . This 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 film with a film thickness of about 30 μm. Next, use an oven to heat the coated silicon wafer at 150°C/30 minutes, 250°C/30 minutes, and 320°C/30 minutes. The obtained cured film was peeled off from the silicon wafer, and the glass transition temperature (Tg) and thermal expansion coefficient (CTE) were measured by TMA (thermomechanical analysis). In addition, the above-mentioned 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 film with a film thickness of about 5 μm. The i-line exposure of 300-600mJ/cm< ² > was implemented with respect to the obtained coating film. After exposure, it was developed in 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 120 seconds, and washed with water to obtain a positive-type cured film pattern.

(Example 8) In addition to changing the polybenzoxazole precursor to A-2, adding 1 mass part of dithiothreitol and 1 mass part of diphenylurea as additives, and not adding TML-BPAF-MF and 1, Except for 4-benzenedimethanol, the others were evaluated in the same manner as in Example 7.

(Example 9) Dissolve 100 parts by mass of polybenzoxazole precursor A-2, 10 parts by mass of azonaphthoquinone compound, 1 part by mass of mercaptotriazole, and 5 parts by mass of KBM-573 in 300 parts by mass of γ-butyrolactone After the portion, it was filtered with a 0.2 μm filter to obtain a varnish of a photosensitive resin composition. This varnish was coated on a 6-inch silicon wafer using a spin coater, and dried on a hot plate at 110°C for 30 minutes to obtain a coating film with a film thickness of about 30 μm. Next, use an oven to heat the coated silicon wafer at 150°C/30 minutes and 320°C/30 minutes. The obtained cured film was peeled off from the silicon wafer, and the glass transition temperature (Tg) and thermal expansion coefficient (CTE) were measured by TMA (thermomechanical analysis). In addition, the remaining film rate, resolution, and sensitivity were evaluated in the same manner as above.

(Example 10) Except that the polybenzoxazole precursor was changed to A-3, it was performed in the same manner as in Example 9 to measure and evaluate.

(Example 11) As a melamine-based compound, except adding 5 parts by mass of MW390, it was performed in the same manner as in Example 10 to measure and evaluate.

(Pattern making) Each of the above-mentioned compositions of Examples 9 to 11 was coated on a 5-inch Cu sputtered silicon wafer using a spin coater, and dried on a hot plate at 110°C for 3 minutes to obtain a film thickness Coating film of about 5 μm. The obtained coating film was subjected to i-line exposure at 500 to 800 mJ/cm ² through a mask for drawing a pattern of 1 to 30 μm. After exposure, it was developed in 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 80 seconds, and washed with water to obtain a positive-type cured film pattern.

(Development resistance) After development, the L/S=20μm/20μm pattern was observed with an electron microscope (SEM "JSM-6010"), and the development resistance was evaluated according to the following criteria. ◎: The remaining film rate after development is over 90% and there is no pattern or crack on the surface of the patterned hardened film. ○: The residual film rate after development is more than 80% but less than 90% and there is no pattern or crack on the surface of the cured film. ×: The remaining film rate is less than 80% or there are patterns or cracks on the surface of the hardened film. (Development residue) Observe the developed L/S=20μm/20μm pattern with an electron microscope (SEM "JSM-6010") to confirm the presence or absence of development residue. If there is no development residue in the size of the mask pattern, it is defined as ◎, the case of a pattern that is narrower than the portion of the mask pattern that has no residue is designated as ○, and the case of a residue is designated as ×.

Mercaptotriazole

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

Claims (9)

A photosensitive resin composition, which is a photosensitive resin containing a polyamide-based resin obtained by reacting a diamine component and a dicarboxylic acid component, that is, a polybenzoxazole precursor (A), and a photosensitive agent (B) The composition is characterized in that in the polyamide structure of the aforementioned polybenzoxazole precursor (A), the ratio of the structure represented by the following general formula (1) is 0.1 to 15%, and the following general formula (2) represents The proportion of the structure is 85~99.9% (Here, the proportion of the so-called polyamide structure, except for the general formula (1), the amide structure composed of a diamine component and a dicarboxylic acid component is taken as a calculation In addition, it means the ratio corresponding to the total number of amide structures in the polyamide structure contained in the polybenzoxazole precursor (A),

(In the general formula (1), P is the residue of the diamine component, which is 2 with any one of the benzoxazole structures in the following general formulas (1-1), (1-2) and (1-3). valent base; R' is the residue of a dicarboxylic acid component, which is a divalent organic group)

(In the general formula (1-1), R ₁ ~ R ₄ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the direct connection between nitrogen atoms in the general formula (1) Any one of the bonds can be the same or different; R ₅ ~ R ₉ are hydrogen atom, organic group, nitro group, halogen atom, sulfo group, sulfonyl group, amino group, and in the general formula (1) Any one of the direct bonds of the nitrogen atom can be the same or different; however, any one of R ₁ ~ R ₄ and any one of R ₅ ~ R ₉ is the same as that of the general formula (1). direct bond to the nitrogen atom)

(In the general formula (1-2), R ₁₀ ~ R ₁₄ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, direct connections with the nitrogen atoms in the general formula (1) Any one of the bonds can be the same or different; R ₁₅ ~ R ₁₉ are hydrogen atom, organic group, nitro group, halogen atom, sulfo group, sulfonyl group, amino group, and in general formula (1) Any one of the direct bonds of the nitrogen atom can be the same or different; however, any one of R ₁₀ ~ R ₁₄ and any one of R ₁₅ ~ R ₁₉ is the same as that of the general formula (1). Direct bonding of nitrogen atom; R ₂₀ and R ₂₁ are respectively any one of hydrogen atom, organic group, nitro group, halogen atom, sulfo group, sulfonyl group, and amino group, which may be the same or different)

(In the general formula (1-3), R ₂₂ ~ R ₂₆ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the direct connection between nitrogen atoms in the general formula (1) Any one of the bonds can be the same or different; R ₂₇ ~ R ₃₁ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the general formula (1) Any one of the direct bonds of the nitrogen atom can be the same or different; however, any one of R ₂₂ ~ R ₂₆ and any one of R ₂₇ ~ R ₃₁ is the same as that of the general formula (1). Direct bonding of nitrogen atom; R ₃₂ and R ₃₃ are respectively any one of hydrogen atom, organic group, nitro group, halogen atom, sulfo group, sulfonyl group, and amino group, which may be the same or different)

(In the general formula (2), X is a residue of dihydroxydiamine, which is a tetravalent organic group; Y is a residue of a dicarboxylic acid component, which is a divalent organic group). A photosensitive resin composition comprising a polyamide-based resin (α-1) obtained by reacting a diamine component and a dicarboxylic acid component, a polybenzoxazole precursor (α-2), and a photosensitive The photosensitive resin composition of agent (B) is characterized in that the aforementioned polyamide-based resin (α-1) has a structure represented by the following general formula (3), and the aforementioned polybenzoxazole precursor (α-2) It has a structure represented by the following general formula (4), and the blending ratio of the aforementioned polyamide-based resin (α-1) to the aforementioned polybenzoxazole precursor (α-2) is 0.1:99.9~15 in terms of mass :85,

(In the general formula (3), P is the residue of the diamine component, which is 2 with any one of the benzoxazole structures in the following general formulas (3-1), (3-2) and (3-3). valent group; R' is the residue of a dicarboxylic acid component, which is a divalent organic group; n is an integer of 1 or more)

(In the general formula (3-1), R ₁ ~ R ₄ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, and the direct connection between nitrogen atoms in the general formula (3) Any one of the bonds can be the same or different; R ₅ ~ R ₉ are hydrogen atom, organic group, nitro group, halogen atom, sulfo group, sulfonyl group, amino group, and in general formula (3) Any one of the direct bonds of the nitrogen atom can be the same or different; however, any one of R ₁ ~ R ₄ and any one of R ₅ ~ R ₉ is the same as that of the general formula (3). direct bond to the nitrogen atom)

(In the general formula (3-2), R ₁₀ ~ R ₁₄ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, direct connections with the nitrogen atoms in the general formula (3) Any one of the bonds can be the same or different; R ₁₅ ~ R ₁₉ are hydrogen atom, organic group, nitro group, halogen atom, sulfo group, sulfonyl group, amino group, and in general formula (3) Any one of the direct bonds of the nitrogen atom can be the same or different; however, any one of R ₁₀ ~ R ₁₄ and any one of R ₁₅ ~ R ₁₉ is the same as that of the general formula (3). Direct bonding of nitrogen atom; R ₂₀ and R ₂₁ are respectively any one of hydrogen atom, organic group, nitro group, halogen atom, sulfo group, sulfonyl group, and amino group, which may be the same or different)

(In the general formula (3-3), R ₂₂ ~ R ₂₆ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, direct connections with the nitrogen atoms in the general formula (3) Any one of the bonds can be the same or different; R ₂₇ ~ R ₃₁ are hydrogen atom, organic group, nitro group, halogen atom, sulfo group, sulfonyl group, amino group, and in general formula (3) Any one of the direct bonds of the nitrogen atom can be the same or different; however, any one of R ₂₂ ~ R ₂₆ and any one of R ₂₇ ~ R ₃₁ is the same as that of the general formula (3). Direct bonding of nitrogen atom; R ₃₂ and R ₃₃ are respectively any one of hydrogen atom, organic group, nitro group, halogen atom, sulfo group, sulfonyl group, and amino group, which may be the same or different)

(In general formula (4), X is the residue of dihydroxydiamine, which is a tetravalent organic group; Y is the residue of a dicarboxylic acid component, which is a divalent organic group; m is an integer of 1 or more) . The photosensitive resin composition according to claim 1 or 2, which further contains a crosslinking agent. The photosensitive resin composition according to Claim 1 or 2, which further contains a triazole compound having a mercapto group. A dry film, characterized by having a resin layer obtained by coating the photosensitive resin composition according to any one of claims 1 to 4 on a film and drying it. A cured product, characterized by curing the photosensitive resin composition according to any one of claims 1 to 4 or curing the resin layer of the dry film according to claim 5. A semiconductor element characterized by having the hardened product as claimed in claim 6. A printed wiring board characterized by having the hardened product as claimed in claim 6. An electronic component characterized by having the hardened product as claimed in claim 6.