TW202311367A - Negative photosensitive resin composition, negative photosensitive polymer, cured film and semiconductor device - Google Patents

Abstract

A negative photosensitive resin composition according to the present invention contains (A) a polyimide, (B) a crosslinking agent that contains a multifunctional (meth)acrylate, and (C) a photo polymerization initiator; and the polyimide (A) comprises a structural unit (a1) represented by general formula (a1) and a structural unit (a2) represented by general formula (a2). (In general formula (a1), each Y represents a group that is selected from among groups represented by general formula (a1-1), general formula (a1-2) and general formula (a1-3); and the plurality of Y moieties may be the same as or different from each other.).

Description

Negative photosensitive resin composition, negative photosensitive polymer, cured film and semiconductor device

The invention relates to a negative photosensitive resin composition, a negative photosensitive polymer, a cured film and a semiconductor device.

Polyimide resin has high mechanical strength, heat resistance, insulation, and solvent resistance, so it is widely used as protective materials in liquid crystal display elements and semiconductors, insulating materials, and films for electronic materials such as color filters.

Patent Document 1 discloses a block-copolymerizable polyimide soluble in a bipolar aprotic solvent, and describes that the block-copolymerizable polyimide can be obtained using a specific acid anhydride.

Patent Document 2 discloses a polyimide resin composed of structural units having a specific structure. Patent Document 2 describes an example in which a polyimide resin was synthesized using 4,4-diamino-3,3-diethyl-5,5-dimethyldiphenylmethane.

In Patent Document 3, a polyimide elastomer resin is disclosed, which is composed of aromatic tetracarboxylic dianhydride, 4,4'- Terpolymer obtained from diaminodiphenylmethane and polyether oligomers with p-aminobenzoate groups at both ends, and has a specific molecular weight. In Patent Document 3, bis(4-amino-3-ethyl-5-methylphenyl)methane is mentioned as 4,4'-diaminodiphenylmethane. Patent Document 3 describes that this resin is excellent in heat and humidity resistance.

In Patent Document 4, a block copolymer composed of polyimide structural unit and dimethylsiloxane structural unit is disclosed, the polyimide structural unit is composed of aromatic tetracarboxylic dianhydride and 4, 4'-Diaminodiphenylmethane derivatives are formed. In Patent Document 4, bis(4-amino-3-ethyl-5-methylphenyl)methane is mentioned as 4,4'-diaminodiphenylmethane. Patent Document 4 describes that the resin is excellent in heat resistance and solvent solubility. [Prior Art Literature] [Patent Document]

[Patent Document 1] International Publication No. 015/091122 [Patent Document 2] Japanese Patent Laid-Open No. 64-16829 [Patent Document 3] Japanese Patent Application Laid-Open No. 8-217874 [Patent Document 4] Japanese Patent Application Laid-Open No. 9-40777

[Problem to be Solved by the Invention]

However, in the conventional techniques described in Patent Documents 1 to 4, there is room for improvement in mechanical strength such as elongation of a film made of polyimide obtained from a photosensitive resin composition.

Conventionally, in order to improve the solubility of polyimide in organic solvents, fluorine atoms were introduced into the polyimide skeleton. In the case of synthesizing polyimide, since the electrons of the imide ring are affected by the strong electron-attracting property of the fluorine atom, the obtained polyimide is easily hydrolyzed, and thus the mechanical strength such as elongation decreases. That is, conventional polyimides have room for improvement from the viewpoint of the balance between solubility in organic solvents and mechanical strength such as elongation. [Technical means to solve the problem]

The inventors of the present invention have found that the above-mentioned problems can be solved as long as the polyimide has a specific structure, and completed the present invention. That is, the present invention can be as follows.

（通式（a1）中，Y選自下述通式（a1-1）、下述通式（a1-2）及下述通式（a1-3）所表示之基，存在複數個之Y可以相同，亦可以不同。

（通式（a1-1）中，R ⁷及R ⁸分別獨立地表示氫原子、碳數1～3的烷基、碳數1～3的烷氧基，存在複數個之R ⁷彼此及存在複數個之R ⁸彼此可以相同，亦可以不同。R ⁹表示氫原子、碳數1～3的烷基、碳數1～3的烷氧基，存在複數個之R ⁹彼此可以相同，亦可以不同。*表示鍵結鍵。 通式（a1-2）中，R ¹⁰及R ¹¹分別獨立地表示氫原子、碳數1～3的烷基、碳數1～3的烷氧基，存在複數個之R ¹⁰彼此及存在複數個之R ¹¹彼此可以相同，亦可以不同。*表示鍵結鍵。 通式（a1-3）中，Z表示碳數1～5的伸烷基、2價的芳香族基。 *表示鍵結鍵。） 通式（a2）中，R ¹～R ⁴分別獨立地表示碳數1～3的烷基或碳數1～3的烷氧基，R ¹和R ²為不同之基，R ³和R ⁴為不同之基。 X ¹表示單鍵、-SO ₂-、-C(=O)-、碳數1～5的直鏈或支鏈的伸烷基或者碳數1～5的直鏈或支鏈的氟伸烷基，存在複數個之X ¹可以相同，亦可以不同。） [2]如[1]之負型感光性樹脂組成物，其中，前述聚醯亞胺（A）進一步包含下述通式（a3）所表示之結構單元（a3）。

（通式（a3）中，Q ¹、Q ²分別獨立地表示羥基、羧基。X ²表示單鍵、-SO ₂-、-C(=O)-、碳數1～5的直鏈或支鏈的伸烷基或者碳數1～5的直鏈或支鏈的氟伸烷基，存在複數個之X ²可以相同，亦可以不同。） [3]如[1]或[2]之負型感光性樹脂組成物，其中，前述聚醯亞胺（A）包含下述通式（1）所表示之結構單元。

（通式（1）中，R ¹～R ⁴、X ¹與通式（a2）的含義相同，Y與通式（a1）的含義相同。） [4]如[2]或[3]之負型感光性樹脂組成物，其中，前述聚醯亞胺（A）包含下述通式（2）所表示之結構單元。

（通式（2）中，Q ¹、Q ²及X ²與通式（a3）的含義相同，Y與通式（a1）的含義相同。） [5]一種負型感光性聚合物，其包含下述通式（a1）所表示之結構單元（a1）和下述通式（a2）所表示之結構單元（a2）。

（通式（a1）中，Y選自下述通式（a1-1）、下述通式（a1-2）及下述通式（a1-3）所表示之基，存在複數個之Y可以相同，亦可以不同。

（通式（a1-1）中，R ⁷及R ⁸分別獨立地表示氫原子、碳數1～3的烷基、碳數1～3的烷氧基，存在複數個之R ⁷彼此及存在複數個之R ⁸彼此可以相同，亦可以不同。R ⁹表示氫原子、碳數1～3的烷基、碳數1～3的烷氧基，存在複數個之R ⁹彼此可以相同，亦可以不同。*表示鍵結鍵。 通式（a1-2）中，R ¹⁰及R ¹¹分別獨立地表示氫原子、碳數1～3的烷基、碳數1～3的烷氧基，存在複數個之R ¹⁰彼此及存在複數個之R ¹¹彼此可以相同，亦可以不同。*表示鍵結鍵。 通式（a1-3）中，Z表示碳數1～5的伸烷基、2價的芳香族基。 *表示鍵結鍵。） 通式（a2）中，R ¹～R ⁴分別獨立地表示碳數1～3的烷基或碳數1～3的烷氧基，R ¹和R ²為不同之基，R ³和R ⁴為不同之基。 X ¹表示單鍵、-SO ₂-、-C(=O)-、碳數1～5的直鏈或支鏈的伸烷基或者碳數1～5的直鏈或支鏈的氟伸烷基，存在複數個之X ¹可以相同，亦可以不同。） [6]如[5]之負型感光性聚合物，其進一步包含下述通式（a3）所表示之結構單元（a3）。

（通式（a3）中，Q ¹、Q ²分別獨立地表示羥基、羧基。X ²表示單鍵、-SO ₂-、-C(=O)-、碳數1～5的直鏈或支鏈的伸烷基或者碳數1～5的直鏈或支鏈的氟伸烷基，存在複數個之X ²可以相同，亦可以不同。） [7]如[5]或[6]之負型感光性聚合物，其包含下述通式（1）所表示之結構單元。

（通式（1）中，R ¹～R ⁴、X ¹與通式（a2）的含義相同，Y與通式（a1）的含義相同。） [8]如[5]或[6]之負型感光性聚合物，其包含下述通式（2）所表示之結構單元。

（通式（2）中，Q ¹、Q ²及X ²與通式（a3）的含義相同，Y與通式（a1）的含義相同。） [9]如[6]至[8]中任一項之負型感光性聚合物，其中，在以下條件測得之重量平均分子量的減少率為9%以下。 條件為下： 在前述負型感光性聚合物100質量份中添加γ-丁內酯400質量份、4-甲基四氫吡喃200質量份及水50質量份並在100℃攪拌了6小時之情況，藉由下述公式進行計算。 公式：[（試驗前的重量平均分子量-試驗後的重量平均分子量）/試驗前的重量平均分子量]×100 [10]一種硬化膜，其由[1]至[4]中任一項之負型感光性樹脂組成物的硬化物構成。 [11]一種半導體裝置，其具備樹脂膜，該樹脂膜包含[1]至[4]中任一項之負型感光性樹脂組成物的硬化物。 [12]一種半導體裝置，其具備： 層間絕緣膜； 樹脂膜，其設置於前述層間絕緣膜上且包含[1]至[4]中任一項之負型感光性樹脂組成物的硬化物；及 再配線，其埋設於前述樹脂膜中。 [發明之效果] [1] A negative photosensitive resin composition comprising (A) polyimide, (B) a crosslinking agent comprising polyfunctional (meth)acrylate, and (C) a photopolymerization initiator, polyamide The imine (A) contains a structural unit (a1) represented by the following general formula (a1) and a structural unit (a2) represented by the following general formula (a2).

(In the general formula (a1), Y is selected from the groups represented by the following general formula (a1-1), the following general formula (a1-2) and the following general formula (a1-3), and there are plural Y Can be the same or different.

(In the general formula (a1-1), R ⁷ and R ⁸ independently represent a hydrogen atom, an alkyl group with 1 to 3 carbons, and an alkoxy group with 1 to 3 carbons, and there are multiple R ⁷ and each other Plural R ⁸ may be the same or different. ^{R 9} represents a hydrogen atom, an alkyl group with 1 to 3 carbons, and an alkoxy group with 1 to 3 carbons. There may be a plurality of R ^9s that are the same or different from each other. Different. * represents a bond. In the general formula (a1-2), R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group with 1 to 3 carbons, and an alkoxy group with 1 to 3 carbons, and there are plural R ¹⁰ of each and plural R ¹¹ may be the same or different from each other. * represents a bonding bond. In the general formula (a1-3), Z represents an alkylene group having 1 to 5 carbon atoms, a divalent Aromatic group. *Represents a bond.) In the general formula (a2), R ¹ to R ⁴ each independently represent an alkyl group with 1 to 3 carbons or an alkoxy group with 1 to 3 carbons, and R ¹ and R ² is a different base, R ³ and R ⁴ are different bases. X ¹ represents a single bond, -SO ₂ -, -C(=O)-, straight-chain or branched chain alkylene with 1 to 5 carbons, or straight-chain or branched fluoroalkylene with 1 to 5 carbons Base, there are plural X ¹ which may be the same or different. ) [2] The negative photosensitive resin composition according to [1], wherein the polyimide (A) further includes a structural unit (a3) represented by the following general formula (a3).

(In the general formula (a3), Q ¹ and Q ² independently represent a hydroxyl group and a carboxyl group. X ² represents a single bond, -SO ₂ -, -C(=O)-, straight or branched chains with 1 to 5 carbons Chain alkylene group or straight chain or branched chain fluoroalkylene group with 1 to 5 carbons, there are multiple X ² can be the same or different.) [3] As in [1] or [2] In the type photosensitive resin composition, the aforementioned polyimide (A) includes a structural unit represented by the following general formula (1).

(In general formula (1), R ¹ ~ R ⁴ , X ¹ have the same meaning as general formula (a2), and Y has the same meaning as general formula (a1). [4] As in [2] or [3] The negative photosensitive resin composition, wherein the aforementioned polyimide (A) includes a structural unit represented by the following general formula (2).

(In the general formula (2), Q ¹ , Q ² and X ² have the same meaning as the general formula (a3), and Y has the same meaning as the general formula (a1).) [5] A negative photosensitive polymer, which A structural unit (a1) represented by the following general formula (a1) and a structural unit (a2) represented by the following general formula (a2) are included.

(In the general formula (a1), Y is selected from the groups represented by the following general formula (a1-1), the following general formula (a1-2) and the following general formula (a1-3), and there are plural Y Can be the same or different.

(In the general formula (a1-1), R ⁷ and R ⁸ independently represent a hydrogen atom, an alkyl group with 1 to 3 carbons, and an alkoxy group with 1 to 3 carbons, and there are multiple R ⁷ and each other Plural R ⁸ may be the same or different. ^{R 9} represents a hydrogen atom, an alkyl group with 1 to 3 carbons, and an alkoxy group with 1 to 3 carbons. There may be a plurality of R ^9s that are the same or different from each other. Different. * represents a bond. In the general formula (a1-2), R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group with 1 to 3 carbons, and an alkoxy group with 1 to 3 carbons, and there are plural R ¹⁰ of each and plural R ¹¹ may be the same or different from each other. * represents a bonding bond. In the general formula (a1-3), Z represents an alkylene group having 1 to 5 carbon atoms, a divalent Aromatic group. *Represents a bond.) In the general formula (a2), R ¹ to R ⁴ each independently represent an alkyl group with 1 to 3 carbons or an alkoxy group with 1 to 3 carbons, and R ¹ and R ² is a different base, R ³ and R ⁴ are different bases. X ¹ represents a single bond, -SO ₂ -, -C(=O)-, straight-chain or branched chain alkylene with 1 to 5 carbons, or straight-chain or branched fluoroalkylene with 1 to 5 carbons Base, there are plural X ¹ which may be the same or different. ) [6] The negative photosensitive polymer according to [5], further comprising a structural unit (a3) represented by the following general formula (a3).

(In the general formula (a3), Q ¹ and Q ² independently represent a hydroxyl group and a carboxyl group. X ² represents a single bond, -SO ₂ -, -C(=O)-, straight or branched chains with 1 to 5 carbons Chain alkylene group or straight chain or branched chain fluoroalkylene group with 1 to 5 carbons, there are multiple X ² can be the same or different.) [7] as negative of [5] or [6] A photosensitive polymer comprising a structural unit represented by the following general formula (1).

(In general formula (1), R ¹ to R ⁴ and X ¹ have the same meaning as general formula (a2), and Y has the same meaning as general formula (a1).) [8] As in [5] or [6] A negative photosensitive polymer comprising a structural unit represented by the following general formula (2).

(In general formula (2), Q ¹ , Q ² and X ² have the same meaning as general formula (a3), and Y has the same meaning as general formula (a1).) [9] As in [6] to [8] Any one of the negative photosensitive polymers, wherein the reduction rate of the weight average molecular weight measured under the following conditions is 9% or less. The conditions are as follows: 400 parts by mass of γ-butyrolactone, 200 parts by mass of 4-methyltetrahydropyran, and 50 parts by mass of water were added to 100 parts by mass of the negative photosensitive polymer, and stirred at 100° C. for 6 hours. In the case of , it is calculated by the following formula. Formula: [(weight average molecular weight before test-weight average molecular weight after test)/weight average molecular weight before test]×100 The cured product of the type photosensitive resin composition. [11] A semiconductor device comprising a resin film comprising a cured product of the negative photosensitive resin composition according to any one of [1] to [4]. [12] A semiconductor device comprising: an interlayer insulating film; a resin film provided on the interlayer insulating film and comprising a cured product of the negative photosensitive resin composition according to any one of [1] to [4]; And rewiring, which is buried in the aforementioned resin film. [Effect of Invention]

According to the present invention, it is possible to provide a negative photosensitive polymer capable of obtaining a cured product such as a film having excellent solubility in organic solvents, suppressed hydrolysis, and excellent mechanical strength such as elongation, and a negative photosensitive polymer including the polymer. permanent resin composition.

Hereinafter, embodiments of the present invention will be described using the drawings. In addition, in all drawings, the same code|symbol is attached|subjected to the same component, and description is abbreviate|omitted suitably. Also, "A to B" means "above A" to "below B" unless otherwise specified.

The negative photosensitive resin composition of the present embodiment includes (A) polyimide, (B) a crosslinking agent including polyfunctional (meth)acrylate, and (C) a photopolymerization initiator.

[Polyimide (A)] The polyimide (A) (negative photosensitive polymer) of this embodiment includes a structural unit (a1) represented by the following general formula (a1) and a structural unit (a2) represented by the following general formula (a2). ).

In the general formula (a1), Y is a divalent organic group. As the divalent organic group, known organic groups can be used within the range of exerting the effect of the present invention, however, from the viewpoint of the effect of the present invention, it is selected from the following general formula (a1-1), the following general formula (a1-2) and a divalent organic group of the following general formula (a1-3) are preferable.

In the general formula (a1-1), R ⁷ and R ⁸ independently represent a hydrogen atom, an alkyl group with 1 to 3 carbons, and an alkoxy group with 1 to 3 carbons, and there are plural R ⁷ and each other and there are plural Each of R ⁸ may be the same as or different from each other. From the viewpoint of the effects of the present invention, R ⁷ and R ⁸ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbons, more preferably a hydrogen atom.

R ⁹ represents a hydrogen atom, an alkyl group having 1 to 3 carbons, and an alkoxy group having 1 to 3 carbons, and a plurality of R ⁹ may be the same or different from each other. From the viewpoint of the effects of the present invention, R ⁹ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbons, more preferably a hydrogen atom. * Indicates a bonded bond.

In the general formula (a1-2), R ¹⁰ and R ¹¹ independently represent a hydrogen atom, an alkyl group with 1 to 3 carbons, and an alkoxy group with 1 to 3 carbons, and there are plural R ^10s with each other and plural Each R ¹¹ may be the same as or different from each other.

From the viewpoint of the effects of the present invention, R ¹⁰ and R ¹¹ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbons, more preferably at least one of R ¹⁰ and at least one of R ¹¹ is carbon An alkyl group with a number of 1 to 3, more preferably three R ¹⁰ are an alkyl group with a carbon number of 1 to 3 and one R ¹⁰ is a hydrogen atom, and three R ¹¹ are an alkyl group with a carbon number of 1 to 3 and 1 R ¹¹ is a hydrogen atom, particularly preferably 3 R ¹⁰ is a methyl group and 1 R ¹⁰ is a hydrogen atom, and 3 R ¹¹ is a methyl group and 1 R ¹¹ is a hydrogen atom. * Indicates a bonded bond.

In the general formula (a1-3), Z represents an alkylene group having 1 to 5 carbon atoms or a divalent aromatic group. * Indicates a bonded bond.

In the general formula (a2), R ¹ to R ⁴ independently represent an alkyl group with 1 to 3 carbons or an alkoxy group with 1 to 3 carbons, R ¹ and R ² are different groups, R ³ and R ⁴ as the basis of difference. From the viewpoint of the effect of the present invention, R ¹ to R ⁴ are preferably an alkyl group having 1 to 3 carbon atoms.

X ¹ represents a single bond, -SO ₂ -, -C(=O)-, straight-chain or branched chain alkylene with 1 to 5 carbons, or straight-chain or branched fluoroalkylene with 1 to 5 carbons Base, there are plural X ¹ which may be the same or different.

From the viewpoint of the effects of the present invention, ^X is preferably a single bond, a straight-chain or branched chain alkylene group having 1 to 5 carbons, or a straight-chain or branched chain fluoroalkylene group having 1 to 5 carbons. , more preferably a straight chain or branched chain alkylene group having 1 to 5 carbons or a straight chain or branched chain fluoroalkylene group having 1 to 5 carbons.

Since the polyimide (A) of this embodiment includes the structural unit represented by the general formula (a2), the influence on the electrons of the imide ring is suppressed, and the hydrolysis of the polyimide is suppressed, so that elongation, etc. It is excellent in mechanical strength and also excellent in solubility to organic solvents. In other words, the polyimide (A) of this embodiment and the negative photosensitive resin composition containing the polyimide (A) are excellent in the balance of these characteristics.

The aforementioned polyimide (A) may further include a structural unit (a3) represented by the following general formula (a3). By including the structural unit (a3), the solvent solubility is further improved.

In the general formula (a3), Q ¹ and Q ² independently represent a hydroxyl group and a carboxyl group, preferably a hydroxyl group.

X ² represents a single bond, -SO ₂ -, -C(=O)-, straight-chain or branched chain alkylene with 1 to 5 carbons, or straight-chain or branched fluoroalkylene with 1 to 5 carbons Base, there are plural X ² which may be the same or different.

From the viewpoint of the effect of the present invention, ^X2 is preferably a straight-chain or branched chain alkylene group having 1 to 5 carbons or a straight chain or branched chain fluoroalkylene group having 1 to 5 carbons.

Specifically, the polyimide (A) of this embodiment can contain the structural unit represented by following General formula (1).

In the general formula (1), R ¹ to R ⁴ and X ¹ have the same meanings as those of the general formula (a2), and Y has the same meanings as those of the general formula (a1).

Specifically, the polyimide (A) of this embodiment may further include a structural unit represented by the following general formula (2).

In the general formula (2), Q ¹ , Q ² , and X ² have the same meaning as the general formula (a3), and Y has the same meaning as the general formula (a1).

It is preferable that at least one of both terminals of the polyimide (A) of this embodiment is a group represented by the following general formula (3). By including this group, hydrolysis is suppressed, and mechanical strength such as elongation is further excellent.

In general formula (3), Y has the same meaning as general formula (a1). * Indicates a bonded bond.

The weight average molecular weight of the polyimide (A) of this embodiment is 5,000-200,000, Preferably it is 10,000-100,000.

In addition, the polyimide (A) of this embodiment has excellent solubility in solvents, and it is not necessary to prepare a varnish in the state of a precursor, so it is possible to prepare a varnish containing the polyimide (A), and it is possible to use this The varnish obtains a hardened product such as a film.

＜Method for producing polyimide (A)＞ The production method of the polyimide (A) (negative photosensitive polymer) having the structural unit represented by the general formula (1) of this embodiment includes the following steps: An acid anhydride (a1') represented by the following general formula (a1') and a diamine (a2') represented by the following general formula (a2') are imidized at a temperature between 100°C and 250°C step. According to this embodiment, the polyimide (A) excellent in the solubility to an organic solvent can be synthesize|combined by a simple method.

In the general formula (a1'), Y is selected from the group represented by the aforementioned general formula (a1-1), (a1-2) or (a1-3).

In general formula (a2'), R ¹ to R ⁴ and X ¹ have the same meanings as in general formula (a2).

The equivalent ratio of the acid anhydride (a1') to the diamine (a2') in the imidization reaction of this step is an important factor determining the molecular weight of the obtained polyimide. In general, it is widely known that there is a correlation between the molecular weight of a polymer and the mechanical properties, and the larger the molecular weight, the better the mechanical properties. Therefore, in order to obtain a polyimide having a strength excellent in practical use, a certain degree of high molecular weight is required. In the present invention, the equivalent ratio of acid anhydride (a1') to diamine (a2') is not particularly limited, and the equivalent ratio of acid anhydride (a1') to diamine (a2') is in the range of 0.85 to 1.15. better. When it is less than 0.85, the molecular weight is low and becomes brittle, so the mechanical strength becomes weak. Moreover, when exceeding 1.15, since molecular weight will become low and brittle, mechanical strength will become weak. That is, as long as the equivalent ratio is in the above-mentioned range, the mechanical strength is excellent and the production stability is excellent.

By this step, it is preferable to obtain a polyimide (A) in which at least one of both terminals is an acid anhydride group represented by the following general formula (3). By including the acid anhydride group, mechanical strength such as elongation of the cured product can be further improved. Specifically, the aforementioned acid anhydride group reacts with the epoxy group of the compound having an epoxy group. When having two or more epoxy groups, the polyimides (A) can be crosslinked with each other using this compound.

In general formula (3), Y has the same meaning as general formula (a1). * Indicates a bonded bond.

Furthermore, in this step, from the viewpoint of the effects of the present invention, the acid anhydride (a1 '), diamine (a2') and diamine (a3') imidization is also preferred.

Thereby, the polyimide (A) (negative photosensitive polymer) which has the structural unit represented by the said General formula (1) and the structural unit represented by the said General formula (2) can be obtained.

In general formula (a3'), Q ¹ , Q ² and X ² have the same meaning as in general formula (a3). In order to control the molecular weight of the obtained polyimide, it is also possible to add a small amount of acid anhydride or aromatic amine as an end-capping agent to react, forming a group capable of reacting with an epoxy group to form a bond at the end.

Examples of the acid anhydride of the blocking agent include phthalic anhydride, maleic anhydride, nadic anhydride, and 1,2,4-benzenetricarboxylic anhydride, and examples of the aromatic amine include p-methylaniline. , p-methoxyaniline, p-phenoxyaniline, 4-carboxyaniline, etc. The addition amount of these acid anhydrides or aromatic amines as end-capping agents is preferably less than 5 mol%. If it exceeds 5 mol %, the molecular weight of the polyimide (A) obtained will fall remarkably, and there will arise a problem with heat resistance or a mechanical characteristic.

The equivalent ratio of acid anhydride (a1') to diamine (a2') to diamine (a3') is an important factor for determining the molecular weight of the obtained polymer. It is generally known that there is a correlation between the molecular weight and mechanical properties of a polymer, the larger the molecular weight, the better the mechanical properties. Therefore, in order to obtain a polymer having a strength excellent in practical use, a certain degree of high molecular weight is required. In the present invention, the equivalent ratio of acid anhydride (a1') to diamine (a2') to diamine (a3') used is not particularly limited, however, diamine (a2') and diamine (a3') The equivalent ratio to the acid anhydride (a1') is preferably in the range of 0.70 to 1.30. As long as the equivalent ratio is within the above range, the mechanical strength is excellent and the production stability is excellent.

This step (imidation reaction step) can be performed in an organic solvent by a known method. Examples of organic solvents include γ-butyrolactone (GBL), N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, diglyme, diethyl Aprotic polar solvents such as glycol diethyl ether, cyclohexanone, and 1,4-dioxane can be used alone or in combination of two or more. In this case, a non-polar solvent having compatibility with the above-mentioned aprotic polar solvent may be mixed and used. Examples of the nonpolar solvent include aromatic hydrocarbons such as toluene, ethylbenzene, xylene, trimethylbenzene, mineral spirits, and ether solvents such as cyclopentyl methyl ether. The ratio of the non-polar solvent in the mixed solvent can be set arbitrarily according to the properties of the resin, such as the ability of the stirring device or the viscosity of the solution, as long as the solubility of the solvent is reduced and the polyamic acid resin obtained by the reaction does not precipitate.

The reaction temperature is between 0°C and 100°C, preferably between 20°C and 80°C for about 30 minutes to 2 hours, and then between 100°C and 250°C, preferably between 120°C and 2 hours. React below 200°C for about 1 to 5 hours.

By the above production method, the reaction solution containing the polyimide (A) (negative photosensitive polymer) of this embodiment can be obtained, and further diluted with an organic solvent or the like as necessary, and used as a polymerization solution. solution (varnish for coating). As an organic solvent, what was illustrated in the said process can be used, and it may be the same organic solvent as this process, and may be a different organic solvent.

In addition, the reaction solution can also be put into a poor solvent to reprecipitate the polyimide (A) resin to remove unreacted monomers, and the solidified product can be redissolved in an organic solvent and used as a refined product. Especially in applications where impurities or foreign substances are a problem, it is preferable to redissolve in an organic solvent and purify by filtration to obtain a varnish.

The polyimide (A) (negative photosensitive polymer) of this embodiment is excellent in hydrolysis resistance, and the reduction rate of the weight average molecular weight measured under the following conditions is 9% or less, preferably 8% or less. The conditions are as follows: 400 parts by mass of γ-butyrolactone, 200 parts by mass of 4-methyltetrahydropyran, and 50 parts by mass of water were added to 100 parts by mass of the aforementioned negative photosensitive polymer and stirred at 100°C for 6 hours. Calculated by the following formula. Formula: [(weight average molecular weight before test-weight average molecular weight after test)/weight average molecular weight before test]×100

When the decrease rate of the weight average molecular weight of the negative photosensitive polymer of this embodiment is in the said range, hydrolysis is suppressed, and hardened|cured products, such as a film excellent in mechanical strength, such as elongation, can be obtained.

The preferable compounding example of the negative photosensitive polymer of this embodiment is shown in following Table 1.

[Table 1] Diamine compound 1 Diamine compound 2 Anhydride Blending Example 1 MED-J none TMPBP-TME Blending Example 2 MED-J BAFA TMPBP-TME Blending example 3 MED-J BAPA TMPBP-TME Blending Example 4 MED-J none BPZ-TME Blending Example 5 MED-J none TMHQ

MED-J: 4,4-diamino-3,3-diethyl-5,5-dimethyldiphenylmethane BAFA: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane BAPA: 2,2-bis(3-amino-4-hydroxyphenyl)propane TMPBP-TME: 4-[4-(1,3-dioxoisobenzofuran-5-ylcarbonyloxy)-2,3,5-trimethylphenyl]-2,3 ,6-Trimethylphenyl 1,3-dioxoisobenzofuran-5-carboxylate BPZ-TME: 4-{[4-(1,3-dioxoisobenzofuran-5-ylcarbonyloxy)phenyl]cyclohexyl}phenyl 1,3-dioxoisobenzofuran -5-carboxylate TMHQ: p-phenylene bis(trimellitate anhydride)

[Crosslinking agent (B)] In this embodiment, polyfunctional (meth)acrylate can be contained as a crosslinking agent (B). Among them, the polyfunctional (meth)acrylate refers to a compound having two or more (meth)acryl groups. In addition, in this embodiment, a (meth)acryl group represents an acryl group or a methacryl group.

From the viewpoint of the effects of the present invention, the polyfunctional (meth)acrylate is preferably trifunctional or more. The upper limit of the number of functional groups of the polyfunctional (meth)acrylate compound is not particularly limited, but from the viewpoint of easiness of obtaining raw materials, the upper limit of the number of functional groups is, for example, 11 functions. As a general tendency, when the polyfunctional (meth)acrylate compound with many functional groups ((meth)acryl groups) is used, there exists a tendency for the chemical resistance of a cured film to improve. On the other hand, when a polyfunctional (meth)acrylate compound with a small number of functional groups ((meth)acryl groups) is used, mechanical properties such as tensile elongation of the cured film tend to become better .

As an example, it is preferable that the polyfunctional (meth)acrylate compound contains the (meth)acrylate compound (B1) more than seven functional.

As an example, it is preferable that a polyfunctional (meth)acrylate compound contains a 5-6 functional (meth)acrylate compound (B2).

As an example, it is preferable that a polyfunctional (meth)acrylate compound contains a 3-4 functional (meth)acrylate compound (B3).

As an example, the polyfunctional (meth)acrylate compound can contain the compound represented by the following general formula. In the general formula below, R' is a hydrogen atom or a methyl group, n is 0 to 3, and R is a hydrogen atom or a (meth)acryloyl group.

Specific examples of the polyfunctional (meth)acrylate compound include the following. Of course, the polyfunctional (meth)acrylate compound is not limited to these.

Ethylene Glycol Di(meth)acrylate, Trimethylolpropane Tri(meth)acrylate, Ditrimethylolpropane Tetra(meth)acrylate, Neopentylthritol Tri(meth)acrylate, Neopentylthritol tetra(meth)acrylate, diperythritol penta(meth)acrylate, diperythritol hexa(meth)acrylate and other polyol polyacrylates, bisphenol A bicyclic Di(meth)acrylate of oxypropyl ether, di(meth)acrylate of hexanediol diglycidyl ether and other epoxy acrylates, by polyisocyanate and hydroxyethyl (meth)acrylic acid The urethane (meth)acrylate (urethane (meth)acrylate) obtained by the reaction of hydroxyl-containing (meth)acrylates such as esters.

ARONIX M-400, ARONIX M-460, ARONIX M-402, ARONIX M-510, ARONIX M-520 (manufactured by TOAKASEI.CO.,LTD.), KAYARAD T-1420, KAYARAD DPHA, KAYARAD DPCA20, KAYARAD DPCA30, KAYARAD DPCA60, KAYARAD DPCA120 (manufactured by Nippon Kayaku Co., Ltd.), Viscoat #230, Viscoat #300, Viscoat #802, Viscoat #2500, Viscoat #1000, Viscoat #1080 (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), NK ester A-BPE-10, NK ester A-GLY-9E, NK ester A-9550, NK ester A-DPH (manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD.) and the like are commercially available.

The photosensitive resin composition may contain only one polyfunctional (meth)acrylate compound, and may contain 2 or more polyfunctional (meth)acrylate compounds. In the latter case, it is preferable to simultaneously use polyfunctional (meth)acrylate compounds having different numbers of functional groups. It is believed that by using multifunctional (meth)acrylate compounds with different functional groups at the same time, a more complex "entangled structure of polyimide with a ring structure and multifunctional (meth)acrylate" can be formed, which can Obtain better heat resistance or mechanical properties. In commercially available polyfunctional (meth)acrylate compounds, there are also mixtures of (meth)acrylates with different functional groups.

The amount of the polyfunctional (meth)acrylate compound relative to 100 parts by mass of the polyimide (A) is, for example, 50 to 200 parts by mass, preferably 60 to 150 parts by mass, further preferably 70 to 120 parts by mass . The usage-amount of a polyfunctional (meth)acrylate compound is not specifically limited, By suitably adjusting a usage-amount as mentioned above, 1 type or 2 or more types of each performance can be further improved. As mentioned above, in the photosensitive resin composition of this embodiment, it is considered that "an entangled structure of polyimide having a ring structure and a polyfunctional (meth)acrylate" is formed by curing, and it is also considered that by Properly adjust the amount of multifunctional (meth)acrylate compound relative to polyimide (A), polyimide (A) and multifunctional (meth)acrylate compound are fully entangled, and do not participate in the winding There are fewer unnecessary components, and as a result, performance is further optimized.

In this embodiment, when at least one of the two terminals of the polyimide (A) is an acid anhydride group represented by the aforementioned general formula (3), an epoxy resin can be included as a crosslinking agent (B) . Thereby, the mechanical strength, such as the elongation rate of a cured product, can be further improved.

As an epoxy resin, all compounds which have 2 or more epoxy groups in 1 molecule can be used suitably. Specific examples of epoxy resins include bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol E epoxy resins, bisphenol S epoxy resins, hydrogenated bisphenol A epoxy resins, and bisphenol A epoxy resins. Resin, bisphenol M epoxy resin (4,4'-(1,3-phenylenediisopropylidene) bisphenol epoxy resin), bisphenol P epoxy resin (4,4'- (1,4-phenylene diisopropylidene) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4'-cyclohexadiene bisphenol type epoxy resin), tetramethyl Bisphenol type epoxy resin such as bisphenol F type epoxy resin; phenol novolac type epoxy resin, brominated phenol novolak type epoxy resin, cresol novolak type epoxy resin, tetraphenol ethane type novolac Novolac-type epoxy resins, novolak-type epoxy resins with condensed ring aromatic hydrocarbon structures and other novolac-type epoxy resins; biphenyl-type epoxy resins; xylylene-type epoxy resins, biphenyl aralkyl (biphenyl aralkyl) type epoxy resin and other aralkyl type epoxy resins; naphthyl ether type epoxy resins, naphthol type epoxy resins, naphthalene type epoxy resins, naphthalene diol type epoxy resins, 2 to 4 Functional epoxy naphthalene resin, binaphthyl epoxy resin, naphthalene aralkyl epoxy resin and other epoxy resins with naphthalene skeleton; anthracene epoxy resin; phenoxy epoxy resin; dicyclopentadiene type epoxy resin; norcamphene type epoxy resin; adamantane type epoxy resin; A novolak type epoxy resin, bixylenol type epoxy resin, trihydroxyphenylmethane type epoxy resin, stilbene type epoxy resin, tetraphenylol ethane type epoxy resin, three epoxy resins Heterocyclic epoxy resins such as propyl isocyanate; N,N,N',N'-tetraepoxypropylmethylxylylenediamine, N,N,N',N'-tetraepoxypropyldiamine Copolymers of glycidylamines such as methylcyclohexane, N,N-diepoxypropylaniline, or glycidyl (meth)acrylate and compounds with ethylenically unsaturated double bonds; Epoxy resin with butadiene structure; Diglycidyl ether compound of bisphenol; Diglycidyl ether compound of naphthalene diol; Glycidyl ether compound of phenols, etc. In addition, examples of epoxy resins include n-butylglycidyl ether, 2-ethoxyhexylglycidyl ether, phenylglycidyl ether, allylglycidyl ether, ethyl Glycol Diglycidyl Ether, Propylene Glycol Diglycidyl Ether, Neopentyl Glycol Diglycidyl Ether, Glycerin Polyglycidyl Ether, Sorbitol Polyglycidyl Ether, Bisphenol A ( or F) Glycidyl ether such as glycidyl ether, glycidyl ether such as glycidyl adipate, glycidyl ester such as diglycidyl phthalate, 3,4-epoxy ring Hexylmethyl (3,4-epoxycyclohexane) carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl (3,4-epoxy-6-methylcyclohexane) carboxylate ester, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, dicyclopentadiene oxide, bis(2,3-epoxycyclopentyl) ether or Cycloaliphatic epoxy resins such as CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, CELLOXIDE 8000, EPOLEAD GT401 manufactured by Daicel Corporation, 2,2'-(((((1-(4-(2-(4 -(oxiran-2-ylmethoxy)phenyl)propan-2-yl)phenyl)ethane-1,1-diyl)bis(4,1-phenylene))bis(oxy base)) bis(methylene))bis(oxirane)) (for example, Techmore VG3101L manufactured by Printec Corporation), Epolite 100MF (manufactured by KYOEISHA CHEMICAL Co., LTD.), epiol TMP (manufactured by NOF CORPORATION), etc. Aliphatic polyglycidyl ether, 1,1,3,3,5,5-hexamethyl-1,5-bis(3-(oxiran-2-ylmethoxy)propyl)tri -Siloxane (eg, DMS-E09 (manufactured by Gelest)) and the like.

As an epoxy resin, what has 2-4 epoxy groups in 1 molecule is preferable, and what has 2-3 epoxy groups in 1 molecule is more preferable. By adjusting the functional groups of the epoxy resin, for example, it is easy to improve the heat resistance of the cured film or the mechanical properties of the cured film in a balanced manner. From another viewpoint, as an epoxy resin, what has an aromatic ring structure and/or an alicyclic structure is preferable. In particular, it is preferable to use such an epoxy resin from the viewpoint of heat resistance.

When using an epoxy resin, only 1 type of epoxy resin may be used, and 2 or more types of epoxy resins may be used together. When an epoxy resin is used, the amount is, for example, 0.5 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 3 to 15 parts by mass relative to 100 parts by mass of the polyimide (A).

[Photopolymerization initiator (C)] As a photoinitiator (C), a photoradical generator can be used, for example. A photoradical generator is effective especially when polymerizing a polyfunctional (meth)acrylate compound.

啉基丙烷-1-酮、2-苄基-2-二甲基胺基-1-（4-

啉基苯基）-丁酮-1,2-（二甲基胺基）-2-〔（4-甲基苯基）甲基〕-1-〔4-（4-

啉基）苯基〕-1-丁酮等烷基苯基酮系化合物；二苯甲酮、4,4′-雙（二甲基胺基）二苯甲酮、2-羧基二苯甲酮等二苯甲酮系化合物；苯偶姻甲醚（benzoin methyl ether）、苯偶姻乙醚、苯偶姻異丙基醚、苯偶姻異丁基醚等苯偶姻系化合物；9-氧硫

、2-乙基9-氧硫

、2-異丙基9-氧硫

、2-氯9-氧硫

、2,4-二甲基9-氧硫

、2,4-二乙基9-氧硫

等9-氧硫

系化合物；2-（4-甲氧基苯基）-4,6-雙（三氯甲基）-對稱三𠯤、2-（4-甲氧基萘基）-4,6-雙（三氯甲基）-對稱三𠯤、2-（4-乙氧基萘基）-4,6-雙（三氯甲基）-對稱三𠯤、2-（4-乙氧基羰基萘基）-4,6-雙（三氯甲基）-對稱三𠯤等鹵甲基化三𠯤系化合物；2-三氯甲基-5-（2′-苯并呋喃）-1,3,4-㗁二唑、2-三氯甲基-5-〔β-（2′-苯并呋喃）乙烯基〕-1,3,4-㗁二唑、4-㗁二唑、2-三氯甲基-5-呋喃基-1,3,4-㗁二唑等鹵甲基化㗁二唑系化合物；2,2′-雙（2-氯苯基）-4,4′,5,5′-四苯基-1,2′-雙咪唑、2,2′-雙（2,4-二氯苯基）-4,4′,5,5′-四苯基-1,2′-雙咪唑、2,2′-雙（2,4,6-三氯苯基）-4,4′,5,5′-四苯基-1,2′-雙咪唑等雙咪唑系化合物；1,2-辛二酮,1-〔4-（苯基硫基）苯基〕-2-（O-苯甲醯基肟）、乙酮,1-〔9-乙基-6-（2-甲基苯甲醯基）-9H-咔唑-3-基〕-,1-（O-苯醯基肟）等肟酯系化合物；雙（η5-2,4-環戊二烯-1-基）-雙（2,6-二氟-3-（1H-吡咯-1-基）-苯基）鈦等環戊二烯鈦系化合物；對二甲基胺基苯甲酸、對二乙基胺基苯甲酸等安息香酸酯系化合物；9-苯基吖啶等吖啶系化合物；等。該等之中，尤其能夠較佳地使用肟酯系化合物。 The photoradical generator that can be used is not particularly limited, and known ones can be used appropriately. For example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl Base-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy- 1-{4-[4-(2-Hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-(4-methylbenzene Sulfuryl) -2-

Linylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-

Linylphenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-

Alkyl phenyl ketone series compounds such as phenyl)phenyl]-1-butanone; benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-carboxybenzophenone Benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin compounds; 9-oxosulfur

, 2-Ethyl 9-oxosulfur

, 2-isopropyl 9-oxosulfur

, 2-chloro 9-oxysulfur

, 2,4-Dimethyl 9-oxosulfur

, 2,4-Diethyl 9-oxosulfur

9-oxosulfur

Department of compounds; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-symmetrical three Chloromethyl)-symmetrical trimethalone, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-symmetrical trimethalone, 2-(4-ethoxycarbonylnaphthyl)- 4,6-bis(trichloromethyl)-symmetrical trichloromethylated trioxane compounds; 2-trichloromethyl-5-(2′-benzofuran)-1,3,4-㗁Oxadiazole, 2-trichloromethyl-5-[β-(2′-benzofuran)vinyl]-1,3,4-oxadiazole, 4-oxadiazole, 2-trichloromethyl- 5-furyl-1,3,4-oxadiazole and other halomethylated oxadiazole compounds; 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetra Phenyl-1,2′-bisimidazole, 2,2′-bis(2,4-dichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-bisimidazole, 2,2′-bis(2,4,6-trichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole and other bisimidazole compounds; 1,2- Octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzene Formyl)-9H-carbazol-3-yl]-, 1-(O-benzoyl oxime) and other oxime ester compounds; bis(η5-2,4-cyclopentadien-1-yl)- Cyclopentadienyl titanium series compounds such as bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium; p-dimethylaminobenzoic acid, p-diethylaminobenzene Benzoate-based compounds such as formic acid; acridine-based compounds such as 9-phenylacridine; etc. Among these, oxime ester type compounds can be used particularly preferably.

The negative photosensitive resin composition of this embodiment may contain only 1 type of photoinitiator (C), and may contain 2 or more types. The usage-amount of a photoinitiator (C) is 1-30 mass parts, for example with respect to 100 mass parts of polyfunctional (meth)acrylate compounds, Preferably it is 5-20 mass parts.

(Thermal radical initiator (D)) It is preferable that the negative photosensitive resin composition of this embodiment contains a thermal radical initiator (D). By using the thermal radical initiator (D), for example, the heat resistance of the cured film and/or the chemical resistance of the cured film can be further improved (resistance to organic solvents, etc.). This is considered to be because the polymerization reaction of the polyfunctional (meth)acrylate compound was further accelerated by using the thermal radical initiator (D).

The thermal radical initiator (D) preferably contains an organic peroxide. Examples of organic peroxides include octyl peroxide, lauryl peroxide, stearyl peroxide, 1,1,3,3-tetramethylbutylperoxyethyl 2-hexanoate ester, oxalate peroxide, 2,5-dimethyl-2,5-bis(2-ethylhexylperoxy)hexane, 1-cyclohexyl-1-methylethylperoxy2 - ethyl hexanoate, tertiary hexylperoxyethyl 2-hexanoate, tertiary butylperoxyethyl 2-hexanoate, m-tolyl peroxide, benzoyl peroxide, benzyl Acyl peroxide, methyl ethyl ketone peroxide, benzoyl peroxide, tertiary butyl hydroperoxide, di-tertiary butyl peroxide, cumene hydroperoxide, di Cumyl peroxide, tertiary butyl perbenzoate, p-chlorobenzoyl peroxide, cyclohexanone peroxide, etc.

When using a thermal radical initiator (D), only 1 type of thermal radical initiator (D) may be used, and 2 or more types of thermal radical initiators (D) may be used. When using a thermal radical initiator (D), it is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of polyfunctional (meth)acrylate compounds, and it is more preferable that it is 1-20 mass parts.

(adhesion aid) The negative photosensitive resin composition of this embodiment may further contain an adhesion assistant. As an adhesion aid, a silane coupling agent can be preferably used. By using a silane coupling agent, for example, the adhesiveness of a board|substrate and a cured film can be improved further.

As the silane coupling agent, for example, an amino group-containing silane coupling agent, an epoxy group-containing silane coupling agent, a (meth)acryl group-containing silane coupling agent, a mercapto group-containing silane coupling agent, a vinyl group-containing silane Coupling agent, silane coupling agent containing urea group, silane coupling agent containing sulfide, silane coupling agent with cyclic anhydride structure and other silane coupling agents.

Examples of amino group-containing silane coupling agents include bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-amino Propyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)γ-aminopropyl Trimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, N -β(aminoethyl)γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-amino-propyltrimethoxysilane, etc. As epoxy-containing silane coupling agents, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3, 4-Epoxycyclohexyl)ethyltrimethoxysilane, γ-epoxypropylpropyltrimethoxysilane, etc. Examples of (meth)acrylyl group-containing silane coupling agents include γ-((meth)acryloxypropyl)trimethoxysilane, γ-((meth)acryloxypropyl) ) Methyldimethoxysilane, γ-((meth)acryloxypropyl)methyldiethoxysilane, etc. As a mercapto group-containing silane coupling agent, 3-mercaptopropyltrimethoxysilane etc. are mentioned, for example. Examples of the vinyl group-containing silane coupling agent include vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, and vinyltrimethoxysilane. As a ureido group containing silane coupling agent, 3-ureidopropyltriethoxysilane etc. are mentioned, for example. Examples of sulfide-containing silane coupling agents include bis(3-(triethoxysilyl)propyl)disulfide and bis(3-(triethoxysilyl)propyl)tetrasulfide wait. Examples of silane coupling agents having a cyclic anhydride structure include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 3-dimethylmethoxysilyl Propyl succinic anhydride, etc.

In this embodiment, particularly, a silane coupling agent having a cyclic acid anhydride structure can be preferably used. The details are not clear, but it is presumed that the cyclic acid anhydride structure easily reacts with the main chain, side chain, and/or terminal of the polyimide (A), so that a particularly good adhesion-improving effect can be obtained.

When using a silane coupling agent, an adhesion aid may be used alone, or two or more types of adhesion aids may be used together. In the case of using a silane coupling agent, when the amount of polyimide (A) used is 100 parts by mass, the amount used is, for example, 0.1 to 20 parts by mass, preferably 0.3 to 15 parts by mass, more preferably 0.4-12 mass parts, More preferably, it is 0.5-10 mass parts.

(surfactant) The photosensitive resin composition of this embodiment preferably contains a surfactant. Thereby, the applicability of a photosensitive resin composition and the flatness of a film can be further improved. Examples of the surfactant include fluorine-based surfactants, silicone-based surfactants, alkyl-based surfactants, acrylic-based surfactants, and the like. From another viewpoint, it is preferable that the surfactant is nonionic. The use of a nonionic surfactant is preferable from the viewpoint of improving the storage stability of the composition, for example, to suppress unexpected reactions with other components in the composition.

The surfactant preferably contains at least one of fluorine atoms and silicon atoms. Thereby, in addition to obtaining a uniform resin film (improving coatability) and improving developability, it also contributes to improving adhesive strength. As such a surfactant, for example, a nonionic surfactant containing at least one of a fluorine atom and a silicon atom is preferable. Commercially available products that can be used as surfactants include, for example, DIC CORPORATION's "MEGAFACE" series, F-251, F-253, F-281, F-430, F-477, F-551, F -552, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-562, F-563, F-565 , F-568, F-569, F-570, F-572, F-574, F-575, F-576, R-40, R-40-LM, R-41, R-94, etc. containing fluorine Oligomer-structured surfactants, fluorine-containing nonionic surfactants such as ftergent 250 and ftergent 251 manufactured by NEOS COMPANY LIMITED, SILFOAM (registered trademark) series manufactured by Wacker Chemie AG (such as SD 100 TS, SD 670, SD 850, SD 860, SD 882) and other polysiloxane surfactants. Moreover, FC4430 and FC4432 etc. made from 3M Company are also mentioned as a preferable surfactant.

When the photosensitive resin composition of this embodiment contains a surfactant, it can contain 1 type, or 2 or more types of surfactants. When the photosensitive resin composition of this embodiment contains a surfactant, when the content of the polyimide (A) is 100 parts by mass, the amount is, for example, 0.001 to 1 part by mass, preferably 0.005 to 100 parts by mass. 0.5 parts by mass.

(water) The photosensitive resin composition of this embodiment may contain water. By the presence of water, for example, the hydrolysis reaction of the silane coupling agent proceeds easily, and there exists a tendency for the adhesiveness of a board|substrate and a cured film to improve further.

When the photosensitive resin composition of this embodiment contains water, the amount is preferably 0.1 to 5 parts by mass, more preferably 0.2 -3 parts by mass, more preferably 0.5-2 parts by mass.

The water content of the photosensitive resin composition can be quantified by the Karl Fischer's method.

(solvent) The photosensitive resin composition of this embodiment preferably contains a solvent. Thereby, a photosensitive resin film can be easily formed on a board|substrate (especially, a board|substrate with a step difference) by a coating method. Solvents generally include organic solvents. The organic solvent is not particularly limited as long as it can dissolve or disperse the above-mentioned components and does not substantially chemically react with the components.

Examples of organic solvents include acetone, methyl ethyl ketone, toluene, propylene glycol methyl ether, propylene glycol dimethyl ether, propylene glycol 1-monomethyl ether 2-acetate, diethylene glycol ethyl methyl ether, Ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, benzyl alcohol, propylene carbonate, ethylene glycol diacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, di Propylene glycol methyl-n-propyl ether, butyl acetate, γ-butyrolactone, methyl lactate, ethyl lactate, butyl lactate, etc. These may be used alone or in combination of two or more types.

When the photosensitive resin composition of this embodiment contains a solvent, the photosensitive resin composition of this embodiment is normally a varnish shape. More specifically, the photosensitive resin composition of this embodiment is preferably a varnish-like composition obtained by dissolving at least polyimide (A) and a polyfunctional (meth)acrylate compound in a solvent. Since the photosensitive resin composition of the present embodiment is in the form of a varnish, a uniform film can be formed by coating. Moreover, a homogeneous cured film can be obtained by "dissolving" a polyimide (A) and a polyfunctional (meth)acrylate compound in a solvent.

When using a solvent, it is used so that the density|concentration of the total solid content (non-volatile content) in a photosensitive resin composition may become 10-50 mass %, More preferably, it may become 20-45 mass %. Each component can be fully dissolved or dispersed by setting it as this range. In addition, good applicability can be ensured, and further, optimization of flatness at the time of spin coating can be realized. Furthermore, the viscosity of the photosensitive resin composition can be appropriately controlled by adjusting the content of the non-volatile components. From another viewpoint, the ratio of the polyimide (A) and the polyfunctional (meth)acrylate compound in the entire composition is preferably 20 to 50% by mass. By using polyimide (A) and polyfunctional (meth)acrylate compound in a large amount to a certain extent, it is easy to form a film with an appropriate thickness.

(other ingredients) The photosensitive resin composition of this embodiment may contain components other than the above-mentioned components as needed, in addition to the above-mentioned components. Examples of such components include antioxidants, fillers such as silica, sensitizers, and film-forming agents.

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

(Negative Photosensitive Resin Composition) Regarding the negative photosensitive resin composition of the present embodiment, the negative photosensitive resin composition is applied to a surface having a metal such as Al, Cu, etc., followed by pre-baking and drying to form a resin. The film is then used by forming a resin film pattern into a desired shape by performing exposure and development, and then curing the resin film by heat treatment to form a cured film.

In addition, when producing the said permanent film, as a prebaking condition, it can heat-process at the temperature 90 degreeC or more and 130 degreeC or less, for 30 seconds or more and 1 hour or less, for example. In addition, as the conditions of the heat treatment, for example, the heat treatment can be performed at a temperature of 150°C to 250°C for 30 minutes to 10 hours, preferably at about 170°C for 1 to 6 hours.

Regarding the film obtained from the negative photosensitive resin composition of this embodiment, the maximum value of the elongation measured by the tensile test carried out with a Tensilon testing machine is 15 to 200%, preferably 20 to 150%, The average value is 10 to 150%, preferably 15 to 120%.

The film obtained from the negative photosensitive resin composition of this embodiment preferably has a tensile strength of 20 MPa or more, more preferably 30 to 300 MPa, as measured by a tensile test using a Tensilon testing machine.

In addition, the negative photosensitive resin composition of this embodiment contains polyimide (A) (negative photosensitive polymer) which is excellent in hydrolysis resistance, so even if the temperature is 130°C, the relative humidity is 85%RH. After 96 hours of HAST test (unsaturated pressurized steam test), the reduction rate of elongation (maximum value, average value) represented by the following formula is also 40% or less, preferably 35% or less, and more preferably Below 33%. [(Elongation before test-Elongation after test)/Elongation before test)]×100

The negative photosensitive resin composition of this embodiment is excellent in low-temperature curability. For example, the glass transition temperature (Tg) of the cured product obtained by curing the negative photosensitive resin composition of the present embodiment at 170°C for 4 hours can be set to 200°C or higher, preferably 210°C or higher, and more preferably Above 220°C.

Furthermore, the storage elastic modulus E' at 30°C of the cured product obtained by curing the negative photosensitive resin composition of the present embodiment at 170°C for 4 hours can be set to 2.0 GPa or more, preferably 2.2 GPa or more, and further Preferably it is 2.5 GPa or more. Furthermore, the storage elastic modulus E' at 200°C can be set to 0.5 GPa or more, preferably 0.8 GPa or more, and still more preferably 1.0 GPa or more.

The viscosity of the negative photosensitive resin composition of the present embodiment can be appropriately set according to the thickness of the required resin film. The adjustment of the viscosity of a negative photosensitive resin composition can be performed by adding a solvent.

Cured products such as films obtained from the negative photosensitive resin composition of this embodiment are excellent in chemical resistance. Specifically, at 40° C., the membrane was immersed in a solution of up to 99% by mass of dimethylsulfoxide and up to 2% by mass of tetramethylammonium hydroxide for 10 minutes, and then sufficiently washed with isopropanol. Air dry and measure the film thickness after treatment. The film thickness change rate between the film thickness after the treatment and the film thickness before the treatment was calculated by the following formula, and evaluated as the reduction rate of the film. Formula: film reduction rate (%)={(film thickness after immersion-film thickness before immersion)/film thickness before immersion×100(%)}

The film thickness change rate is preferably 40% or less, more preferably 30% or less. Thereby, even when the cured film is subjected to the step of immersing in dimethyl sulfide, the film thickness hardly decreases. Therefore, it is possible to obtain a cured film capable of maintaining functions even after being subjected to this step.

The curing shrinkage of the negative-type photosensitive resin composition of this embodiment is suppressed, and it is spin-coated on the surface of a silicon wafer so that the film thickness after drying becomes 10 μm. After pre-baking at 120° C. for 3 minutes, The mercury lamp was exposed to 600mJ/cm ² , and then heat-treated at 170°C for 120 minutes in a nitrogen atmosphere to prepare a film. In this case, the film thickness of the film after the aforementioned prebaking was defined as film thickness A And when the film thickness of the film after the heat treatment is taken as film thickness B, the cure shrinkage calculated by the following formula can be preferably set to 12% or less, more preferably 10% or less. Formula: hardening shrinkage [%]={(film thickness A-film thickness B)/film thickness A}×100

The negative photosensitive resin composition of this embodiment has high heat resistance, and the weight loss temperature (Td5) measured by thermogravimetric differential thermal simultaneous measurement (TG-DTA) can be set to 200 for the obtained film. °C or higher, preferably 300 °C or higher.

The curing shrinkage of the film composed of the negative photosensitive resin composition of this embodiment is suppressed, and the coefficient of linear thermal expansion (CTE) can be set to 200 ppm/°C or less, preferably 100 ppm/°C or less.

The film composed of the negative photosensitive resin composition of this embodiment is excellent in mechanical strength, and the modulus of elasticity at 25° C. can be 1.0 to 5.0 GPa, preferably 1.5 to 3.0 GPa.

(use) The negative photosensitive resin composition of this embodiment is used to form resin films for semiconductor devices such as permanent films and resist layers. Among them, the improvement of the adhesiveness of the negative photosensitive resin composition after prebaking and the Al pad and the suppression of the residue generation of the negative photosensitive resin composition during development are exhibited in a balanced manner. From the point of view, from the point of view of improving the adhesion between the cured film of the negative photosensitive resin composition after heat treatment and the metal, and from the point of view of improving the chemical resistance of the negative photosensitive resin composition after heat treatment, it is used for permanent film The use is better.

In addition, in the present embodiment, the resin film includes a cured film of a negative photosensitive resin composition. That is, the resin film of this embodiment is what hardened the negative photosensitive resin composition.

The above-mentioned permanent film is composed of a resin film, which is obtained by prebaking, exposing and developing the negative photosensitive resin composition, and patterning it into a desired shape. Heat treatment to harden it. The permanent film can be used as a protective film, interlayer film, dam material, etc. of a semiconductor device.

The above-mentioned resist layer is composed of a resin film obtained by, for example, coating a negative-type photosensitive resin composition by spin coating, roll coating, flow coating, dip coating, spray coating, blade coating, and the like. On the object masked by the resist layer, and remove the solvent from the negative photosensitive resin composition. An example of the semiconductor device of this embodiment is shown in FIG. 1 .

The semiconductor device 100 of the present embodiment can be a semiconductor 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 semiconductor device 100 can be used as a resin film including the cured product of this embodiment. Among them, the resin film is preferably the above-mentioned permanent film.

The semiconductor device 100 is, for example, a semiconductor wafer. In this case, for example, a semiconductor package can be obtained by mounting the semiconductor device 100 on a wiring board via bumps 52 .

The semiconductor 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 . An opening exposing the uppermost layer wiring 34 is provided in a part of the passivation film 32 .

A rewiring layer 40 is provided on the passivation film 32 . The redistribution 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 , and is connected to the uppermost layer wiring 34 . An opening connected to the redistribution line 46 is provided in the insulating layer 44 .

The bump 52 is formed in the opening provided in the insulating layer 44 via the UBM (Under Bump Metallurgy: Under Bump Metallurgy) layer 50 , for example. The semiconductor device 100 is connected to a wiring board or the like via bumps 52 , for example. As mentioned above, although embodiment of this invention was described, these are illustrations of this invention, Various structures other than the above can be employ|adopted in the range which does not impair the effect of this invention. [Example]

Hereinafter, the present invention will be described in more detail by way of examples, however, the present invention is not limited thereto. In Examples, the following compounds were used.

4,4-diamino-3,3-diethyl-5,5-dimethyldiphenylmethane represented by the following formula (hereafter also referred to as MED-J)

4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl represented by the following formula (hereinafter also referred to as TFMB)

2,2-bis(3-amino-4-hydroxyphenyl)propane represented by the following formula (hereinafter also referred to as BAPA)

2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane represented by the following formula (hereinafter also referred to as BAFA)

4-[4-(1,3-dioxoisobenzofuran-5-ylcarbonyloxy)-2,3,5-trimethylphenyl]-2,3,6 represented by the following formula -Trimethylphenyl-1,3-dioxoisobenzofuran-5-carboxylate (hereinafter also referred to as TMPBP-TME)

3,3',4,4'-Benzophenonetetracarboxylic dianhydride represented by the following formula (hereinafter also referred to as BTDA)

[Example 1] First, 10.83 g (38.3 mmol) of MED-J and 25.77 g (41.7 mmol) of TMPBP-TME were placed in a reaction vessel of an appropriate size equipped with a stirrer and a cooling pipe. Thereafter, 109.80 g of GBL was further added to the reaction container. After blowing nitrogen gas for 10 minutes, the temperature was raised to 60° C. while stirring, and the reaction was carried out for 1.5 hours. Then, it was made to react at 180 degreeC for 3 hours, and diamine and an acid anhydride were polymerized, and the polymerization solution was produced. The obtained reaction solution was diluted with tetrahydrofuran to prepare a diluted solution, and the diluted solution was added dropwise to methanol to precipitate a white solid. The obtained white solid was recovered and vacuum-dried at a temperature of 80° C. to obtain 31.17 g of a polymer. As a result of GPC measurement of the polymer, the weight average molecular weight Mw was 55,900, and the polydispersity (weight average molecular weight Mw/number average molecular weight Mn) was 2.64. The obtained polymer partially contained a repeating unit represented by the following formula.

[Example 2] First, 3.87 g (13.7 mmol) of MED-J, 5.02 g (13.7 mmol) of BAFA, and 20.17 g (32.6 mmol) of TMPBP-TME were placed in a reaction vessel of an appropriate size equipped with a stirrer and a cooling pipe. Then, GBL87.17g was further added to the reaction container. After blowing nitrogen gas for 10 minutes, the temperature was raised to 60° C. while stirring, and the reaction was carried out for 1.5 hours. Then, it reacted at 180 degreeC for 3 hours, diamine, bisaminophenol, and an acid anhydride were polymerized, and the polymerization solution was produced. The obtained reaction solution was diluted with tetrahydrofuran to prepare a diluted solution, and the diluted solution was added dropwise to methanol to precipitate a white solid. The obtained white solid was recovered and vacuum-dried at a temperature of 80° C. to obtain 24.70 g of a polymer. As a result of GPC measurement of the polymer, the weight average molecular weight Mw was 18,500, and the polydispersity (weight average molecular weight Mw/number average molecular weight Mn) was 1.81. The obtained polymer partially contained a repeating unit represented by the following formula.

[Example 3] First, 3.87 g (13.7 mmol) of MED-J, 3.54 g (13.7 mmol) of BAPA, and 20.17 g (32.6 mmol) of TMPBP-TME were placed in a reaction vessel of an appropriate size equipped with a stirrer and a cooling pipe. Thereafter, 82.73 g of GBL was further added to the reaction container. After blowing nitrogen gas for 10 minutes, the temperature was raised to 60° C. while stirring, and the reaction was carried out for 1.5 hours. Then, it reacted at 180 degreeC for 3 hours, diamine, bisaminophenol, and an acid anhydride were polymerized, and the polymerization solution was produced. The obtained reaction solution was diluted with tetrahydrofuran to prepare a diluted solution, and the diluted solution was added dropwise to methanol to precipitate a white solid. The obtained white solid was recovered and vacuum-dried at a temperature of 80° C. to obtain 23.13 g of a polymer. As a result of GPC measurement of the polymer, the weight average molecular weight Mw was 20,900, and the polydispersity (weight average molecular weight Mw/number average molecular weight Mn) was 1.92. The obtained polymer partially contained a repeating unit represented by the following formula.

[Comparative examples 1 to 3] About Comparative Examples 1-3, except the conditions described in Table 2, it synthesize|combined by the method similar to Example 2. In Comparative Examples 1 and 2, the reaction was difficult to continue due to gelation during the polymerization reaction, so the solvent solubility in GBL was made x.

[Comparative example 4] First, 12.55 g (44.4 mmol) of MED-J and 17.90 g (55.6 mmol) of BTDA were placed in a reaction vessel of an appropriate size equipped with a stirrer and a cooling tube. Thereafter, 91.36 g of GBL was further added to the reaction container. After blowing nitrogen gas for 10 minutes, the temperature was raised to 60° C. while stirring, and the reaction was carried out for 1.5 hours. Then, it was made to react at 180 degreeC for 3 hours, and diamine and an acid anhydride were polymerized, and the polymerization solution was produced. The obtained reaction solution was diluted with tetrahydrofuran to prepare a diluted solution, and the diluted solution was added dropwise to methanol to precipitate a white solid. The obtained white solid was recovered and vacuum-dried at a temperature of 60° C. to obtain 23.77 g of a polymer. As a result of GPC measurement of the polymer, the weight average molecular weight Mw was 8,900, and the polydispersity (weight average molecular weight Mw/number average molecular weight Mn) was 1.69.

[Comparative Example 5] First, 13.53 g (47.9 mmol) of MED-J and 16.78 g (52.1 mmol) of BTDA were placed in a reaction vessel of an appropriate size equipped with a stirrer and a cooling tube. Thereafter, 90.95 g of GBL was further added to the reaction container. After blowing nitrogen gas for 10 minutes, the temperature was raised to 60° C. while stirring, and the reaction was carried out for 1.5 hours. Then, it was made to react at 180 degreeC for 3 hours, and diamine and an acid anhydride were polymerized, and the polymerization solution was produced. The obtained reaction solution was diluted with tetrahydrofuran to prepare a diluted solution, and the diluted solution was added dropwise to methanol to precipitate a white solid. The obtained white solid was recovered and vacuum-dried at a temperature of 60° C. to obtain 26.16 g of a polymer. As a result of GPC measurement of the polymer, the weight average molecular weight Mw was 28,400, and the polydispersity (weight average molecular weight Mw/number average molecular weight Mn) was 1.95.

[Solubility in organic solvents] The solubility of the negative photosensitive polymer obtained in Examples 1 to 3 and Comparative Examples 3 to 5 in γ-butyrolactone (GBL) was evaluated on the basis of the following criteria. The results are shown in Table 2. (Evaluation criteria for solubility) ○: 5% by mass or more of the polymer dissolved Δ: 1 to 5% by mass of polymer dissolved ×: Dissolution of the polymer does not reach 1% by mass

[hydrolysis resistance] The decrease rate of the weight average molecular weight of the negative photosensitive polymer obtained in the Example and the comparative example was measured on the following conditions. The results are shown in Table 2. (Condition (without addition of triethylamine)) When 400 parts by mass of γ-butyrolactone, 200 parts by mass of 4-methyltetrahydropyran, and 50 parts by mass of water were added to 100 parts by mass of a negative photosensitive polymer and stirred at 100° C. for 6 hours, the The following formula is used for calculation. Formula: [(weight average molecular weight before test-weight average molecular weight after test)/weight average molecular weight before test]×100 (conditions (addition of triethylamine)) 10 parts by mass of triethylamine, 400 parts by mass of γ-butyrolactone, 200 parts by mass of 4-methyltetrahydropyran, and 50 parts by mass of water were added to 100 parts by mass of a negative photosensitive polymer, and stirred at 100°C. In the case of 6 hours, it is calculated by the following formula. Formula: [(weight average molecular weight before test-weight average molecular weight after test)/weight average molecular weight before test]×100

[Polymer stability] The GBL solution of the polymer obtained in Example 1 and Comparative Example 5 (100 parts by mass of the polymer) contained the adhesion aid KBM-503P (2 parts by mass) and the surfactant FC4432 (0.1 parts by mass) As a result, only the composition of Comparative Example 5 became viscous and gelled, and thus evaluation of elongation and the like could not be performed.

[Table 2] Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative Example 5 Diamine 1 Kinds added to Morbi MED-J92 MED-J 42 MED-J 42 Tetramethylbenzidine 42 m-toluidine 42 TFMB 42 MED-J 80 MED-J92 Diamine 2 Kinds added to Morbi BAFA 42 BAPA 42 BAFA 42 BAFA 42 BAFA 42 Anhydride Type Join Morbi TMPBP-TME 100 TMPBP-TME 100 TMPBP-TME 100 TMPBP-TME 100 TMPBP-TME 100 TMPBP-TME 100 BTDA 100 BTDA 100 mw 55,900 18,500 20,900 - - 18,200 8,900 28,400 PDI 2.64 1.81 1.92 - - 1.82 1.69 1.95 Solvent Solubility GBL ○ ○ ○ x x ○ ○ ○ Hydrolysis resistance (Mw reduction rate) No TEA 8% 6% 2% - - 10% 0% - There are TEAs 17% twenty three% twenty three% - - 49% 3% - polymer stability Stablize gelation

As shown in Table 1, it is presumed that the negative photosensitive polymer of the present invention obtained in Examples has excellent solubility in organic solvents, and furthermore, hydrolysis is suppressed, so the reduction in elongation is small and the reduction in mechanical strength is suppressed. .

When preparing the negative photosensitive resin composition, the following compounds were used. (Crosslinking agent) Acrylate compound 1: Dineopentaerythritol hexaacrylate (NK ester A-DPH, manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD.) Epoxy compound 1: epoxy represented by the following chemical formula Compound (manufactured by Printec Corporation, VG3101L)

(Additives) Additive 1: phenol compound represented by the following formula (manufactured by Honshu Chemical Industry Co., Ltd., TrisP-PA)

(polymerization initiator) Photoradical generator: Oxime ester-based photoradical generator (manufactured by ADEKA CORPORATION, NCI-730) · Thermal radical generator: dicumyl peroxide (Perkadox BC, peroxide, manufactured by KAYAKU NOURYON CORPORATION)

(adhesion aid) Adhesion aid 1: 3-methacryloxypropyltrimethoxysilane (KBM-503P, manufactured by Shin-Etsu Chemical Co., Ltd.) Adhesion aid 2: 3-trimethoxysilylpropyl succinic anhydride (X-12-967C, manufactured by Shin-Etsu Chemical Co., Ltd.)

(surfactant) · Surfactant 1: Surfactant having a fluorocarbon chain (FC-4432, manufactured by Sumitomo 3M Limited)

(solvent) ·Solvent 1: water Solvent 2: γ-butyrolactone (GBL)

[Example 4] (Preparation of Negative Photosensitive Resin Composition) The polymer of Example 1 (100 parts by mass of the polymer) was mixed and the components shown in Table 3 were previously dissolved so as to become a 26.5 wt% GBL solution. obtainers, thereby preparing a photosensitive resin composition. The obtained negative photosensitive resin composition was spin-coated on the surface of the silicon wafer so that the film thickness after drying was 10 μm, pre-baked at 120°C for 3 minutes, and then exposed to 600mJ/cm ² with a high-pressure mercury lamp , and thereafter, heat treatment was performed at 170° C. for 120 minutes in a nitrogen atmosphere, thereby preparing a film. Regarding the obtained film, the elongation was measured by the following method, and the pattern forming characteristics were evaluated. The results are shown in Table 3.

[Elongation] A tensile test was performed on a test piece (6.5 mm×60 mm×10 μm thick) cut out from the film obtained in Example 4 in an environment of 23° C. (tensile speed: 5 mm/minute). The tensile test was performed using a tensile testing machine (Tensilon RTC-1210A) manufactured by ORIENTEC CO., LTD. Measure 5 pieces of test pieces, calculate the tensile elongation according to the breaking distance and the initial distance, and calculate the average value and maximum value of the elongation. Furthermore, under the conditions of a temperature of 130° C. and a relative humidity of 85% RH, the aforementioned test piece cut out from the film obtained in Example 4 was subjected to HAST (unsaturated pressurized steam test) for 96 hours, and then compared with the aforementioned The average value and maximum value of the elongation are obtained in the same manner.

[Evaluation related to pattern formation characteristics] It was confirmed that the photosensitive resin composition of Example 4 can sufficiently perform pattern formation by exposure and image development as follows. The photosensitive resin composition of Example 4 was coated on an 8-inch silicon wafer using a spin coater. After the coating, the coating was prebaked at 110° C. for 3 minutes on a hot plate in the atmosphere, thereby obtaining a coating film with a film thickness of about 5.0 μm. The coating film was irradiated with i-rays through a mask in which a via-hole pattern with a width of 20 μm was drawn. For irradiation, an i-ray stepper (NSR-4425i manufactured by Nikon Corporation) was used. After the exposure, cyclopentanone was used as a developer for 30 seconds, and PGMEA was used as a developer for 10 seconds to dissolve and remove the unexposed portion, thereby obtaining a via hole pattern. The cross-section of the obtained via hole pattern was observed using a desktop SEM. The width in the height between the bottom surface of the via pattern and the middle of the opening was defined as the via width, and evaluated based on the following references. Good pattern formation: via pattern with 20μm opening Poor pattern formation: 20 μm via hole pattern without opening The pattern formability of the coating film obtained from the photosensitive resin composition of Example 4 was favorable.

[table 3] Example 4 polyimide Polymer of Example 1 parts by mass 100 crosslinking agent Acrylate compound 1 75 epoxy compound 1 10 additive 5 polymerization initiator photoradical generator 10 thermal free radical generator 10 Adhesives Adhesion aid 1 2 Adhesion aid 2 4 Surfactant Surfactant 1 0.05 solvent Solvent 1 3 Solvent 2 595 Elongation (MAX) Before uHAST % twenty one Elongation (MAX) After uHAST % 16 Elongation (Ave.) Before uHAST % 18 Elongation (Ave.) After uHAST % 12 Patterning properties ok

As described in Table 3, it is clear that the elongation of the film obtained from the negative photosensitive resin composition containing the negative photosensitive polymer of the present invention is excellent, and because the negative photosensitive polymer excellent in hydrolysis resistance is contained , so even after the HAST test, the mechanical strength is excellent. Moreover, it confirmed that pattern formability is also favorable and it is suitable as a negative photosensitive resin composition.

This application claims priority based on Japanese Application Japanese Patent Application No. 2021-105686 filed on June 25, 2021, and incorporates all the contents of the disclosure herein.

100: Semiconductor device 30: interlayer insulating film 32: Passivation film 34: Top layer wiring 40: Redistribution layer 42: Insulation layer 44: Insulation layer 46: Rewiring 50: UBM layer 52: Bump

[ Fig. 1] Fig. 1 is a schematic cross-sectional view of a semiconductor device according to the present embodiment.

30: interlayer insulating film

32: Passivation film

34: Top layer wiring

40: Redistribution layer

42: Insulation layer

44: Insulation layer

46: Rewiring

50: UBM layer

52: Bump

100: Semiconductor device

Claims (12)

A negative photosensitive resin composition, which includes (A) polyimide, (B) a crosslinking agent containing multifunctional (meth)acrylate and (C) a photopolymerization initiator, polyimide ( A) comprising a structural unit (a1) represented by the following general formula (a1) and a structural unit (a2) represented by the following general formula (a2),

In the general formula (a1), Y is selected from the groups represented by the following general formula (a1-1), the following general formula (a1-2) and the following general formula (a1-3), and there may be a plurality of Y same or different,

In the general formula (a1-1), R ⁷ and R ⁸ independently represent a hydrogen atom, an alkyl group with 1 to 3 carbons, and an alkoxy group with 1 to 3 carbons, and there are plural R ⁷ and each other and there are plural The individual R ⁸ may be the same or different, and R ⁹ represents a hydrogen atom, an alkyl group with 1 to 3 carbons, or an alkoxy group with 1 to 3 carbons, and a plurality of R ⁹ may be the same or different from each other , * represents a bonding bond. In the general formula (a1-2), R ¹⁰ and R ¹¹ independently represent a hydrogen atom, an alkyl group with 1 to 3 carbons, and an alkoxy group with 1 to 3 carbons, and there are multiple The R ^10s and multiple R ^11s may be the same or different. * represents a bond. In the general formula (a1-3), Z represents an alkylene group with 1 to 5 carbons, a divalent aromatic group, * represents a bond, in the general formula (a2), R ¹ to R ⁴ independently represent an alkyl group with 1 to 3 carbons or an alkoxy group with 1 to 3 carbons, and R ¹ and R ² are Different groups, R ³ and R ⁴ are different groups, X ¹ represents a single bond, -SO ₂ -, -C(=O)-, a linear or branched chain alkylene or carbon number of 1 to 5 In the linear or branched fluoroalkylene group having a number of 1 to 5, plural X ¹ may be the same or different. The negative photosensitive resin composition according to claim 1, wherein the aforementioned polyimide (A) further comprises a structural unit (a3) represented by the following general formula (a3),

In the general formula (a3), Q ¹ and Q ² independently represent a hydroxyl group and a carboxyl group, and X ² represents a single bond, -SO ₂ -, -C(=O)-, straight chain or branched chain with 1 to 5 carbons Alkylene groups or straight-chain or branched-chain fluoroalkylene groups having 1 to 5 carbon atoms, and plural ^X2 may be the same or different. The negative photosensitive resin composition according to claim 1 or 2, wherein the aforementioned polyimide (A) includes a structural unit represented by the following general formula (1),

In the general formula (1), R ¹ to R ⁴ and X ¹ have the same meanings as those of the general formula (a2), and Y has the same meanings as those of the general formula (a1). The negative photosensitive resin composition according to claim 2, wherein the aforementioned polyimide (A) includes a structural unit represented by the following general formula (2),

In the general formula (2), Q ¹ , Q ² , and X ² have the same meaning as the general formula (a3), and Y has the same meaning as the general formula (a1). A negative photosensitive polymer comprising a structural unit (a1) represented by the following general formula (a1) and a structural unit (a2) represented by the following general formula (a2),

In the general formula (a1), Y is selected from the groups represented by the following general formula (a1-1), the following general formula (a1-2) and the following general formula (a1-3), and there may be a plurality of Y same or different,

In the general formula (a1-1), R ⁷ and R ⁸ independently represent a hydrogen atom, an alkyl group with 1 to 3 carbons, and an alkoxy group with 1 to 3 carbons, and there are plural R ⁷ and each other and there are plural The individual R ⁸ may be the same or different, and R ⁹ represents a hydrogen atom, an alkyl group with 1 to 3 carbons, or an alkoxy group with 1 to 3 carbons, and a plurality of R ⁹ may be the same or different from each other , * represents a bonding bond. In the general formula (a1-2), R ¹⁰ and R ¹¹ independently represent a hydrogen atom, an alkyl group with 1 to 3 carbons, and an alkoxy group with 1 to 3 carbons, and there are multiple The R ^10s and multiple R ^11s may be the same or different. * represents a bond. In the general formula (a1-3), Z represents an alkylene group with 1 to 5 carbons, a divalent aromatic group, * represents a bond, in the general formula (a2), R ¹ to R ⁴ independently represent an alkyl group with 1 to 3 carbons or an alkoxy group with 1 to 3 carbons, and R ¹ and R ² are Different groups, R ³ and R ⁴ are different groups, X ¹ represents a single bond, -SO ₂ -, -C(=O)-, a linear or branched chain alkylene or carbon number of 1 to 5 In the linear or branched fluoroalkylene group having a number of 1 to 5, plural X ¹ may be the same or different. The negative photosensitive polymer according to claim 5, which further comprises a structural unit (a3) represented by the following general formula (a3),

In the general formula (a3), Q ¹ and Q ² independently represent a hydroxyl group and a carboxyl group, and X ² represents a single bond, -SO ₂ -, -C(=O)-, straight chain or branched chain with 1 to 5 carbons Alkylene groups or straight-chain or branched-chain fluoroalkylene groups having 1 to 5 carbon atoms, and plural ^X2 may be the same or different. The negative photosensitive polymer according to claim 5 or 6, which comprises a structural unit represented by the following general formula (1),

In the general formula (1), R ¹ to R ⁴ and X ¹ have the same meanings as those of the general formula (a2), and Y has the same meanings as those of the general formula (a1). The negative photosensitive polymer according to claim 5 or 6, which comprises a structural unit represented by the following general formula (2),

In the general formula (2), Q ¹ , Q ² , and X ² have the same meaning as the general formula (a3), and Y has the same meaning as the general formula (a1). Such as the negative photosensitive polymer of claim 6, wherein, The reduction rate of the weight average molecular weight measured under the following conditions is 9% or less, The conditions are as follows: 400 parts by mass of γ-butyrolactone, 200 parts by mass of 4-methyltetrahydropyran, and 50 parts by mass of water were added to 100 parts by mass of the aforementioned negative photosensitive polymer and stirred at 100° C. for 6 hours. Calculated by the following formula, Formula: [(weight average molecular weight before test-weight average molecular weight after test)/weight average molecular weight before test]×100. A cured film comprising a cured product of the negative photosensitive resin composition according to any one of claims 1 to 4. A semiconductor device comprising a resin film comprising a cured product of the negative photosensitive resin composition according to any one of claims 1 to 4. A semiconductor device comprising: interlayer insulating film; A resin film provided on the interlayer insulating film and comprising a cured product of the negative photosensitive resin composition according to any one of claims 1 to 4; and Further wiring is embedded in the aforementioned resin film.

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