TWI793136B - Photosensitive resin composition, resin film and electronic device - Google Patents

Abstract

The present invention provides: a photosensitive resin composition, which includes: a silane compound with a specific structure, an alkali-soluble resin, and a photosensitizer. The silane compound with a specific structure has a secondary amine structure, and a specific compound containing silicon structure. Also, a resin film obtained by curing the photosensitive resin composition. Also, an electronic device includes the resin film. As the alkali-soluble resin, polyamide resin is preferable. The sensitizer is preferably a diazide quinone compound.

Description

Photosensitive resin composition, resin film and electronic device

The invention relates to a photosensitive resin composition, a resin film and an electronic device.

So far, in the field of photosensitive resin compositions, for the purpose of obtaining a cured film that does not cause pattern peeling and floating during development, and has good adhesion to the underlying substrate after thermal curing treatment and chemical treatment, efforts are being made. Develop various technologies. As such a technique, the technique described in patent document 1 is mentioned, for example. According to Document 1, it is described that by using a silane compound of a specific structure, peeling and bleeding during alkaline development of a photosensitive resin composition on a metal substrate can be suppressed. Moreover, according to Patent Document 1, it is described that a cured film formed by thermosetting a photosensitive resin composition exhibits good adhesiveness on a metal substrate.

Patent Document 1: International Publication No. 2013/146130

When the present inventors use the photosensitive resin composition described in Patent Document 1 as a permanent film of an electronic device, aluminum (Al) pads and circuits, that is, copper (Cu), which are provided for input and output of the substrate of the electronic device The adhesion between the circuit and the permanent film is studied. Furthermore, the so-called permanent film is a cured film obtained by pre-baking, exposing and developing a resin film formed of a photosensitive resin composition, patterning it into a desired shape, and then post-baking And harden the resin film. As a result of the above study, it was found that in the photosensitive resin composition described in Patent Document 1, if the prebaking temperature is not as high as 120° C. or higher, for example, the adhesion to the Al pad does not develop. Accordingly, there is a disadvantage that the photosensitive resin composition peels off from the Al pad. On the other hand, when the prebaking temperature is high, for example, 120° C. or higher, it was found that the adhesion between the copper circuit and the photosensitive resin composition described in Patent Document 1 becomes too large before development. Accordingly, when the photosensitive resin composition is developed to form a via hole exposing the Cu circuit, the photosensitive resin composition cannot be completely removed by development, resulting in residues of the photosensitive resin composition in the via hole. In addition, if the residue is generated, there is a disadvantage in that the electrical reliability of the electronic device is lowered. From the above, it can be seen that the adhesiveness between the photosensitive resin composition after prebaking and the Al pad and the generation of residue of the photosensitive resin composition during development are in a trade-off relationship with the temperature of the prebaking.

Here, when the photosensitive resin composition described in Patent Document 1 is used as a permanent film of an electronic device, the present inventors investigated the gap between the cured film of the post-baked photosensitive resin composition and metals such as Al pads and copper circuits. The closeness is studied. As a result, it was determined that the photosensitive resin composition described in Patent Document 1 has insufficient adhesiveness to metals such as Al pads and copper circuits. Thereby, fine relief patterns and the like are formed in the photosensitive resin composition, but when the contact area between the cured film of the photosensitive resin composition and the metal is very small, there is a problem that the cured film peels off.

The permanent film of the electronic device mentioned above specifically includes an insulating film of the electronic device and the like. The present inventors studied the chemical resistance of the insulating film when a two-layer insulating film was formed using the photosensitive resin composition described in Patent Document 1 as the insulating film of an electronic device. Here, an example of a method of forming a two-layer insulating film will be described. In the manufacturing process of electronic devices, after the first insulating film is formed, the interlayer insulating film is pre-baked, exposed and developed to form via holes, and after post-baking, metal wirings are formed through the via holes. Next, a second insulating film is formed on the first insulating film and the metal wiring. Here, as a method of forming the second-layer insulating film, a method of applying a varnish of a photosensitive resin composition is used. In addition, the varnish of the photosensitive resin composition contains solvents such as N-methylpyrrolidone (NMP). As a result of the above studies, if the first insulating film is formed using the photosensitive resin composition described in Patent Document 1, when the second insulating film is formed, the first insulating film is dissolved by NMP and cracks occur. Condition.

From the above, the object of the present invention is to express the improvement of the adhesiveness between the prebaked photosensitive resin composition and the Al pad and the suppression of the generation of the residue of the photosensitive resin composition during development in a good balance. Furthermore, the object of this invention is to improve the adhesiveness between the cured film of the postbaked photosensitive resin composition and metals, such as Al, and to improve the chemical resistance of the postbaked photosensitive resin composition.

The inventors of the present invention have found that the improvement of the adhesion between the photosensitive resin composition after prebaking and the Al pad and the suppression of the generation of residues of the photosensitive resin composition during development can be achieved in a well-balanced manner even if prebaking is performed at a low temperature. The raw material components of the photosensitive resin composition which can improve the adhesiveness between Al pads were studied. As a result, it was found that by using a silane compound with a specific structure as a raw material component, even when prebaking is performed at a low temperature lower than 120°C, it is possible to increase the adhesion between the prebaked photosensitive resin composition and the Al mat. Closeness. Moreover, it was found that the adhesiveness between the cured film of the photosensitive resin composition after postbaking and metals, such as Al, can be improved by using the silane compound of the said specific structure. Furthermore, it was found that the chemical resistance of the photosensitive resin composition after postbaking can be improved by using the silane compound of the said specific structure. From the above, the present inventors found that by containing a silane compound with a specific structure, the improvement of the adhesion between the prebaked photosensitive resin composition and the Al pad and the residue of the photosensitive resin composition during development can be expressed in a good balance The suppression of the generation of the photosensitive resin composition after post-baking can further improve the adhesion between the cured film of the photosensitive resin composition after post-baking and metals such as Al, and in addition, the chemical resistance of the photosensitive resin composition after post-baking can be improved, thereby completing this invention.

According to the present invention, there is provided a photosensitive resin composition comprising: a silane compound represented by the following general formula (1); an alkali-soluble resin; and a photosensitive agent.

（上述通式（1）中，R¹ 表示碳數1以上且30以下的有機基。其中，將R¹ 中含有芳香環者除外。 R² 及R³ 分別獨立地表示碳數1以上且30以下的有機基。 A分別獨立地表示羥基或碳數1以上且30以下的有機基。A可彼此相同，亦可彼此不同。A中的至少一個係選自羥基及碳數1以上且30以下的烷氧基中之一種。 B分別獨立地表示羥基或碳數1以上且30以下的有機基。B可彼此相同，亦可彼此不同。B中的至少一個係選自羥基及碳數1以上且30以下的烷氧基中之一種。）

(In the above general formula (1), R ¹ represents an organic group with a carbon number of 1 to 30. Among them, those containing an aromatic ring in R ¹ are excluded. R ² and R ³ each independently represent a carbon number of 1 to 30 The following organic groups. A each independently represents a hydroxyl group or an organic group with a carbon number of 1 or more and 30 or less. A may be the same as or different from each other. At least one of A is selected from a hydroxyl group and a carbon number of 1 or more and 30 or less. One of the alkoxy groups. B each independently represents a hydroxyl group or an organic group with a carbon number of 1 or more and a carbon number of 30 or less. B may be the same or different from each other. At least one of B is selected from hydroxyl groups and carbon numbers of 1 or more And one of the alkoxy groups below 30.)

Moreover, according to this invention, the resin film which hardened the said photosensitive resin composition can be provided.

Also, according to the present invention, an electronic device including the above resin film can be provided.

The present invention provides a photosensitive resin composition that exhibits improved adhesion between the prebaked photosensitive resin composition and an Al pad and suppresses generation of residues of the photosensitive resin composition during development with a good balance, further improving Adhesiveness between the cured film of the photosensitive resin composition after postbaking and metals such as Al, and chemical resistance of the photosensitive resin composition after postbaking are improved.

The above-mentioned object and other objects, features, and advantages will become clearer by referring to preferred embodiments described below and the following drawings accompanying them.

Hereinafter, this embodiment will be described using drawings as appropriate. In addition, in all drawings, the same code|symbol is attached|subjected to the same component, and description is abbreviate|omitted. Moreover, in this specification, the case of the silane compound represented by General formula (1) may be described as "the silane compound of a specific structure", etc. in some cases.

The photosensitive resin composition of this embodiment includes a silane compound with a specific structure, an alkali-soluble resin, and a photosensitive agent.

In order to obtain a photosensitive resin composition that exhibits improved adhesion between the prebaked photosensitive resin composition and the Al pad and suppresses generation of residues of the photosensitive resin composition during development with a good balance, The raw material components of the photosensitive resin composition which can improve the adhesiveness with the Al pad even if it prebaked at low temperature were investigated. As a result, it was found that by using a silane compound with a specific structure as a raw material component, even when prebaking is performed at a low temperature lower than 120°C, it is possible to increase the adhesion between the prebaked photosensitive resin composition and the Al mat. Closeness. Although the detailed mechanism is not clear, it is presumed to be as follows. First, the molecule of the silane compound of the above-mentioned specific structure has a group represented by -SiA ₃ or -SiB ₃ at both ends of the molecular structure. And it is presumed that a crosslinked structure is formed with the alkali-soluble resin which is a component of a photosensitive resin composition via these groups. Here, the silane compound of the above-mentioned specific structure has two lone electron pairs derived from the nitrogen atom of the secondary amine, and is considered to interact more strongly with the Al atom than conventional silane compounds. Moreover, the nitrogen atom of the secondary amine is contained in the above-mentioned crosslinked structure. From this, it is considered that the crosslinked structure of the silane compound including the above specific structure strongly interacts with Al atoms. Therefore, it is presumed that the photosensitive resin composition of this embodiment can fully improve the adhesiveness with Al even when it prebaked at the low temperature of less than 120 degreeC.

In addition, the present inventors found a photosensitive resin composition that can improve the adhesion between the cured film of the photosensitive resin composition after post-baking and metals such as Al pads when using the photosensitive resin composition as a permanent film of an electronic device. The raw material composition of the product is studied. As a result, it was found that the adhesiveness between the cured film of the post-baked photosensitive resin composition and metals such as Al pads can be improved by using the silane compound of the above-mentioned specific structure as a raw material component. Although the detailed mechanism is not clear, the reason is presumed as follows. As described above, it is presumed that the silane compound of the above-mentioned specific structure forms a crosslinked structure with the alkali-soluble resin. Here, it is considered that the molecular structure of the above-mentioned specific silane compound functions as a flexible skeleton in the photosensitive resin composition. Thereby, it is considered that the internal stress of the post-baked photosensitive resin composition can be reduced by the above-mentioned flexible skeleton. Therefore, it is considered that the breakage of the interface between the photosensitive resin composition and the metal contact surface due to an increase in internal stress when the photosensitive resin composition is post-baked is suppressed.

Furthermore, the present inventors studied the raw material components of the photosensitive resin composition which can improve the chemical resistance of the photosensitive resin composition after postbaking. As a result, it was found that the chemical resistance of the cured film of the photosensitive resin composition after post-baking can be improved by using the silane compound of the above-mentioned specific structure as a raw material component. Although the detailed mechanism is not clear, the reason is presumed as follows. As described above, it is presumed that the silane compound of the above-mentioned specific structure forms a crosslinked structure with the alkali-soluble resin. Thereby, it is considered that the crosslink density of the photosensitive resin composition is improved, and the intrusion of chemical molecules into the photosensitive resin composition can be suppressed.

Based on the above, it is presumed that the photosensitive resin composition of this embodiment contains a silane compound of a specific structure, so that even in the case of prebaking at a low temperature lower than 120°C, the photosensitive resin after prebaking can be sufficiently improved. Adhesion between the composition and the Al pad. Furthermore, since prebaking at a low temperature of less than 120° C. can be realized, generation of residues of the photosensitive resin composition during image development can be suppressed. Furthermore, it is presumed that the adhesiveness between the cured film of the photosensitive resin composition after post-baking and metals, such as an Al pad, can be improved by containing the silane compound of a specific structure in the photosensitive resin composition of this embodiment. Moreover, since the photosensitive resin composition of this embodiment contains the silane compound of a specific structure, the chemical resistance of the photosensitive resin composition after postbaking can be improved.

First, each raw material component of the photosensitive resin composition of this embodiment is demonstrated.

(Silane compound) The silane compound is represented by the following general formula (1), for example, the one represented by the following general formula (2) is preferable, and the one represented by the following general formula (3) is more preferable . Thereby, the silane compound easily forms a cross-linked structure, thereby appropriately reducing internal stress. Therefore, the adhesiveness between the cured film of a photosensitive resin composition, and a metal can be improved.

（上述通式（1）中，R¹ 表示碳數1以上且30以下的有機基。其中，將R¹ 中包含芳香環者除外。 R² 及R³ 分別獨立地表示碳數1以上且30以下的有機基。 A分別獨立地表示羥基或碳數1以上且30以下的有機基。A可彼此相同，亦可彼此不同。A中的至少一個係選自羥基及碳數1以上且30以下的烷氧基中之一種。 B分別獨立地表示羥基或碳數1以上且30以下的有機基。B可彼此相同，亦可彼此不同。B中的至少一個係選自羥基及碳數1以上且30以下的烷氧基中之一種。）

(In the above-mentioned general formula (1), R ¹ represents an organic group with a carbon number of 1 to 30. Among them, those containing an aromatic ring in R ¹ are excluded. R ² and R ³ each independently represent a carbon number of 1 to 30 The following organic groups. A each independently represents a hydroxyl group or an organic group with a carbon number of 1 or more and 30 or less. A may be the same as or different from each other. At least one of A is selected from a hydroxyl group and a carbon number of 1 or more and 30 or less. One of the alkoxy groups. B each independently represents a hydroxyl group or an organic group with a carbon number of 1 or more and a carbon number of 30 or less. B may be the same or different from each other. At least one of B is selected from hydroxyl groups and carbon numbers of 1 or more And one of the alkoxy groups below 30.)

（上述通式（2）中，R¹ 表示碳數1以上且30以下的有機基。其中，將R¹ 中包含芳香環者除外。 R² 表示碳數1以上且30以下的有機基。 A分別獨立地表示羥基或碳數1以上且30以下的有機基。A可彼此相同，亦可彼此不同。A中的至少一個係選自羥基及碳數1以上且30以下的烷氧基中之一種。 B分別獨立地表示羥基或碳數1以上且30以下的有機基。B可彼此相同，亦可彼此不同。B中的至少一個係選自羥基及碳數1以上且30以下的烷氧基中之一種。）

(In the above-mentioned general formula (2), R ¹ represents an organic group with a carbon number of 1 to 30. Among them, those containing an aromatic ring in R ¹ are excluded. R ² represents an organic group with a carbon number of 1 to 30. A Each independently represents a hydroxyl group or an organic group with a carbon number of 1 to 30. A may be the same as or different from each other. At least one of A is selected from a hydroxyl group and an alkoxy group with a carbon number of 1 to 30. A. B independently represents a hydroxyl group or an organic group with a carbon number of 1 or more and 30 or less. B may be the same as or different from each other. At least one of B is selected from a hydroxyl group and an alkoxy group with a carbon number of 1 or more and 30 or less. one of the bases.)

（上述通式（3）中，R¹ 表示碳數1以上且30以下的有機基。其中，將R¹ 中包含芳香環者除外。 A分別獨立地表示羥基或碳數1以上且30以下的有機基。A可彼此相同，亦可彼此不同。A中的至少一個係選自羥基及碳數1以上且30以下的烷氧基中之一種。 B分別獨立地表示羥基或碳數1以上且30以下的有機基。B可彼此相同，亦可彼此不同。B中的至少一個係選自羥基及碳數1以上且30以下的烷氧基中之一種。）

(In the above general formula (3), ^R1 represents an organic group with a carbon number of 1 to 30. Among them, those containing an aromatic ring in ^R1 are excluded. A each independently represents a hydroxyl group or a carbon number of 1 to 30. Organic group. A may be the same as each other or different from each other. At least one of A is selected from a hydroxyl group and an alkoxy group with a carbon number of 1 or more and a carbon number of 30 or less. B each independently represents a hydroxyl group or a carbon number of 1 or more and An organic group of 30 or less. B may be the same or different from each other. At least one of B is selected from a hydroxyl group and an alkoxy group with a carbon number of 1 or more and 30 or less.)

R ¹ to R ³ in the above general formulas (1) to (3) are an organic group with 1 to 30 carbons, for example, an organic group with 1 to 10 carbons is preferred, and an organic group with 1 to 10 carbons is preferred. An organic group having 7 or less carbon atoms is more preferable, an organic group having 1 or more carbon atoms and 5 or less carbon atoms is still more preferable, and an organic group having 1 or more carbon atoms and 3 or less carbon atoms is particularly preferable. Thereby, the crosslink density can be further increased. Therefore, the chemical resistance of the cured film of a photosensitive resin composition can be improved.

The organic groups constituting R ¹ to R ³ in the above general formulas (1) to (3) may contain atoms other than hydrogen and carbon in the structure of the organic group, for example. Specific examples of atoms other than hydrogen and carbon include oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, silicon atoms, fluorine atoms, and chlorine atoms. As atoms other than hydrogen and carbon, one kind or two or more kinds can be contained in the above specific examples.

Specific examples of R ¹ in the general formulas (1) to (3) include alkylene groups and the like. As the alkylene group, for example, a linear alkylene group or a branched chain alkylene group may be used. Specific examples of the linear alkylene group include methylene, ethylene, propylene, butyl, pentylene, hexylene, heptyl, octylene, nonylene, Decyl, trimethylene, tetramethylene, pentamethylene, hexamethylene, etc. Also, as the branched chain alkylene group, specifically, -C(CH ₃ ) ₂ -, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ )( CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ - and other alkyl methylene groups; -CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C(CH ₂ CH ₃ ) ₂ -CH ₂ -, etc. Alkyl ethylene etc. As R ¹ , for example, an alkylene group is preferred, and a linear alkylene group is more preferred. Thereby, ^R1 has a flexible structure, so that internal stress can be appropriately relieved. Therefore, the adhesiveness between the cured film of a photosensitive resin composition, and a metal can be improved. In addition, around the nitrogen atom of the secondary amine derived from the silane compound, the limitation of stereo configuration is reduced, and the nitrogen atom can better interact with metal atoms such as Al. Therefore, even when prebaking is performed at a low temperature lower than 120° C., the adhesiveness between the prebaked photosensitive resin composition and the Al pad can be sufficiently improved.

As R ¹ in the above-mentioned general formulas (1) to (3), those containing an aromatic ring are excluded. Thereby, since the aromatic ring which is a rigid structure does not exist, it becomes possible to suppress the increase of internal stress at the time of post-baking. Therefore, the adhesiveness between the cured film of a photosensitive resin composition, and a metal can be improved. Furthermore, as the aromatic ring, specifically, a benzene ring; a condensed aromatic ring such as a naphthalene ring, an anthracene ring, and a pyrene ring; a heteroaromatic ring such as a pyridine ring or a pyrrole ring; and the like.

Specific examples of R ² in the above general formulas (1) to (2) and R ³ in the above general formula (1) include alkylene groups, arylylene groups, and the like. The alkylene group may be, for example, a linear alkylene group or a branched chain alkylene group. Specific examples of the linear alkylene group include methylene, ethylene, propylene, butyl, pentylene, hexylene, heptyl, octylene, nonylene, Decyl, trimethylene, tetramethylene, pentamethylene, hexamethylene, etc. Specific examples of the branched alkylene group include -C(CH ₃ ) ₂ -, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ - and other alkyl methylene groups; -CH(CH ₃ )CH ₂ -, -CH (CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C(CH ₂ CH ₃ ) ₂ -CH ₂ -etc. Ethyl etc. Specific examples of the arylylene group include a phenylene group, a biphenylene group, a naphthylene group, an anthracenyl group, and those in which two or more arylylene groups are bonded to each other. R ² and R ³ are preferably alkylene, for example. Thereby, an increase in internal stress can be suppressed during post-baking. Therefore, the adhesiveness between the cured film of a photosensitive resin composition, and a metal can be improved.

A plurality of A in the above general formulas (1) to (3) are each independently a hydroxyl group or an organic group with a carbon number of 1 to 30, preferably a hydroxyl group or an organic group with a carbon number of 1 to 10, and the hydroxyl group Or an organic group having 1 to 3 carbon atoms is more preferred, and a hydroxyl group or an organic group having 1 to 2 carbon atoms is still more preferred. Accordingly, it is considered that the molecular chains of the silane compound are easily incorporated into the crosslinked structure.

As A in the above general formulas (1) to (3), at least one is selected from hydroxyl group and alkoxy group having 1 to 30 carbon atoms, and two or more of A are selected from hydroxyl group. and an alkoxy group with a carbon number of 1 to 30 are preferred, and three of A are selected from hydroxyl groups and alkoxy groups with a carbon number of 1 to 30. More preferably. From this, it is presumed that the molecular chains of the silane compound are bonded to each other to easily oligomerize. Therefore, a flexible molecular chain of a more appropriate shape can be formed.

A plurality of A in the general formulas (1) to (3) may be the same as or different from each other. As a plurality of A, for example, it is preferable that they are the same as each other. Thereby, the molecular chains of the silane compound are uniformly introduced into the crosslinked structure. Therefore, local concentration of internal stress can be suppressed.

Examples of A other than the alkoxy group having 1 to 30 carbon atoms in the general formulas (1) to (3) above include methyl, ethyl, n-propyl, isopropyl, and n-butyl. , isobutyl, secondary butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl and other alkyl groups; allyl, pentenyl, vinyl, etc. Alkenyl; alkynyl such as ethynyl; alkylene such as methine and ethylene; aryl such as tolyl, xylyl, phenyl, naphthyl and anthracenyl; aralkyl such as benzyl and phenethyl ; Cycloalkyl groups such as adamantyl, cyclopentyl, cyclohexyl, cyclooctyl, etc.; alkaryl groups such as tolyl, xylyl, etc.

B in the above-mentioned general formulas (1) to (3) can be made the same as the above-mentioned A. In addition, a plurality of Bs and As may be the same as each other or different from each other.

Specific examples of the silane compound represented by the general formula (1) in this embodiment include N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, N,N' -Bis(3-triethoxysilylpropyl)ethylenediamine, N,N'-bis[3-(methyldimethoxysilyl)propyl]ethylenediamine, N,N' -Bis[3-(methyldiethoxysilyl)propyl]ethylenediamine, N,N'-bis[3-(dimethylmethoxysilyl)propyl]ethylenediamine, N-[3-(methyldimethoxysilyl)propyl]-N'-[3-(trimethoxysilyl)propyl]ethylenediamine, N,N'-bis[3- (trimethoxysilyl)propyl]diaminopropane, N,N'-bis[3-(trimethoxysilyl)propyl]diaminohexane, N,N'-bis[3 -(trimethoxymethylsilyl)propyl]diethylenetriamine, etc. Also, as the silane compound represented by the above-mentioned general formula (1), 3-methacryloxypropyl trimethoxysilane and N-2-(aminoethyl)-3-aminopropyl Reaction product of trimethoxysilane. As a commercial item of this reaction product, KBM-425 by Shin-Etsu Chemical Co., Ltd. etc. are mentioned.

The lower limit of the content of the silane compound in the photosensitive resin composition is, for example, preferably 0.01 parts by mass or more, more preferably 1.0 parts by mass or more, further preferably 2.0 parts by mass or more, relative to 100 parts by mass of the alkali-soluble resin described later. Preferably, 2.5 mass parts or more are still more preferable, and 3.0 mass parts or more are especially preferable. Thereby, the alkali-soluble resin can be crosslinked suitably by a silane compound. Therefore, the adhesiveness of the prebaked photosensitive resin composition and the Al pad can be improved, and the chemical resistance of the postbaked photosensitive resin composition can be improved. Also, the upper limit of the content of the silane compound in the photosensitive resin composition is, for example, preferably 30 parts by mass or less, more preferably 15 parts by mass or less, further preferably 10 parts by mass or less, based on 100 parts by mass of the alkali-soluble resin. better. Thereby, the silane compound exerts a flexible function without impairing the mechanical strength of the resin film formed from the photosensitive resin composition. Therefore, the adhesiveness between the photosensitive resin composition after postbaking and metals, such as Al, can be improved.

(Alkali-Soluble Resin) The alkali-soluble resin is not limited, and can be selected according to physical properties such as mechanical properties and optical properties required for the resin film. The alkali-soluble resin specifically includes phenol resin, hydroxystyrene resin, cyclic olefin resin, polyamide resin, polyimide resin, polybenzoxazole resin, and the like. As the alkali-soluble resin, for example, polyamide resin or polybenzoxazole resin is preferably used, and polyamide resin is more preferably used. Thereby, the alkali-soluble resin and the silane compound can preferably form a cross-linked structure. As the alkali-soluble resin, one or two or more of the above-mentioned specific examples can be contained.

Specific examples of the phenol resin include novolak-type phenol resins such as phenol novolac resin, cresol novolac resin, bisphenol novolac resin, and phenol-biphenol novolak resin; Reaction products of phenolic compounds such as resin-type phenol resins and cresol novolak resins and aldehyde compounds; reaction products of phenol compounds such as phenol aralkyl resins and dimethanol compounds, etc. In addition, as a phenolic resin, one type or two or more types of the above-mentioned specific examples can be contained.

The above-mentioned phenol compound used as the reactant of the phenol compound and the aldehyde compound or the reactant of the phenol compound and the dimethanol compound is not limited. Specific examples of such phenolic compounds include cresols such as phenol, o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-dimethyl Cresol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol and other xylenols; o-ethylphenol, m-ethylphenol, p-ethylphenol and other ethylphenols Alkylphenols such as isopropylphenol, butylphenol, and p-tertiary butylphenol; polyphenols such as resorcinol, catechol, hydroquinone, gallicol, and phloroglucinol; 4 , 4'-biphenol and other biphenyl phenols. As the phenol compound, one or two or more of the specific examples above can be used.

The above-mentioned aldehyde compound used as the reactant of the phenol compound and the aldehyde compound is not limited as long as it is a compound having an aldehyde group. Specific examples of such aldehyde compounds include formaldehyde, polyoxymethylene, acetaldehyde, benzaldehyde, salicaldehyde, and the like. As the aldehyde compound, one or two or more of the specific examples above can be used.

The aforementioned dimethanol compound used as the reactant of the phenol compound and the dimethanol compound is not limited. Specific examples of such dimethanol compounds include 1,4-benzenedimethanol, 1,3-benzenedimethanol, 4,4'-biphenyldimethanol, 3,4'-biphenyldimethanol, 3, 3'-biphenyldimethanol, 2,6-naphthalene dimethanol, 2,6-bis(hydroxymethyl)-p-cresol and other dimethanol compounds; 1,4-bis(methoxymethyl)benzene, 1 ,3-bis(methoxymethyl)benzene, 4,4'-bis(methoxymethyl)biphenyl, 3,4'-bis(methoxymethyl)biphenyl, 3,3'- Bis(methoxymethyl)biphenyl, bis(alkoxymethyl) compounds such as methyl 2,6-naphthalene dicarboxylate, or 1,4-bis(chloromethyl)benzene, 1,3-bis (Chloromethyl)benzene, 1,4-bis(bromomethyl)benzene, 1,3-bis(bromomethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 3,4'- Bis(chloromethyl)biphenyl, 3,3'-bis(chloromethyl)biphenyl, 4,4'-bis(bromomethyl)biphenyl, 3,4'-bis(bromomethyl)biphenyl Or bis(haloalkyl) compounds such as 3,3'-bis(bromomethyl)biphenyl, 4,4'-bis(methoxymethyl)biphenyl, 4,4'-bis(methoxymethyl) ) biphenyl and other biphenyl aralkyl compounds, etc. As the dimethanol compound, one or two or more of the above specific examples can be used.

The above-mentioned hydroxystyrene resin is not limited, and specifically, one or two or more kinds selected from the group consisting of hydroxystyrene, hydroxystyrene derivatives, styrene and styrene derivatives can be used. Polymerized or copolymerized reactants.

The above-mentioned cyclic olefin resin is not particularly limited, and for example, a polymerized or copolymerized product obtained by polymerizing or copolymerizing one or two or more selected from the group consisting of norcamphene and norcamphene derivatives can be used. Here, specific examples of the norbornene derivatives include norbasadiene, bicyclo[2.2.1]-hept-2-ene (common name: 2-norcamphene), 5-methyl-2 -norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5- Allyl-2-norcamphene, 5-(2-propenyl)-2-norcamphene, 5-(1-methyl-4-pentenyl)-2-norcamphene, 5-ethynyl -2-Norcamphene, 5-Benzyl-2-Norcamphene, 5-Phenylethyl-2-Norcamphene, 2-Acetyl-5-Norcamphene, 5-Norcamphene-2- Methyl carboxylate, 5-norbornene-2,3-dicarboxylic anhydride, etc. Furthermore, the cyclic olefin resin may have structural units other than the cyclic olefin monomer (for example, the aforementioned norbornene derivative). For example, it may be a copolymer of a cyclic olefin monomer and maleic anhydride. Alkali solubility can be remarkably improved by copolymerizing maleic anhydride and cyclic olefin resin.

For the polyamide resin of this embodiment, it is preferable to use, for example, an aromatic polyamide containing an aromatic ring in a polyamide structural unit, and it is more preferable to use a structural unit represented by the following formula (PA1). Thereby, the molecular chains of the polyamide resin are hydrogen-bonded with each other to form a tight structure through the amide group, and the chemical molecules can be prevented from immersing into the photosensitive resin composition. Therefore, chemical resistance after post-baking can be improved. In this embodiment, the term "aromatic ring" means a benzene ring; a condensed aromatic ring such as a naphthalene ring, an anthracene ring, and a pyrene ring; a heteroaromatic ring such as a pyridine ring or a pyrrole ring; and the like. From the viewpoint of forming the above-mentioned compact structure, it is preferable that the polyamide resin of this embodiment contains a benzene ring as an aromatic ring.

A precursor of a polyamide resin-based polybenzoxazole resin comprising a structural unit represented by the above formula (PA1). The polyamide resin comprising the structural unit represented by the above formula (PA1) can be dehydrated and ring-closed to form a polyamide resin, for example, by heat treatment at a temperature of 150°C to 380°C for 30 minutes to 50 hours. Benzoazole resins. Here, the structural unit of the above-mentioned formula (PA1) becomes a structural unit represented by the following formula (PBO1) through dehydration ring closure. In the case where the alkali-soluble resin of this embodiment is a polyamide resin containing the structural unit represented by the above-mentioned formula (PA1), for example, by performing the above-mentioned heat treatment on the photosensitive resin composition, thereby dehydrating and closing the ring to form polyphenylene And oxazole resin. That is, the photosensitive resin composition subjected to the heat treatment includes polybenzoxazole resin as an alkali-soluble resin. In addition, in the case of the alkali-soluble resin containing the polyamide resin of the structural unit represented by the above formula (PA1), the above-mentioned heat treatment can be performed after the resin film and electronic device described later are produced, thereby dehydrating and closing the ring to form polyphenylene resin. And oxazole resin. In the case of forming a polybenzoxazole resin, the tensile elongation at break can be increased. Thereby, it is advantageous from a viewpoint that the strength of a resin film and an electronic device can be improved.

Moreover, as a polyamide resin, the thing containing the structural unit represented by the following general formula (PAM), for example can be used. A polyamide resin comprising a structural unit represented by the following general formula (PAM) is a precursor of a polyimide resin. A polyamide resin comprising a structural unit represented by the following general formula (PAM) can be dehydrated and ring-closed by, for example, heat-treating at a temperature of 150°C to 380°C for 30 minutes to 50 hours , forming a polyimide resin. Here, the structural unit of the following formula (PAM) becomes the structural unit represented by the following formula (PI1) through dehydration ring closure. When the alkali-soluble resin is a polyamide resin including a structural unit represented by the following formula (PAM), the polyimide resin can be formed by dehydrating and ring-closing the photosensitive resin composition by heat treatment. That is, the heat-treated photosensitive resin composition may contain polyimide resin as an alkali-soluble resin. In addition, when the alkali-soluble resin is a polyamide resin containing a structural unit represented by the following formula (PAM), for example, heat treatment can be performed after the electronic device described later is produced, thereby dehydrating and ring-closing to form polyimide resin.

In the general formula (PAM), R ^B and R ^C are each independently an organic group having 1 to 30 carbon atoms.

In the general formula (PI1), R ^B and R ^C are the same as the above-mentioned general formula (PAM).

As R ^B and R ^C in the general formula (PAM) and the general formula (PI1), specifically, an organic group having an aromatic ring is preferable. Specifically, the organic group having an aromatic ring is preferably one containing a benzene ring, a naphthalene ring, or an anthracene ring, and more preferably one containing a benzene ring.

For example, when the total solid content of the photosensitive resin composition is 100 parts by mass, the lower limit of the content of the alkali-soluble resin in the photosensitive resin composition is preferably 30 parts by mass or more, more preferably 40 parts by mass or more , more preferably 50 parts by mass or more, still more preferably 60 parts by mass or more, and particularly preferably 70 parts by mass or more. Thereby, the photosensitive resin composition can express appropriate photosensitivity. Therefore, generation of residues of the photosensitive resin composition can be suppressed at the time of image development. Therefore, improvement of the adhesiveness of the prebaked photosensitive resin composition and the Al pad and suppression of generation|occurrence|production of the residue of the photosensitive resin composition at the time of image development can be expressed with a more favorable balance. Also, for example, when the total solid content of the photosensitive resin composition is 100 parts by mass, the upper limit of the content of the alkali-soluble resin in the photosensitive resin composition is preferably 90 parts by mass or less, and preferably 85 parts by mass or less. More preferably, it is still more preferable that it is 80 mass parts or less. Thereby, the alkali-soluble resin can properly form a cross-linked structure through the silane compound, and the chemical resistance of the photosensitive resin composition after post-baking can be improved. In addition, in the present embodiment, the total solid content of the photosensitive resin composition means the total of the components contained in the photosensitive resin composition excluding surfactants and solvents.

(Manufacturing method of polyamide resin) The polyamide resin of this embodiment is polymerized as follows, for example. First, the polyamide is polymerized by polycondensing the diamine monomer and the dicarboxylic acid monomer in the polymerization step (S1). Next, the low molecular weight component is removed by the low molecular weight component removal step ( S2 ), and a polyamide resin mainly composed of polyamide is obtained.

(Polymerization Step (S1)) In the polymerization step (S1), a diamine monomer and a dicarboxylic acid monomer are polycondensed. The polycondensation method for polymerizing polyamide is not limited, and specific examples thereof include melt polycondensation, the amide chloride method, direct polycondensation, and the like. Furthermore, instead of the dicarboxylic acid monomer, a compound selected from the group consisting of tetracarboxylic dianhydride, 1,2,4-benzenetricarboxylic anhydride, dichlorinated dicarboxylic acid, or active ester type dicarboxylic acid can also be used. . As a method of obtaining an active ester type dicarboxylic acid, the method of making a dicarboxylic acid react with 1-hydroxy-1,2,3-benzotriazole etc. is mentioned specifically,.

The diamine monomers and dicarboxylic acid monomers used in the polymerization of polyamide resins will be described below. In addition, a diamine monomer and a dicarboxylic acid monomer may be prepared individually by 1 type, and may use 2 or more types together.

The diamine monomer used for polymerization is not limited. For example, it is preferable to use a diamine monomer containing an aromatic ring in the structure, and it is more preferable to use a diamine monomer containing a phenolic hydroxyl group in the structure. Here, as a diamine monomer containing a phenolic hydroxyl group in a structure, what is represented, for example by following general formula (DA1) is preferable. By using the diamine monomer as a raw material to manufacture the polyamide resin, the configuration of the polyamide resin is controlled, and the molecular chains of the polyamide resin can form a tighter structure. Therefore, it is possible to suppress the penetration of chemical molecules into the photosensitive resin composition, and improve the chemical resistance after post-baking. Furthermore, for example, when using the diamine monomer represented by the following general formula (DA1), the polyamide resin contains the structural unit represented by the following general formula (PA2). That is, it is preferable that the polyamide resin of this embodiment contains the structural unit represented by the following general formula (PA2), for example.

（在上述通式（DA1）中，R⁴ 係藉由選自由氫原子、碳原子、氧原子、氮原子、硫原子、磷原子、矽原子、氯原子、氟原子、溴原子組成的群中之一種或兩種以上的原子所形成之基。R⁵ ～R¹⁰ 分別獨立地表示氫或碳數1以上且30以下的有機基。）

(In the above general formula (DA1), ^R4 is selected from the group consisting of hydrogen atom, carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, silicon atom, chlorine atom, fluorine atom, bromine atom A group formed by one or two or more atoms. R ⁵ to R ¹⁰ each independently represent hydrogen or an organic group with 1 to 30 carbons.)

（在上述通式（PA2）中，R⁴ 、R⁵ ～R¹⁰ 係與上述通式（DA1）相同。）

(In the above general formula (PA2), R ⁴ , R ⁵ to R ¹⁰ are the same as those in the above general formula (DA1).)

The ^R in the above-mentioned general formula (DA1) and (PA2) is by being selected from hydrogen atom, carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, silicon atom, chlorine atom, fluorine atom, bromine atom The group formed by one or more than two kinds of atoms. Furthermore, R ⁴ is a divalent group. Here, a divalent group means an atomic valence. That is, it means that R ⁴ is bonded to other atoms in two.

When R ⁴ in the above general formulas (DA1) and (PA2) contains carbon atoms, R ⁴ is, for example, a group with a carbon number of 1 to 30, preferably a carbon number of 1 to 10, and carbon A group having 1 to 5 carbon atoms is more preferable, and a group having 1 to 3 carbon atoms is still more preferable.

When R ⁴ in the above general formulas (DA1) and (PA2) contains carbon atoms, specific examples of R ⁴ include alkylene, arylylene, alkylene substituted with halogen, and alkylene substituted with halogen. The extended aryl group and so on. The alkylene group may be, for example, a linear alkylene group or a branched chain alkylene group. Specific examples of the linear alkylene group include methylene, ethylene, propylene, butyl, pentylene, hexylene, heptyl, octylene, nonylene, Decyl, trimethylene, tetramethylene, pentamethylene, hexamethylene, etc. Specific examples of the branched alkylene group include -C(CH ₃ ) ₂ -, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ - and other alkyl methylene groups; -CH(CH ₃ )CH ₂ -, -CH (CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C(CH ₂ CH ₃ ) ₂ -CH ₂ -etc. Ethyl etc. Specific examples of the arylylene group include a phenylene group, a biphenylene group, a naphthylene group, an anthracenyl group, and those in which two or more arylylene groups are bonded to each other. As the alkylene group substituted by halogen and the arylylene group substituted by halogen, specifically, those obtained by substituting hydrogen atoms in the above-mentioned alkylene group and arylylene group with halogen atoms such as fluorine atom, chlorine atom, bromine atom, etc. Winner. Among these, those obtained by substituting a fluorine atom for a hydrogen atom are preferably used.

When R ⁴ in the above-mentioned general formulas (DA1) and (PA2) does not contain a carbon atom, specific examples of R ⁴ include a group composed of an oxygen atom or a sulfur atom.

R ⁵ to R ¹⁰ in the above general formulas (DA1) and (PA2) are each independently hydrogen or an organic group with a carbon number of 1 to 30, for example, hydrogen or an organic group with a carbon number of 1 to 10 is relatively Preferably, hydrogen or an organic group with a carbon number of 1 to 5 is more preferred, hydrogen or an organic group with a carbon number of 1 to 3 is further preferred, and hydrogen or an organic group with a carbon number of 1 to 2 is still more preferred. better. This is advantageous in that the molecular chains of the polyamide resin form hydrogen bonds through amide bonds, and it is possible to suppress the infiltration of chemical molecules into the photosensitive resin composition.

Specific examples of organic groups having 1 to 30 carbon atoms in R ⁵ to R ¹⁰ in the general formulas (DA1) and (PA2) include methyl, ethyl, n-propyl, isopropyl, n- Butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl and other alkyl groups; allyl, pentenyl, ethylene alkenyl such as ethynyl; alkynyl such as ethynyl; alkylene such as methine and ethylene; aryl such as tolyl, xylyl, phenyl, naphthyl and anthracenyl; aromatic such as benzyl and phenethyl Alkyl group; cycloalkyl group such as adamantyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, etc.; alkaryl group group such as tolyl group, xylyl group, etc.

Specific examples of the diamine monomer represented by the general formula (DA1) include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 4,4'-methylene Bis(2-amino-3,6-dimethylphenol), 4,4'-methylenebis(2-aminophenol), 1,1-bis(3-amino-4-hydroxyphenyl ) Ethane, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, etc. By using these diamine monomers, the aromatic rings of the polyamide resin can be closely arranged with each other. Therefore, penetration of chemical molecules into the photosensitive resin composition can be suppressed, and chemical resistance can be improved. In addition, as a diamine monomer, it is possible to use one kind or a combination of two or more kinds of the above specific examples. The structural formulas of these diamine monomers are shown below.

Although the dicarboxylic acid monomer used for polymerization is not limited, for example, it is preferable to use a dicarboxylic acid monomer containing an aromatic ring in the structure. As a dicarboxylic acid monomer containing an aromatic ring, it is preferable to use what is represented by following general formula (DC1), for example. Furthermore, for example, when using a dicarboxylic acid monomer represented by the following general formula (DC1), the polyamide resin contains a structural unit represented by the following general formula (PA3). That is, it is preferable that the polyamide resin of this embodiment contains the structural unit represented by the following general formula (PA3), for example.

（上述通式（DC1）中，R¹¹ 係藉由選自由氫原子、碳原子、氧原子、氮原子、硫原子、磷原子、矽原子、氯原子、氟原子、溴原子組成的群中之一種或兩種以上的原子所形成之基。R¹² ～R¹⁹ 分別獨立地表示氫或碳數1以上且30以下的有機基。）

(In the above general formula (DC1), ^R11 is selected from the group consisting of hydrogen atom, carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, silicon atom, chlorine atom, fluorine atom, bromine atom A group formed by one or more types of atoms. R ¹² to R ¹⁹ each independently represent hydrogen or an organic group having 1 to 30 carbons.)

（在上述通式（PA3）中，R¹¹ 、R¹² ～R¹⁹ 係與上述通式（DC1）相同。）

(In the above general formula (PA3), R ¹¹ , R ¹² to R ¹⁹ are the same as those in the above general formula (DC1).)

R ¹¹ in the above general formula (DC1) is one selected from the group consisting of hydrogen atom, carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, silicon atom, chlorine atom, fluorine atom, bromine atom Or a base formed by two or more atoms. Furthermore, R ¹¹ is a divalent group. Here, a divalent group means an atomic valence. That is, it means that R ¹¹ is bonded to other atoms with two bonds.

In the case where R ¹¹ in the above general formula (DC1) contains carbon atoms, R ¹¹ is, for example, a group with 1 to 30 carbon atoms, preferably a group with 1 to 10 carbon atoms, and a group with 1 or more carbon atoms and 10 or less carbon atoms. A group having 5 or less is more preferable, and a group having 1 to 3 carbon atoms is still more preferable.

When R ¹¹ in the above general formulas (DC1) and (PA3) contains carbon atoms, specific examples of R ¹¹ include alkylene, arylylene, alkylene substituted with halogen, and alkylene substituted with halogen. The extended aryl group and so on. The alkylene group may be, for example, a linear alkylene group or a branched chain alkylene group. Specific examples of the linear alkylene group include methylene, ethylene, propylene, butyl, pentylene, hexylene, heptyl, octylene, nonylene, Decyl, trimethylene, tetramethylene, pentamethylene, hexamethylene, etc. Specific examples of the branched alkylene group include -C(CH ₃ ) ₂ -, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ - and other alkyl methylene groups; -CH(CH ₃ )CH ₂ -, -CH (CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C(CH ₂ CH ₃ ) ₂ -CH ₂ -etc. Ethyl etc. Specific examples of the arylylene group include a phenylene group, a biphenylene group, a naphthylene group, an anthracenyl group, and those in which two or more arylylene groups are bonded to each other. As the halogen-substituted alkylene group and the halogen-substituted arylylene group, specifically, a hydrogen atom in the above-mentioned alkylene group and arylylene group can be used, respectively, by replacing a hydrogen atom in the above-mentioned alkylene group or arylylene group with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom. By. Among these, it is preferable to use what replaced the hydrogen atom with a fluorine atom.

When R ¹¹ in the above general formulas (DC1) and (PA3) does not contain a carbon atom, specific examples of R ¹¹ include a group composed of an oxygen atom or a sulfur atom.

R ¹² to R ¹⁹ in the above general formulas (DC1) and (PA3) are each independently hydrogen or an organic group with a carbon number of 1 to 30, for example, hydrogen or an organic group with a carbon number of 1 to 10 is relatively Preferably, hydrogen or an organic group having 1 to 5 carbon atoms is more preferred, hydrogen or an organic group having 1 to 3 carbon atoms is still more preferred, and hydrogen is still more preferred.

Specific examples of organic groups having 1 to 30 carbon atoms in R ¹² to R ¹⁹ in the general formulas (DC1) and (PA3) include methyl, ethyl, n-propyl, isopropyl, n- Butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl and other alkyl groups; allyl, pentenyl, ethylene alkenyl such as ethynyl; alkynyl such as ethynyl; alkylene such as methine and ethylene; aryl such as tolyl, xylyl, phenyl, naphthyl and anthracenyl; aromatic such as benzyl and phenethyl Alkyl group; cycloalkyl group such as adamantyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, etc.; alkaryl group group such as tolyl group, xylyl group, etc.

As the dicarboxylic acid monomer, specifically, diphenyl ether-4,4'-dicarboxylic acid, isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, and the like can be used. As the dicarboxylic acid monomer, it is better to use diphenyl ether-4,4'-dicarboxylic acid or isophthalic acid in the above specific examples, and it is more preferable to use diphenyl ether-4,4'-dicarboxylic acid .

Furthermore, it is preferable to modify the amine group present at the end of the polyamide resin simultaneously with the polymerization step (S1) or after the polymerization step (S1). Modification can be performed, for example, by reacting a specific acid anhydride or a specific monocarboxylic acid with a diamine monomer or a polyamide resin. Therefore, it is preferable that the amine group at the end of the polyamide resin system of this embodiment is modified with a specific anhydride or a specific monocarboxylic acid. Furthermore, the above-mentioned specific acid anhydride and the above-mentioned specific monocarboxylic acid have one or more functional groups selected from the group consisting of alkenyl groups, alkynyl groups, and hydroxyl groups. Moreover, as said specific acid anhydride and specific monocarboxylic acid, those containing a nitrogen atom are preferable, for example. Thereby, the adhesiveness between the photosensitive resin composition after prebaking and postbaking, and metals, such as Al, can be improved. Specific examples of the aforementioned specific acid anhydrides include maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, exo- 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3- Dicarboxylic anhydride, itaconic anhydride, chlorobridge anhydride, 4-ethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, 4-hydroxyphthalic anhydride, etc. As the specific acid anhydride, one of the above-mentioned specific examples can be used, or two or more can be used in combination. Furthermore, when the amino group present at the terminal of the polyamide resin is modified with a specific acid anhydride of a ring shape, the ring-opening of the specific acid anhydride of a ring shape is performed. Here, after modifying the polyamide resin, an imide ring can be formed by ring-closing a structural unit derived from a specific acid anhydride in a ring shape. As a method of performing ring closure, heat treatment etc. are mentioned, for example. Moreover, as said specific monocarboxylic acid, 5-norcamphene-2-carboxylic acid, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid etc. are mentioned specifically,. As the above-mentioned specific monocarboxylic acid, one of the above-mentioned specific examples can be used, or two or more of them can be used in combination.

Moreover, the carboxyl group present at the terminal of the polyamide resin may be modified simultaneously with the polymerization step (S1) or after the polymerization step (S1). Modification can be performed, for example, by reacting a specific nitrogen atom-containing heteroaromatic compound with a dicarboxylic acid monomer or polyamide resin. Therefore, the polyamide resin of this embodiment is preferably modified by the terminal carboxyl group with a specific nitrogen atom-containing heteroaromatic compound. Furthermore, the above-mentioned specific heteroaromatic compounds containing nitrogen atoms have a group selected from 1-(5-1H-triazolyl)methylamine, 3-(1H-pyrazolyl)amine, 4-(1H -pyrazolyl)amino, 5-(1H-pyrazolyl)amino, 1-(3-1H-pyrazolyl)methylamino, 1-(4-1H-pyrazolyl)methylamine Base, 1-(5-1H-pyrazolyl)methylamino, (1H-tetrazol-5-yl)amino, 1-(1H-tetrazol-5-yl)methyl-amine and 3 One or more functional groups in the group consisting of -(1H-tetrazol-5-yl)phenyl-amine groups. Thereby, the number of lone electron pairs in a photosensitive resin composition can be increased. Therefore, the adhesiveness between the photosensitive resin composition after prebaking and postbaking, and metals, such as Al, can be improved. Specific examples of the specific nitrogen-atom-containing heteroaromatic compound include 5-aminotetrazole and the like.

(Low-molecular-weight component removal step (S2)) Following the above-mentioned polymerization step (S1), a low-molecular-weight component removal step (S2) is performed to remove low-molecular-weight components to obtain a polyamide resin mainly composed of polyamide. After concentrating the organic layer containing the mixture of the low-molecular-weight component and the polyamide resin by filtration or the like, it is redissolved in an organic solvent such as water/isopropanol. Thereby, the precipitate can be filtered and the polyamide resin from which the low molecular weight component was removed can be obtained.

As the polyamide resin, for example, one obtained by condensing a diamine monomer represented by the above-mentioned general formula (DA1) and a dicarboxylic acid monomer represented by the above-mentioned general formula (DC1) is preferable. That is, the polyamide resin preferably has structural units of the general formulas (PA2) and (PA3), more preferably has structural units of the general formulas (PA2) and (PA3) alternately.

(Sensitizer) As the photosensitizer, a photoacid generator that generates acid by absorbing light energy can be used. Specific examples of photoacid generators include diazoquinone compounds; diarylodonium salts; 2-nitrobenzyl ester compounds; N-iminosulfonate compounds; Compounds; 2,6-bis(trichloromethyl)-1,3,5-three well compounds; dihydropyridine compounds, etc. Among these, it is preferable to use a diazide quinone compound. Thereby, the sensitivity of a photosensitive resin composition can be improved. Therefore, the accuracy of the pattern can be improved, and the appearance can be improved. In addition, as a photoacid generator, one type or two or more types of the above-mentioned specific examples can be contained. In addition, when the photosensitive resin composition is a positive type, as a photosensitizer, in addition to the above-mentioned specific examples, triaryl permeic acid salts; onium salts such as percale-borates, etc. may be used in combination. Thereby, the sensitivity of a photosensitive resin composition can be further improved.

As the diazide quinone compound, for example, one or two or more of the compounds shown below can be used.

（n係1以上且5以下之整數。）

(n is an integer between 1 and 5.)

In each of the above diazoquinone compounds, Q is a structure or a hydrogen atom represented by the following formula (a), the following formula (b) and the following formula (c). Among them, at least one of Q in each diazoquinone compound is a structure represented by the following formula (a), the following formula (b) and the following formula (c). Q as the diazoquinone compound preferably includes the following formula (a) or the following formula (b). Thereby, the transparency of a photosensitive resin composition can be improved. Therefore, the appearance of the photosensitive resin composition can be improved.

When the alkali-soluble resin is 100 parts by mass, the lower limit of the content of the photosensitive agent in the photosensitive resin composition is, for example, preferably 1 part by mass or more, more preferably 3 parts by mass or more, further preferably 5 parts by mass or more. better. Thereby, the photosensitive resin composition can exhibit appropriate sensitivity. Also, when the alkali-soluble resin is 100 parts by mass, the upper limit of the content of the photosensitive agent in the photosensitive resin composition is preferably, for example, 30 parts by mass or less, more preferably 20 parts by mass or less. Thereby, the photosensitive resin composition can be hardened suitably, and can express adhesiveness to metals, such as Al and Cu, after prebaking and postbaking.

The photosensitive resin composition of this embodiment can further add additives such as adhesion aids, silane coupling agents, solvents, thermal crosslinking agents, surfactants, antioxidants, dissolution accelerators, fillers, and sensitizers. Representative components are described in detail below.

(Adhesion assistant) The photosensitive resin composition of this embodiment can contain an adhesion assistant, for example. As an adhesion aid, specifically, a triazole compound can be used. Specific examples of the triazole compound include 4-amino-1,2,4-triazole, 4H-1,2,4-triazol-3-amine, 4-amino-3,5-di- 2-pyridyl-4H-1,2,4-triazole, 3-amino-5-methyl-4H-1,2,4-triazole, 4-methyl-4H-1,2,4- Triazol-3-amine, 3,4-diamino-4H-1,2,4-triazole, 3,5-diamino-4H-1,2,4-triazole, 1,2,4 -Triazole-3,4,5-triamine, 3-pyridyl-4H-1,2,4-triazole, 4H-1,2,4-triazole-3-carbonamide, 3,5- Diamino-4-methyl-1,2,4-triazole, 3-pyridyl-4-methyl-1,2,4-triazole, 4-methyl-1,2,4-triazole -3-formamide and other 1,2,4-triazoles. As the triazole compound, one of the above-mentioned specific examples can be used, or two or more can be used in combination.

In addition, it is also preferable to use a compound having an imide structure as an adhesion aid. Usable imide compounds are exemplified below.

(Silane coupling agent) The photosensitive resin composition of this embodiment may contain a silane coupling agent, for example. As a silane coupling agent, the silane coupling agent of the structure different from the said silane compound can be used together with the said silane compound. As a silane coupling agent having a structure different from the above-mentioned silane compound, specifically, a condensate of cyclohexene-1,2-dicarboxylic anhydride and 3-aminopropyltriethoxysilane, 3,3', 4,4'-diphenyl ketone tetracarboxylic dianhydride and condensate of 3-aminopropyltriethoxysilane and other amidosilanes; vinyltrimethoxysilane, vinyltriethoxysilane, etc. Vinylsilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethylsilane Oxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and other epoxysilanes; p-styryltrimethoxysilane and other benzene Vinylsilane; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane Ethoxysilane, 3-methacryloxypropyltriethoxysilane and other methacrylic silanes; 3-acryloxypropyltrimethoxysilane and other acrylic silanes; N-2-(aminoethyl base)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxy Amino silanes such as silane; Trimeric isocyanate silane; Alkyl silane; ureido silane such as 3-ureidopropyl trialkoxy silane; Mercaptosilanes such as trimethoxysilane; isocyanate silanes such as 3-isocyanate propyltriethoxysilane; titanium compounds; aluminum chelates; aluminum/zirconium compounds, etc. As the silane coupling agent, one or two or more of the above-mentioned specific examples can be blended. When the photosensitive resin composition of this embodiment contains a silane coupling agent, the content is, for example, 0.1 to 5 parts by mass, preferably 0.5 to 3 parts by mass relative to 100 parts by mass of the alkali-soluble resin. servings or less.

(Solvent) The photosensitive resin composition of this embodiment can be used, for example as a varnish obtained by dissolving raw material components other than a solvent in a solvent. The solvent is not limited, but specific examples include N-methyl-2-pyrrolidone (NMP), 3-methoxy-N,N-dimethylacrylamide, N,N-dimethylformamide Amide, N,N-Dimethylpropionamide, N,N-Diethylacetamide, 3-Butoxy-N,N-Dimethylpropionamide, N,N-Dibutylformamide Isoamide-based solvents; N,N-dimethylacetamide, tetramethylurea (TMU), 1,3-dimethyl-2-imidazolidinone, tetrabutylurea, N,N'-di Methacrylurea, 1,3-dimethoxy-1,3-dimethylurea, N,N'-diisopropyl-O-methylisourea, O,N,N'-triisopropyl Diisopropylisourea, O-tertiary butyl-N,N'-diisopropylisourea, O-ethyl-N,N'-diisopropylisourea, O-benzyl-N,N'- Urea-based solvents such as diisopropylisourea; propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol, ethylene Ether solvents such as glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, 1,3-butanediol-3-monomethyl ether; propylene glycol monomethyl ether acetic acid Ester (PGMEA), methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butanediol acetate and other acetate-based solvents; tetrahydrofurfuryl alcohol, benzyl alcohol, 2-ethylhexanol , butanediol, isopropanol and other alcohol-based solvents; cyclopentanone, cyclohexanone, diacetone alcohol, 2-heptanone and other ketone-based solvents; γ-butyrolactone (GBL), γ-valerolactone, etc. Ester-based solvents; carbonate-based solvents such as ethyl carbonate and propylene carbonate; dimethylsulfoxide (DMSO), cyclobutane and other ethylene-based solvents; methyl pyruvate, ethyl pyruvate, methyl-3- Ester-based solvents such as methoxypropionate; aromatic hydrocarbon-based solvents such as trimethylbenzene, toluene, and xylene, etc. As the solvent, one or two or more of the above-mentioned specific examples can be contained. The solvent is used so that the solid content concentration of the photosensitive resin composition may be, for example, 5 to 60% by mass, preferably 10 to 50% by mass. The photosensitive resin composition of this embodiment has high chemical resistance. Therefore, even if a plurality of interlayer insulating films are produced using N-methyl-2-pyrrolidone as a solvent, cracks will not occur. From this point of view It is beneficial to consider.

(Thermal crosslinking agent) The photosensitive resin composition of this embodiment may contain the thermal crosslinking agent which can react with alkali-soluble resin by heat. Thereby, the mechanical characteristic of tensile elongation at break can be improved about the hardened|cured material which after-baked the photosensitive resin composition. Specific examples of the thermal crosslinking agent include 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol (p-xylene glycol), 1,3,5-benzene Trimethanol, 4,4-biphenyldimethanol, 2,6-pyridinedimethanol, 2,6-bis(hydroxymethyl)-p-cresol, 4,4'-methylenebis(2,6-bis Alkoxymethylphenol) and other compounds with hydroxymethyl groups; phenols such as phloroglucide; 1,4-bis(methoxymethyl)benzene, 1,3-bis(methoxymethyl) base) benzene, 4,4'-bis(methoxymethyl)biphenyl, 3,4'-bis(methoxymethyl)biphenyl, 3,3'-bis(methoxymethyl)biphenyl Benzene, methyl 2,6-naphthalene dicarboxylate, 4,4'-methylenebis(2,6-dimethoxymethylphenol) and other compounds with alkoxymethyl groups; Methylol melamine compounds such as melamine and hexabutanol melamine; alkoxy melamine compounds such as hexamethoxy melamine; alkoxy methyl acetylene carbamide compounds such as tetramethoxy methyl acetylene carbamide; methylol benzo Guanamine compounds, dimethylol ethylene urea and other methylol urea compounds; dicyanoaniline, dicyanophenol, cyanobenzenesulfonic acid and other cyano compounds; 1,4-phenylene diisocyanate, 3,3 Isocyanate compounds such as '-dimethyldiphenylmethane-4,4'-diisocyanate; ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, triglycidyl isocyanurate Ester, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, phenol novolac resin type epoxy resin and other compounds containing epoxy groups; N,N Maleimide compounds such as '-1,3-phenylene dismaleimide and N,N'-methylene dismaleimide, etc. As the thermal crosslinking agent, one kind or a combination of two or more kinds of the above specific examples can be used.

When the total solid content of the photosensitive resin composition is 100 parts by mass, the upper limit of the content of the thermal crosslinking agent in the photosensitive resin composition is preferably 15 parts by mass or less, more preferably 12 parts by mass or less. Preferably, 10 parts by mass or less is still more preferable. Also, when the total solid content of the photosensitive resin composition is 100 parts by mass, the lower limit of the content of the thermal crosslinking agent in the photosensitive resin composition is, for example, preferably 0.1 parts by mass or more, preferably 1 part by mass or more. More preferably, 5 parts by mass or more is still more preferable, and 7 parts by mass or more is still more preferable.

(Surfactant) The photosensitive resin composition of this embodiment may further contain a surfactant. The surfactant is not limited, but specific examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octyl ether. Polyoxyethylene aryl ethers such as phenyl ether and polyoxyethylene nonylphenyl ether; non-ionic systems such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate Surfactant: EFTOP EF301, EFTOP EF303, EFTOP EF352 (manufactured by Shin-Akita Chemical), MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F177, MEGAFACE F444, MEGAFACE F470, MEGAFACE F471, MEGAFACE F475, MEGAFACEFA F482, F477 (manufactured by DIC), FLUORAD FC-430, FLUORAD FC-431, NOVEC FC4430, NOVEC FC4432 (manufactured by 3M Japan), SURFLON S-381, SURFLON S-382, SURFLON S-383, SURFLON S-393, SURFLON Commercially available fluorine-based surfactants such as SC-101, SURFLON SC-102, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, SURFLON SC-106 (manufactured by AGC SEIMI CHEMICAL); organosiloxane Alkane copolymer KP341 (manufactured by Shin-Etsu Chemical Co.); (meth)acrylic copolymer Polyflow No.57, 95 (manufactured by KYOEISHA CHEMICAL Co., Ltd.); and the like. Among these, it is preferable to use a fluorine-based surfactant having a perfluoroalkyl group. As the fluorine-based surfactant having a perfluoroalkyl group, one selected from MEGAFACE F171, MEGAFACE F173, MEGAFACE F444, MEGAFACE F470, MEGAFACE F471, MEGAFACE F475, MEGAFACE F482, MEGAFACE F477 (manufactured by DIC Corporation), One or more of SURFLON S-381, SURFLON S-383, SURFLON S-393 (manufactured by AGC SEIMI CHEMICAL), NOVEC FC4430 and NOVEC FC4432 (manufactured by 3M Japan) are preferred.

Also, as the surfactant, a polysiloxane-based surfactant (for example, polyether-modified dimethylsiloxane, etc.) can be preferably used. Specific examples of polysiloxane-based surfactants include SH series, SD series, and ST series from Dow Corning Toray, BYK series from BYK Japan, KP series from Shin-Etsu Chemical Co., Ltd., and NOF Co., Ltd. DISFOAM (registered trademark) series, Toshiba Silicones Co., Ltd. TSF series, etc.

When the photosensitive resin composition of this embodiment contains a surfactant, its amount is appropriately adjusted within a range of, for example, 1 ppm to 1000 ppm, preferably 1 ppm to 100 ppm, based on the entire composition.

(Antioxidant) The photosensitive resin composition of this embodiment may further contain an antioxidant. As the antioxidant, one or more selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, and thioether antioxidants can be used. An antioxidant can suppress the oxidation of the resin film formed from the photosensitive resin composition. Examples of phenolic antioxidants include neopentylthritol-tetrakis[3-(3,5-di-tertiary butyl-4-hydroxyphenyl) propionate], 3,9-bis{2-[3 -(3-tertiary butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}2,4,8,10-tetraoxaspiro[5 ,5) Undecane, octadecyl-3-(3,5-di-tertiary butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis[3-(3 ,5-di-tertiary butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris(3,5-di-tertiary butyl- 4-hydroxybenzyl)benzene, 2,6-di-tertiary butyl-4-methylphenol, 2,6-di-tertiary butyl-4-ethylphenol, 2,6-diphenyl- 4-octadecyloxyphenol, stearyl (3,5-di-tertiary butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tertiary butyl- 4-hydroxybenzyl)phosphonate, thiodiethylene glycol bis[(3,5-di-tertiary butyl-4-hydroxyphenyl)propionate], 4,4'-thiobis(6 - tertiary butyl-m-cresol), 2-octylthio-4,6-di(3,5-di-tertiary butyl-4-hydroxyphenoxy) - symmetrical three wells, 2,2' -Methylene bis(4-methyl-6-tertiary butyl-6-butylphenol), 2,2'-methylene bis(4-ethyl-6-tertiary butylphenol), bis [3,3-bis(4-hydroxy-3-tertiary butylphenyl)butanoic acid]ethylene glycol ester, 4,4'-butylene bis(6-tertiary butyl-m-cresol), 2 ,2'-Ethylenebis(4,6-di-tertiary butylphenol), 2,2'-ethylenebis(4-secondary butyl-6-tertiary butylphenol), 1, 1,3-tris(2-methyl-4-hydroxy-5-tertiary butylphenyl)butane, bis[2-tertiary butyl-4-methyl-6-(2-hydroxy-3- Tertiary butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tertiary butylbenzyl ) Trimeric isocyanate, 1,3,5-tris(3,5-di-tertiary butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tris[ (3,5-di-tertiary butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, tetrakis[methylene-3-(3,5-di-tertiary butyl-4 -Hydroxyphenyl)propionate]methane, 2-tertiary butyl-4-methyl-6-(2-acryloyloxy-3-tertiary butyl-5-methylbenzyl)phenol, 3 ,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane-bis[β-(3-tertiary Butyl-4-hydroxy-5-methylphenyl)propionate], triethylene glycol bis[β-(3-tertiary butyl-4-hydroxy-5-methylphenyl)propionate] , 1,1'-bis(4-hydroxyphenyl)cyclohexane, 2,2'-methylenebis(4-methyl-6-tertiary butylphenol), 2,2'-methylene Bis(4-ethyl-6-tertiary butylphenol ), 2,2'-methylenebis(6-(1-methylcyclohexyl)-4-methylphenol), 4,4'-butylenebis(3-methyl-6-tertiary butyl phenol), 3,9-bis(2-(3-tert-butyl-4-hydroxy-5-methylphenylpropanyloxy)1,1-dimethylethyl)-2,4,8 ,10-tetraoxaspiro(5,5)undecane, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 4,4'-bis(3,5- Di-tertiary butyl-4-hydroxybenzyl) sulfide, 4,4'-thiobis(6-tertiary butyl-2-methylphenol), 2,5-di-tertiary butyl hydrogen Quinone, 2,5-di-tertiary pentyl hydroquinone, 2-tertiary butyl-6-(3-tertiary butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl Acrylates, 2,4-dimethyl-6-(1-methylcyclohexyl), styrenated phenol, 2,4-bis((octylthio)methyl)-5-methylphenol, etc. Examples of phosphorus antioxidants include bis(2,6-di-tertiary butyl-4-methylphenyl) neopentylitol diphosphite, tris(2,4-di-tertiary butylbenzene phosphite), tetrakis(2,4-di-tertiary butyl-5-methylphenyl)-4,4'-biphenylene diphosphite, 3,5-di-tertiary butyl Diethyl-4-hydroxybenzyl phosphate-diethyl ester, bis-(2,6-dicumylphenyl) neopentylthritol diphosphite, 2,2-methylenebis(4, 6-di-tertiary butylphenyl) octyl phosphate, tris(mixed mono- and di-nonylphenyl phosphite), bis(2,4-di-tertiary butylphenyl) neopentyl tetra Alcohol diphosphite, bis(2,6-di-tertiary butyl-4-methoxycarbonylethyl-phenyl) neopentylthritol diphosphite, bis(2,6-di-tertiary Butyl-4-octadecyloxycarbonylethylphenyl) neopentylthritol diphosphite, etc. Examples of thioether-based antioxidants include dilauryl 3,3'-thiodipropionate, bis(2-methyl-4-(3-n-dodecyl)thiopropionyloxy)-5 - Tertiary butylphenyl) sulfide, 3,3'-thiodipropionate, neopentylthritol-tetrakis(3-lauryl)thiopropionate, etc.

(Filler) The photosensitive resin composition of this embodiment may contain a filler, for example. As the filler, an appropriate filler can be selected according to the mechanical properties and thermal properties required for the resin film made of the photosensitive resin composition. As a filler, an inorganic filler, an organic filler, etc. are mentioned specifically,. Specific examples of the inorganic filler include silica such as fused crushed silica, fused spherical silica, crystalline silica, secondary agglomerated silica, and micropowder silica; Silicon, aluminum nitride, boron nitride, titanium oxide, silicon carbide, aluminum hydroxide, magnesium hydroxide, titanium dioxide and other metal compounds; talc; clay; mica; glass fiber, etc. As the inorganic filler, one kind or a combination of two or more kinds of the above specific examples can be used. As said organic filler, organopolysiloxane powder, polyethylene powder, etc. are mentioned specifically,. As the organic filler, one of the above-mentioned specific examples can be used, or two or more of them can be used in combination.

(Preparation of Photosensitive Resin Composition) The method for preparing the photosensitive resin composition in this embodiment is not limited, and known methods can be used depending on the components contained in the photosensitive resin composition. For example, it can manufacture by mixing and dissolving each said component and a solvent. Thereby, the photosensitive resin composition as a varnish can be obtained.

(Applications) The photosensitive resin composition of the present embodiment is used to form resin films for electronic devices such as permanent films and resists. Among them, from the viewpoint of improving the adhesion between the photosensitive resin composition after prebaking and the Al pad and suppressing the generation of residues of the photosensitive resin composition during development with a good balance, improving the photosensitivity after postbaking From the viewpoint of the adhesiveness between the cured film of the permanent resin composition and the metal and the viewpoint of improving the chemical resistance of the photosensitive resin composition after post-baking, it is preferably used in applications using a permanent film. In addition, in this embodiment, a resin film means the dry film or cured film of a photosensitive resin composition. That is, the resin film of this embodiment is what dried or hardened the photosensitive resin composition.

The above-mentioned permanent film is composed of a resin film obtained by prebaking, exposing and developing a photosensitive resin composition, patterning it into a desired shape, and post-baking to harden it. The permanent film can be used for a protective film, an interlayer film, a dam material, etc. of an electronic device. In addition, when producing the said permanent film, as a prebaking condition, it can set as the heat treatment of temperature 90 degreeC or more and 130 degreeC or less, and 3 minutes or more and 1 hour or less, for example. In addition, as conditions of the post-baking, for example, heat treatment at a temperature of 150° C. to 350° C. and 45 minutes to 2 hours can be used.

The above-mentioned resist is composed of, for example, a resin film obtained by applying a photosensitive resin composition to the resist by spin coating, roll coating, flow coating, dip coating, spray coating, blade coating, and the like. Remove the solvent from the photosensitive resin composition on the object covered by the solvent.

An example of an electronic device according to this embodiment is shown in FIG. 1 . The electronic device 100 of the present embodiment can be an electronic device including the above-mentioned resin film. Specifically, one or more of the group consisting of the passivation film 32 , the insulating layer 42 , and the insulating layer 44 in the electronic device 100 can be used as a resin film. Here, it is preferable that the resin film is the above-mentioned permanent film.

The electronic device 100 is, for example, a semiconductor wafer. In this case, for example, the electronic device 100 is mounted on the wiring board via the bumps 52 to obtain a semiconductor package. The electronic device 100 includes: a semiconductor substrate provided with semiconductor elements such as transistors; and a multilayer wiring layer (not shown) provided on the semiconductor substrate. An interlayer insulating film 30 and an uppermost layer wiring 34 provided on the interlayer insulating film 30 are provided on the uppermost layer among the multilayer wiring layers. The uppermost layer wiring 34 is made of, for example, aluminum (Al). In addition, a passivation film 32 is provided on the interlayer insulating film 30 and the uppermost wiring 34 . Part of the passivation film 32 is provided with an opening exposing the uppermost layer wiring 34 .

A rewiring layer 40 is provided on the passivation film 32 . The rewiring layer 40 has: an insulating layer 42 provided on the passivation film 32 ; a rewiring 46 provided on the insulating layer 42 ; and an insulating layer 44 provided on the insulating layer 42 and the rewiring 46 . An opening connected to the uppermost layer wiring 34 is formed in the insulating layer 42 . The rewiring 46 is formed on the insulating layer 42 and disposed in the opening of the insulating layer 42 to be connected to the uppermost layer wiring 34 . The insulating layer 44 is provided with an opening connected to the redistribution line 46 .

In the opening provided in the insulating layer 44 , for example, a bump 52 is formed through a UBM (Under Bump Metallurgy) layer 50 . The electronic device 100 is connected to a wiring board or the like via bumps 52 , for example.

In addition, this invention is not limited to the said embodiment, The modification, improvement, etc. within the range which can achieve the objective of this invention are included in this inventor. [Example]

Hereafter, although an Example demonstrates this invention in detail, this invention is not limited at all by description of these Examples.

First, the raw materials used in Examples and Comparative Examples will be described in detail.

<Silane Compound> First, the silane compound used in the examples will be described in detail.

(Silane compound 1) As the silane compound 1, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine (manufactured by Shin-Etsu Chemical Co., Ltd.) represented by the following formula (S1) was prepared. X-12-5263HP).

<Silane coupling agent> Moreover, the silane coupling agent of the structure different from the silane compound demonstrated in this embodiment is demonstrated in detail.

(Silane coupling agent 1) The silane coupling agent 1 which is a condensate of cyclohexene-1,2-dicarboxylic anhydride and 3-aminopropyltriethoxysilane was synthesized by the following method. The synthesis method will be described in detail. In an appropriately sized reaction vessel equipped with a stirrer and cooling tube, cyclohexene-1,2-dicarboxylic anhydride (45.6 g, 300 mmol) was dissolved in N-methyl-2-pyrrolidone (970 g), and Adjust to 30°C in a constant temperature bath. Next, 3-aminopropyltriethoxysilane (62 g, 280 mmol) was placed in the dropping funnel, and was added dropwise to the dissolving solution over 60 minutes. After completion of the dropwise addition, stirring was performed at 30° C. for 18 hours to obtain a silane coupling agent 1 represented by the following formula (S2).

(Silane coupling agent 2) A silane coupling agent that is a condensate of 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 3-aminopropyltriethoxysilane was synthesized by the following method 2. The synthesis method will be described in detail. 3,3',4,4'-Benzophenonetetracarboxylic dianhydride (32.2 g, 100 mmol) was dissolved in N-methyl-2-pyrrole in an appropriately sized reaction vessel equipped with a stirrer and cooling tube Pyridone (669g), and adjusted to 30°C in a constant temperature bath. Next, 3-aminopropyltriethoxysilane (42.1 g, 190 mmol) was placed in the dropping funnel, and was added dropwise to the dissolving solution over 60 minutes. After completion of the dropwise addition, stirring was performed at 30° C. for 18 hours to obtain a compound represented by the following formula (S3) as a silane coupling agent 2 .

<Alkali-soluble resin> Next, the alkali-soluble resin used in each Example and a comparative example is demonstrated in detail.

(Alkali-Soluble Resin 1) Alkali-soluble resin 1, which is a polyamide resin, was prepared by the following procedure. Put 206.58 g of diphenyl ether-4,4'-dicarboxylic acid represented by the following formula (DC2) into a four-necked separable glass flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen inlet tube. 170.20 g (0.346 mol) of a mixture of dicarboxylic acid derivatives obtained by reacting 1-hydroxy-1,2,3-benzotriazole･monohydrate 216.19 g (1.600 mol) with 170.20 g (0.346 mol), 5 - 4.01 g (0.047 mol) of aminotetrazole, 45.22 g (0.196 mol) of 4,4'-methylenebis(2-aminophenol) represented by the following formula (DA2), and the following formula (DA3) 56.24 g (0.196 mol) of 4,4'-methylene bis(2-amino-3,6-dimethylphenol) represented. Thereafter, 578.3 g of N-methyl-2-pyrrolidone was charged into the separable flask to dissolve each raw material component. Next, it was made to react at 90 degreeC for 5 hours using an oil bath. Next, 24.34 g (0.141 mol) of 4-ethynyl phthalic anhydride and 121.7 g of N-methyl-2-pyrrolidone were added to the above separable flask, stirred at 90°C for 2 hours while allowing After the reaction, the reaction was terminated after cooling to 23°C. The filtrate obtained by filtering the reaction mixture in the separable flask was poured into a solution of water/isopropanol=7/4 (volume ratio). Thereafter, the precipitate was collected by filtration, washed sufficiently with water, and then dried under vacuum to obtain the target alkali-soluble resin 1 . The weight average molecular weight Mw of the obtained alkali-soluble resin 1 was 18081.

<Sensitizer> Next, the photosensitizer used in each of Examples and Comparative Examples will be described in detail.

(Sensitizer 1) The photosensitizer 1 which is a diazoquinone compound was synthesized by the following procedure. 11.04 g (0.026 mol) of phenol represented by the following formula (P-1), 1,2-naphthoquinone- 18.81 g (0.070 mol) of 2-diazide-5-sulfonyl chloride and 170 g of acetone were stirred to dissolve them. Then, while cooling the flask with a water bath so that the temperature of the reaction solution would not become 35° C. or higher, a mixed solution of 7.78 g (0.077 mol) of triethylamine and 5.5 g of acetone was slowly added dropwise. After reacting at room temperature in this state for 3 hours, 1.05 g (0.017 mol) of acetic acid was added and reacted for 30 minutes. Next, after filtering the reaction mixture, the filtrate was poured into a mixed solution of water/acetic acid (990 mL/10 mL). Next, the precipitate was collected by filtration, washed sufficiently with water, and then dried under vacuum. Thereby, the photosensitizer 1 represented by the structure of following formula (Q-1) was obtained.

<Thermal crosslinking agent> As the thermal crosslinking agent, the following thermal crosslinking agent 1 was used. ･Thermal crosslinking agent 1: p-xylene glycol (PXG manufactured by IHARANIKKEI CHEMICAL INDUSTRY)

<Surfactant> As the surfactant, the following Surfactant 1 was used. ･Surfactant 1: Fluorinated surfactant (FC4430 manufactured by 3M Japan)

<Solvent> As a solvent, the following mixed solvent 1 was used. ･Mixed solvent 1: N-methylpyrrolidone (NMP)/γ-butyrolactone (GBL)=6/4 (mass ratio)

(Preparation of Photosensitive Resin Composition of Each Example and Comparative Example) The photosensitive resin composition of each Example and Comparative Example was prepared as follows. First, the above-mentioned mixed solvent 1 and each raw material component other than the solvent are prepared. Next, according to the blending ratio shown in the following Table 1, each raw material was added to the mixed solvent 1 and stirred, and then filtered with a PTFE membrane filter with a pore size of 0.2 μm, thereby obtaining each example and comparative example. The varnish of the photosensitive resin composition. In addition, in the mixing ratio of each raw material shown in the following Table 1, silane compound, silane coupling agent, alkali-soluble resin, photosensitizer, thermal crosslinking agent are described in mass parts. Also, as the mixed solvent 1, 108 parts by mass of N-methylpyrrolidone (NMP) and 72 parts by mass of γ-butyrolactone (GBL) were used with respect to 100 parts by mass of the alkali-soluble resin. Furthermore, surfactant is the concentration (ppm) with respect to the whole varnish of the photosensitive resin composition containing a solvent.

The following evaluations were performed about the photosensitive resin composition of each Example and a comparative example.

(Adhesiveness after prebaking) Using the photosensitive resin composition of each Example and the comparative example, the adhesiveness of the photosensitive resin composition after prebaking and an Al pad was evaluated as follows. First, an Al substrate is prepared as a base material. Next, the varnish of the photosensitive resin composition was applied on the Al substrate using a spin coater. Next, after prebaking at a temperature of 105° C. for 4 minutes using a hot plate, a prebaked photosensitive resin composition of 10.9 μm was obtained. Next, the pre-baked photosensitive resin composition was patterned, and broadband exposure was performed using a broadband mask alignment exposure machine (MA8 manufactured by SUSS MicroTec Co., Ltd.). Then, at a temperature of 23°C, 2.38% Tetramethylammonium hydroxide aqueous solution, the development time was adjusted so that the difference between the film thickness after prebaking and the film thickness after development was 3.0 μm, and paddle development was performed twice to remove pattern masking. In addition, for pattern masking, the mask (reticle made by Toppan Printing Co., Ltd., test chart No. 1) in which the remaining pattern and punching pattern of width 0.88 micrometers - 50 micrometers were drawn was used. Next, whether or not the photosensitive resin composition patterned here can form a desired pattern was observed with the naked eye, and evaluated by the following evaluation criteria. ○ (good): Desired patterning was completed as pattern masking was performed. × (defective): A part of the patterned photosensitive resin composition was peeled off from the Al substrate, and desired patterning was not completed. Moreover, about the photosensitive resin composition for each of each Example and the comparative example, the case where the temperature of pre-baking was made into 110 degreeC and 115 degreeC was also evaluated. The evaluation results are shown in Table 1 below.

(Generation of residue during development) Using the photosensitive resin composition of each example and comparative example, the generation of residue of the photosensitive resin composition during development was evaluated as follows with respect to the photosensitive resin composition after prebaking . First, a Cu substrate was prepared as a base material. Next, the varnish of the photosensitive resin composition was applied on the Cu substrate using a spin coater. Next, after prebaking at a temperature of 105° C. for 4 minutes using a hot plate, a prebaked photosensitive resin composition of 10.9 μm was obtained. Next, the pre-baked photosensitive resin composition was patterned and exposed using a broadband mask alignment exposure machine (MA8 manufactured by SUSS MicroTec Co., Ltd.), and then, at a temperature of 23°C, 2.38% With the aqueous solution of tetramethylammonium hydroxide, the development time was adjusted so that the difference between the film thickness after prebaking and the film thickness after development was 3.0 μm, and flood development was performed twice to remove pattern masking. In addition, for pattern masking, the mask for WLP manufactured by Mitani Micronics was used. Next, whether or not residues of the photosensitive resin composition after development were generated on the Cu substrate was observed with the naked eye, and evaluated by the following evaluation criteria. ◯ (good): No residue of the photosensitive resin composition was generated at the exposed and developed portion on the Cu substrate. × (defective): Residue of the photosensitive resin composition was generated at the exposed and developed portion on the Cu substrate, and desired patterning was not completed. Moreover, about the photosensitive resin composition for each of each Example and the comparative example, the case where the temperature of pre-baking was made into 110 degreeC and 115 degreeC was also evaluated. The evaluation results are shown in Table 1 below.

(Adhesion after post-baking) Using the photosensitive resin composition of each example and comparative example, the adhesiveness between the photosensitive resin composition after post-baking and aluminum (Al) was tested by the following two methods evaluate. First, the first method will be described. The first method uses a cutter as a method of singulating the Al and photosensitive resin composition. First, a silicon wafer is prepared as a base material. Next, after coating titanium (Ti) on the base material so as to have a thickness of 0.03 μm (300 Å), Al was sputtered onto Ti so as to have a thickness of 0.3 μm (3000 Å), and then, using a spin coater, The varnish of the photosensitive resin composition is coated on the Al. Next, after prebaking at a temperature of 120° C. for 4 minutes using a hot plate, it was further post-baked at a temperature of 220° C. for 1 hour in a nitrogen atmosphere using an oven to obtain a cured film with a thickness of 7 μm. Here, the cured film is in close contact with Al. That is, a laminated structure in which the substrate, Ti, Al, and cured film are sequentially laminated is obtained. Using this laminated structure, the adhesiveness was evaluated according to JIS D 0202. Specifically, from the surface where the cured film exists in the laminated structure, scratches were performed on the cured film and Al so that 100 squares of 1 mm square could be formed and singulated. Next, a cellophane tape was attached to the cured film. After 1 minute of attachment, the cellophane tape was peeled off from the hardened film. After peeling, among 100 squares, count the number of squares remaining without peeling of the cured film and Al and the number of squares after peeling, and use this as the evaluation result of the case without PCT process. The evaluation results are shown in Table 1 below. In Table 1 the number of peeled squares is shown. Moreover, in the above, after attaching the cellophane tape to the cured film, the cellophane tape was peeled off from the cured film after leaving to stand at a temperature of 125° C., a humidity of 100%, and an air pressure of 2.3 atm for 24 hours. After peeling, among 100 squares, the number of squares remaining without peeling of the cured film and Al and the number of squares after peeling were counted, and this was regarded as the evaluation result of the presence of the PCT process. The evaluation results are shown in Table 1 below. Table 1 shows the number of peeled squares. Furthermore, the second method will be described. The second method uses a pattern as a method of singulating the photosensitive resin composition. First, a silicon wafer is prepared as a base material. After coating titanium (Ti) on the base material to a thickness of 0.05 μm (500 Å), Al was sputtered on Ti to a thickness of 0.3 μm (3000 Å), and then the photosensitive film was coated with a spin coater. The varnish of the resin composition is coated on Al. Next, after pre-baking at 120° C. for 4 minutes using a hot plate, the photosensitive resin composition was patterned and exposed using a broadband mask alignment exposure machine (MA8 manufactured by SUSS MicroTec Co., Ltd.). The temperature is 23° C., and a 2.38% tetramethylammonium hydroxide aqueous solution is used as a developing solution to carry out flood development. Then, the masking of the pattern was removed, and the oven was further baked at 220° C. for 1 hour under a nitrogen atmosphere to obtain a single-piece cured film with a thickness of 7 μm. Here, the cured film is in close contact with Al. That is, a laminated structure in which a base material, Al, and a cured film were sequentially laminated was obtained, and the laminated portion of the cured film was separated into 100 pieces in a square of 1 mm square. Next, with respect to this laminate, according to JIS D 0202, the same evaluation as the case where the above-mentioned method of singulating Al was performed by a cutter was performed, and the adhesiveness was evaluated. Furthermore, those who used a cutter as a method of singulation were able to evaluate higher adhesiveness than those who used a pattern. The evaluation results are shown in Table 1 below for the case of no PCT procedure and the case of PCT procedure respectively. In addition, the evaluation results of the adhesiveness are all small values, that is, the smaller the number of squares showing peeling, the higher the adhesiveness between the cured film and Al. In addition, the PCT program is intended to accelerate the test, and is performed for evaluating the long-term adhesion between the photosensitive resin composition and Al after the post-baking.

(Chemical resistance after post-baking) Using the photosensitive resin composition of each Example and the comparative example, the chemical resistance of the photosensitive resin composition after post-baking was evaluated as follows. First, a silicon wafer is prepared as a base material. Next, the varnish of the photosensitive resin composition was applied on the substrate using a spin coater. Next, the photosensitive resin composition was pre-baked at 120° C. for 4 minutes, and then post-baked at 220° C. for 60 minutes, thereby obtaining a cured film of the photosensitive resin composition. Here, the thickness of the cured film was 7 μm. Next, the photosensitive resin composition is coated on the above-mentioned cured film. Next, prebaking was carried out at a temperature of 120° C. for 4 minutes to form a dry film on the cured film. Here, whether or not there is no crack in the cured film of the photosensitive resin composition was observed by dark field using an optical microscope (MX50 manufactured by Olympus Co., Ltd.), and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1 below. ⊚ (very good): No cracks were observed in the cured film. ○ (good): Cracks were observed in the cured film, but the number of cracks was extremely small, and since the cracks were very short, there was no problem in practical use. x (poor): Cracks were observed in the cured film.

[Table 1]

As shown in the above Table 1, it was confirmed that the photosensitive resin composition of the example achieved the adhesion between the photosensitive resin composition after prebaking and the Al pad in a good balance compared with the photosensitive resin composition of Comparative Example 1. Suppression of generation of residue of the photosensitive resin composition during improvement and development. Furthermore, it was confirmed that the photosensitive resin composition of Example can improve the adhesiveness between the cured film of the photosensitive resin composition after post-baking and metals such as Al, compared with the photosensitive resin composition of Comparative Example 1. The chemical resistance of the photosensitive resin composition after postbaking can be improved.

This application claims priority based on Japanese Patent Application No. 2017-129668 filed on June 30, 2017, and the entire disclosure thereof is incorporated herein.

30‧‧‧interlayer insulating film 32‧‧‧passivation film 34‧‧‧upper wiring 40‧‧‧rewiring layer 42‧‧‧insulating layer 44‧‧‧insulating layer 46‧‧‧rewiring 50‧‧‧UBM Layer 52‧‧‧Bump 100‧‧‧Electronic Device

FIG. 1 is a cross-sectional view showing an example of an electronic device according to this embodiment.

30‧‧‧Interlayer insulating film

32‧‧‧passivation film

34‧‧‧Wiring on the top layer

40‧‧‧Redistribution layer

42‧‧‧Insulation layer

44‧‧‧Insulation layer

46‧‧‧Rewiring

50‧‧‧UBM layer

52‧‧‧Bump

100‧‧‧electronic devices

Claims (7)

A photosensitive resin composition comprising: a silane compound represented by the following general formula (1); an alkali-soluble resin; and a photosensitive agent,

In the above general formula (1), ^R1 represents an organic group with a carbon number of 1 or more and 30 or less; wherein, those containing an aromatic ring in ^R1 are excluded; ^R2 and ^R3 independently represent a carbon number of 1 or more and 30 or less. The organic groups; A each independently represent a hydroxyl group or an organic group with a carbon number of 1 to 30; A can be the same as each other or different from each other; One of the alkoxy groups; B each independently represents a hydroxyl group or an organic group with a carbon number of 1 or more and a carbon number of 30 or less; B may be the same as or different from each other, and at least one of B is selected from a hydroxyl group and a carbon number of 1 or more and One of the alkoxy groups below 30; and the alkali-soluble resin comprises a polyamide resin; the polyamide resin comprises a structural unit represented by the following formula (PA1),

Such as the photosensitive resin composition of claim 1, wherein the R ¹ in the general formula (1) is an alkylene group with a carbon number of 1 or more and 30 or less. Such as the photosensitive resin composition of claim 1 or 2 of the patent scope, wherein, The content of the silane compound is not less than 0.01 parts by mass and not more than 30 parts by mass with respect to 100 parts by mass of the alkali-soluble resin. Such as the photosensitive resin composition of claim 1 or 2, wherein the photosensitive agent is a diazoquinone compound. Such as the photosensitive resin composition of item 1 or 2 of the scope of the patent application, which is used to form a permanent film used as an interlayer film, surface protection film or dam material. A resin film, which is formed by hardening the photosensitive resin composition in any one of claims 1 to 5. An electronic device comprising the resin film described in claim 6 of the patent application.

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