TW202039638A - Negative photosensitive resin composition, manufacturing method of polyimide and manufacturing method of cured protruded pattern wherein the negative photosensitive resin composition includes a polyimide precursor, a photopolymerization initiator, a silane coupling agent and an organic solvent - Google Patents

Abstract

The present invention provides a negative photosensitive resin composition that can obtain a higher chemical resistance and resolution and can prevent voids from being generated at an interface between a Cu layer and a resin layer after a high temperature storage test. The negative photosensitive resin composition comprises (A) a polyimide precursor, (B) a photopolymerization initiator, (C) a silane coupling agent, which is represented by a general formula (1); and (D) an organic solvent, which is selected from a group consisting of [gamma]-butyrolactone, dimethyl sulfide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate and [epsilon]-caprolactone. In the general formula (1), a is an integer of 1 to 3, n is an integer of 1 to 6, R21 is each independently an alkyl group with 1 to 4 carbons, R22 is a hydroxyl group or an alkyl group with 1 to 4 carbons, and R20 is selected from a group consisting of epoxy groups, phenylamino groups, urea groups and isocyanate groups.

Description

Negative photosensitive resin composition, method for producing polyimide, and method for producing hardened relief pattern

The present invention relates to a negative photosensitive resin composition, a manufacturing method of polyimide, and a manufacturing method of hardened relief patterns.

Previously, insulating materials of electronic parts, passivation films, surface protection films, and interlayer insulating films of semiconductor devices used polyimide resins, polybenzoxazole resins, etc., which have excellent heat resistance, electrical properties, and mechanical properties. Phenolic resin, etc. Among these resins, the provider in the form of a photosensitive resin composition can easily form a heat-resistant float through the coating, exposure, development, and thermal imidization treatment of the composition. Convex pattern film. This photosensitive resin composition has the feature of greatly shortening the steps compared with the previous non-photosensitive materials.

In addition, semiconductor devices (hereinafter also referred to as "devices") are mounted on a printed circuit board by various methods according to the purpose. The previous devices are generally manufactured by wire bonding using thin wires to connect the external terminals (pads) of the device to the lead frame. However, with the rapid development of components and the operating frequency reaching GHz today, the difference in the wiring length of each terminal during installation affects the operation of the component. Therefore, in the installation of high-end components, the length of the installed wiring must be accurately controlled, and it is difficult for wire bonding to meet this requirement.

Therefore, flip-chip mounting is proposed, which is to form a rewiring layer on the surface of a semiconductor wafer, form bumps (electrodes) thereon, turn the wafer over, and directly mount it on a printed circuit board (for example, refer to Patent Document 1). In the flip-chip installation, because the wiring distance can be accurately controlled, it is used for high-end components for processing high-speed signals, or because the installation size is small, it is used for mobile phones, etc., and the demand is rapidly expanding. In the case of flip-chip mounting using polyimide, polybenzoxazole, phenol resin, etc., after the pattern of the resin layer is formed, the metal wiring layer forming step is passed. The metal wiring layer is usually plasma etched on the surface of the resin layer to roughen the surface, and then sputtered with a thickness of 1 μm or less to form a metal layer that becomes the seed layer for plating, and then use the metal layer as an electrode , Formed by electroplating. At this time, titanium (Ti) is generally used as the metal for the seed layer, and copper (Cu) is used as the metal for the rewiring layer formed by electroplating.

In addition, in recent years, fan-out semiconductor packages have attracted attention. In the fan-out semiconductor package, the semiconductor chip is covered with a sealing material (resin layer) to form a chip sealing body larger than the chip size of the semiconductor chip. Furthermore, a rewiring layer reaching the area of the semiconductor wafer and the sealing material is formed. The rewiring layer is formed with a thinner film thickness. In addition, the rewiring layer can be formed to the area of the sealing material, so the number of external connection terminals can be increased.

For this kind of metal rewiring layer, it is required to have high adhesion between the metal layer and the resin layer of the rewiring after the reliability test. Especially in recent years, it is required to heat and harden the rewiring layer at a lower temperature. As a reliability test, for example, the following test can be exemplified: a high-temperature storage test in the air at a high temperature of 125°C or higher for more than 100 hours; while assembling the wiring and applying a voltage, it is confirmed that it is in the air at a temperature of about 125°C High-temperature action test when stored for more than 100 hours; in the air, a low temperature state of -65℃～-40℃ and a high temperature state of 125℃～150℃ cyclically reciprocate temperature cycle test; temperature above 85℃ High-temperature and high-humidity storage test at a temperature of 85% or more in a water vapor atmosphere; while assembling wiring and applying voltage, while performing the same high-temperature and high-humidity storage test as the high-temperature and high-humidity storage test; and in the air Or pass the solder reflow test in a 260℃ solder reflow furnace under nitrogen. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2001-338947

[The problem to be solved by the invention]

However, previously, in the above-mentioned reliability test, in the case of the high-temperature storage test, there was a problem that voids were generated at the interface between the rewiring Cu layer and the resin layer after the test. Especially when the temperature of heat hardening is low, there is a more obvious tendency. If a void is generated at the interface between the Cu layer and the resin layer, the adhesion between the two will decrease.

In addition to the problem of voids, chemical resistance is also required for the metal rewiring layer, and the requirements for miniaturization are also increasing. Therefore, the photosensitive resin composition used to form the rewiring layer of a semiconductor is particularly required to suppress the generation of voids and exhibit high chemical resistance and resolution.

The present invention was conceived in view of this previous actual situation, and one of its objects is to provide a method that can obtain higher chemical resistance and resolution, and can inhibit the high temperature storage (high temperature storage) test after the Cu layer and the resin A negative photosensitive resin composition (hereinafter, also referred to as "photosensitive resin composition" in this specification) in which voids are generated at the interface between the layers. In addition, another object is to provide a method for forming a hardened relief pattern using the negative photosensitive resin composition of the present invention. [Technical means to solve the problem]

{式中，a為1～3之整數，n為1～6之整數，R₂₁ 分別獨立地為碳數1～4之烷基，R₂₂ 為羥基或碳數1～4之烷基，而且，R₂₀ 係選自由包含環氧基、苯基胺基、脲基及異氰酸基之取代基所組成之群中之至少1種}； 及 (D)有機溶劑，其含有選自由γ-丁內酯、二甲基亞碸、四氫糠醇、乙醯乙酸乙酯、丁二酸二甲酯、丙二酸二甲酯及ε-己內酯所組成之群中之至少1種。 [2] 如[1]所記載之負型感光性樹脂組合物，其中於上述通式(1)中，R₂₀ 係選自由包含苯基胺基及脲基之取代基所組成之群中之至少1種。 [3] 如[1]或[2]所記載之負型感光性樹脂組合物，其中於上述通式(1)中，R₂₀ 係包含苯基胺基之取代基。 [4] 如[1]至[3]中任一項所記載之負型感光性樹脂組合物，其進而包含(E)熱產鹼劑。 [5] 如[1]至[4]中任一項所記載之負型感光性樹脂組合物，其中上述(D)有機溶劑含有選自由γ-丁內酯、二甲基亞碸、四氫糠醇、乙醯乙酸乙酯、丁二酸二甲酯、丙二酸二甲酯及ε-己內酯所組成之群中之至少2種。 [6] 如[1]至[5]中任一項所記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物具有下述通式(2)所表示之結構單元： [化2]

{式中，X₁ 為四價有機基，Y₁ 為二價有機基，n₁ 為2～150之整數，而且，R₁ 及R₂ 分別獨立地為氫原子或一價有機基，而且，R₁ 及R₂ 之至少一者為一價有機基}。 [7] 如[6]所記載之負型感光性樹脂組合物，其中於上述通式(2)中，R₁ 及R₂ 之至少一者為下述通式(3)所表示之一價有機基： [化3]

{式中，L₁ 、L₂ 及L₃ 分別獨立地為氫原子或碳數1～3之有機基，而且，m₁ 為2～10之整數}。 [8] 如[6]或[7]所記載之負型感光性樹脂組合物，其中於上述通式(2)中，X₁ 具有下述通式(20a)所表示之結構： [化4]

。 [9] 如[6]或[7]所記載之負型感光性樹脂組合物，其中於上述通式(2)中，X₁ 具有下述通式(20b)所表示之結構： [化5]

。 [10] 如[6]或[7]所記載之負型感光性樹脂組合物，其中於上述通式(2)中，X₁ 具有下述通式(20c)所表示之結構： [化6]

。 [11] 如[6]至[10]中任一項所記載之負型感光性樹脂組合物，其中於上述通式(2)中，Y₁ 包含下述通式(21b)所表示之結構： [化7]

。 [12] 如[6]至[10]中任一項所記載之負型感光性樹脂組合物，其中於上述通式(2)中，Y₁ 包含下述通式(21c)所表示之結構： [化8]

{式中，R₆ 係選自由氫原子、氟原子、碳數1～10之烴基、及碳數1～10之含氟烴基所組成之群中之一價基，而且，n係選自0～4之整數}。 [13] 如[6]或[7]所記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物具有下述通式(4)所表示之結構單元： [化9]

{式中，R₁ 及R₂ 分別獨立地為氫原子或一價有機基，R₁ 及R₂ 之至少一者為一價有機基，而且，n₁ 為2～150之整數}。 [14] 如[6]或[7]所記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物具有下述通式(5)所表示之結構單元： [化10]

{式中，R₁ 及R₂ 分別獨立地為氫原子或一價有機基，R₁ 及R₂ 之至少一者為一價有機基，而且，n₁ 為2～150之整數}。 [15] 如[6]或[7]所記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物同時包含下述通式(4)所表示之結構單元： [化11]

{式中，R₁ 及R₂ 分別獨立地為氫原子或一價有機基，R₁ 及R₂ 之至少一者為一價有機基，而且，n₁ 為2～150之整數}；及 下述通式(5)所表示之結構單元： [化12]

{式中，R₁ 及R₂ 分別獨立地為氫原子或一價有機基，R₁ 及R₂ 之至少一者為一價有機基，而且，n₁ 為2～150之整數。該等可與通式(4)中之R₁ 、R₂ 及n₁ 相同，或者亦可不同}。 [16] 如[15]所記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物係上述通式(4)與(5)所表示之結構單元之共聚物。 [17] 如[6]或[7]所記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物具有下述通式(6)所表示之結構單元： [化13]

{式中，R₁ 及R₂ 分別獨立地為氫原子或一價有機基，R₁ 及R₂ 之至少一者為一價有機基，而且，n₁ 為2～150之整數}。 [18] 如[1]至[17]中任一項所記載之負型感光性樹脂組合物，其包含 100質量份之上述(A)聚醯亞胺前驅物、 以上述(A)聚醯亞胺前驅物100質量份作為基準為0.1～20質量份之上述(B)光聚合起始劑、及 以上述(A)聚醯亞胺前驅物100質量份作為基準為0.1～20質量份之上述(C)矽烷偶合劑。 [19] 一種聚醯亞胺之製造方法，其包括將如[1]至[18]中任一項所記載之負型感光性樹脂組合物轉化為聚醯亞胺之步驟。 [20] 一種硬化浮凸圖案之製造方法，其包括以下之步驟： (1)將如[1]至[18]中任一項所記載之負型感光性樹脂組合物塗佈於基板上，於上述基板上形成感光性樹脂層； (2)將上述感光性樹脂層進行曝光； (3)使曝光後之上述感光性樹脂層顯影，形成浮凸圖案；及 (4)對上述浮凸圖案進行加熱處理，形成硬化浮凸圖案。 [發明之效果]The inventors of the present invention found that the above-mentioned problems can be solved by combining a specific polyimide precursor, a silane coupling agent with a specific structure, and a specific organic solvent, thereby completing the present invention. That is, the present invention is as follows. [1] A negative photosensitive resin composition comprising the following components: (A) a polyimide precursor; (B) a photopolymerization initiator; (C) a silane coupling agent, which is generally described by Formula (1) means: [化1]

{In the formula, a is an integer of 1 to 3, n is an integer of 1 to 6, R _{21 is} each independently an alkyl group with 1 to 4 carbons, R ₂₂ is a hydroxyl group or an alkyl group with 1 to 4 carbons, and , R ₂₀ is at least one selected from the group consisting of substituents including epoxy groups, phenylamino groups, urea groups and isocyanate groups}; and (D) organic solvents, which contain γ- At least one of the group consisting of butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetamide, dimethyl succinate, dimethyl malonate and ε-caprolactone. [2] The negative photosensitive resin composition as described in [1], wherein in the general formula (1), R ₂₀ is selected from the group consisting of substituents containing a phenylamino group and a ureido group At least one. [3] The negative photosensitive resin composition as described in [1] or [2], wherein in the general formula (1), R ₂₀ is a substituent containing a phenylamino group. [4] The negative photosensitive resin composition as described in any one of [1] to [3], which further contains (E) a thermal base generator. [5] The negative photosensitive resin composition as described in any one of [1] to [4], wherein the organic solvent (D) contains selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, and tetrahydro At least two of the group consisting of furfuryl alcohol, ethyl acetate, dimethyl succinate, dimethyl malonate and ε-caprolactone. [6] The negative photosensitive resin composition as described in any one of [1] to [5], wherein the (A) polyimide precursor has a structural unit represented by the following general formula (2) : [化2]

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, and R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, and, At least one of R ₁ and R ₂ is a monovalent organic group}. [7] The negative photosensitive resin composition as described in [6], wherein in the above general formula (2), at least one of R ₁ and R ₂ is a valence represented by the following general formula (3) Organic base: [化3]

{In the formula, L ₁ , L ₂ and L ₃ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10}. [8] The negative photosensitive resin composition as described in [6] or [7], wherein in the above general formula (2), X ₁ has a structure represented by the following general formula (20a): [化4] ]

. [9] The negative photosensitive resin composition as described in [6] or [7], wherein in the above general formula (2), X ₁ has a structure represented by the following general formula (20b): [化5] ]

. [10] The negative photosensitive resin composition as described in [6] or [7], wherein in the above general formula (2), X ₁ has a structure represented by the following general formula (20c): [化6] ]

. [11] The negative photosensitive resin composition as described in any one of [6] to [10], wherein in the above general formula (2), Y ₁ includes a structure represented by the following general formula (21b) : [化7]

. [12] The negative photosensitive resin composition as described in any one of [6] to [10], wherein in the above general formula (2), Y ₁ includes a structure represented by the following general formula (21c) : [化8]

{In the formula, R ₆ is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group with 1 to 10 carbons, and a fluorine-containing hydrocarbon group with 1 to 10 carbons, and n is selected from 0 An integer of ~4}. [13] The negative photosensitive resin composition as described in [6] or [7], wherein the (A) polyimide precursor has a structural unit represented by the following general formula (4): [化9] ]

{In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, at least one of R ₁ and R ₂ is a monovalent organic group, and n ₁ is an integer of 2 to 150}. [14] The negative photosensitive resin composition as described in [6] or [7], wherein the polyimide precursor (A) has a structural unit represented by the following general formula (5): [化10] ]

{In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, at least one of R ₁ and R ₂ is a monovalent organic group, and n ₁ is an integer of 2 to 150}. [15] The negative photosensitive resin composition as described in [6] or [7], wherein the (A) polyimide precursor also contains a structural unit represented by the following general formula (4): [化11]

{Wherein, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, at least one of R ₁ and R ₂ is a monovalent organic group, and n ₁ is an integer from 2 to 150}; and The structural unit represented by the general formula (5): [化12]

{In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, at least one of R ₁ and R ₂ is a monovalent organic group, and n ₁ is an integer of 2 to 150. These may be the same as R ₁ , R ₂ and n ₁ in the general formula (4), or may be different}. [16] The negative photosensitive resin composition according to [15], wherein the (A) polyimide precursor is a copolymer of structural units represented by the general formulas (4) and (5). [17] The negative photosensitive resin composition as described in [6] or [7], wherein the polyimide precursor (A) has a structural unit represented by the following general formula (6): [化13] ]

{In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, at least one of R ₁ and R ₂ is a monovalent organic group, and n ₁ is an integer of 2 to 150}. [18] The negative photosensitive resin composition as described in any one of [1] to [17], which contains 100 parts by mass of the (A) polyimide precursor, and the (A) polyimide 100 parts by mass of the imine precursor are 0.1-20 parts by mass of the aforementioned (B) photopolymerization initiator, and 0.1-20 parts by mass of the aforementioned (A) polyimine precursor as the basis of 100 parts by mass The above (C) Silane coupling agent. [19] A method for producing polyimide, which includes a step of converting the negative photosensitive resin composition as described in any one of [1] to [18] into polyimide. [20] A method of manufacturing a hardened relief pattern, which includes the following steps: (1) Coating the negative photosensitive resin composition as described in any one of [1] to [18] on a substrate, Forming a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer; (3) developing the photosensitive resin layer after exposure to form a relief pattern; and (4) applying the relief pattern Heat treatment to form a hardened relief pattern. [Effects of Invention]

According to the present invention, it is possible to provide a negative photosensitive resin composition that can obtain higher chemical resistance and resolution, and suppress the generation of voids at the interface between the Cu layer and the resin layer after a high temperature storage test And the manufacturing method of polyimide, and can provide a method for forming a hardened relief pattern using the negative photosensitive resin composition.

Hereinafter, a mode for implementing the present invention (hereinafter referred to as "embodiment") will be described in detail. In addition, the present invention is not limited to the following embodiments, and can be implemented with various changes within the scope of the gist. Furthermore, according to this specification, when there are plural structures represented by the same symbol in the general formula, they may be the same or different from each other.

<Negative photosensitive resin composition> The negative photosensitive resin composition of this embodiment contains the following components: (A) Polyimide precursor; (B) Photopolymerization initiator; (C) Silane coupling agent with specific structure; and (D) Specific organic solvents.

From the viewpoint of obtaining higher resolution, the negative photosensitive resin composition preferably contains 100 parts by mass of the (A) polyimide precursor and 100 parts by mass of the (A) polyimide precursor as The reference is 0.1-20 parts by mass of (B) photopolymerization initiator, and (A) 100 parts by mass of the polyimide precursor as the reference is 0.1-20 parts by mass (C) silane couple with a specific structure mixture.

{式中，X₁ 為四價有機基，Y₁ 為二價有機基，n₁ 為2～150之整數，而且，R₁ 及R₂ 分別獨立地為氫原子或一價有機基}。(A) Polyimide precursor The (A) polyimine precursor in this embodiment is a resin component contained in the negative photosensitive resin composition, and is converted into polyimide by performing a heat cyclization treatment Imine. The polyimide precursor is preferably a polyimide having a structural unit represented by the following general formula (2): [formation 14]

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, and R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group}.

{式中，L₁ 、L₂ 及L₃ 分別獨立地為氫原子或碳數1～3之有機基，而且，m₁ 為2～10之整數}。At least one of R ₁ and R ₂ is preferably a monovalent organic group represented by the following general formula (3): [化15]

{In the formula, L ₁ , L ₂ and L ₃ are each independently a hydrogen atom or an organic group having 1 to 3 carbons, and m ₁ is an integer of 2 to 10}.

In the general formula (2), n ₁ is not limited as long as it is an integer of 2 to 150, and it is preferably an integer of 3 to 100 from the viewpoint of the photosensitive properties and mechanical properties of the negative photosensitive resin composition , More preferably an integer of 5 to 70.

{式中，R₆ 係選自由氫原子、氟原子、碳數1～10之烴基、及碳數1～10之含氟烴基所組成之群中之一價基，l係選自0～2之整數，m係選自0～3之整數，而且，n係選自0～4之整數}。又，X₁ 之結構可為1種，亦可為2種以上之組合。具有上述式(20)所表示之結構之X₁ 基係就同時實現耐熱性與感光特性之觀點而言較佳。From the viewpoint of achieving both heat resistance and photosensitivity, the tetravalent organic group represented by X _{1 in} the general formula (2) is preferably an organic group with 6 to 40 carbon atoms, more preferably -COOR ₁ group and -COOR An aromatic group or an alicyclic aliphatic group in which the ₂ group and the -CONH- group are in the ortho position to each other. As the tetravalent organic group represented by X ₁ , specifically, an organic group having 6 to 40 carbon atoms containing an aromatic ring can be exemplified, for example, an organic group having a structure represented by the following general formula (20) Basis, but not limited to these: [化16]

{In the formula, R ₆ is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group with 1 to 10 carbons, and a fluorine-containing hydrocarbon group with 1 to 10 carbons, and l is selected from 0 to 2 M is an integer selected from 0 to 3, and n is an integer selected from 0 to 4}. In addition, the structure of X ₁ may be one type or a combination of two or more types. The X ₁ group having the structure represented by the above formula (20) is preferable from the viewpoint of achieving both heat resistance and photosensitive characteristics.

[化18]

[化19]

， 尤佳為下述式(20a)、(20b)或(20c)所表示之結構： [化20]

[化21]

[化22]

。As the X ₁ group, in the structure represented by the above formula (20), in terms of chemical resistance, resolution, and void suppression after a high temperature storage test, the following formulas (20A), (20B) The structure represented by) or (20C): [化17]

[化18]

[化19]

, Particularly preferably the structure represented by the following formula (20a), (20b) or (20c): [化20]

[化21]

[化22]

.

{式中，R₆ 係選自由氫原子、氟原子、碳數1～10之烴基、及碳數1～10之含氟烴基所組成之群中之一價基，而且，n係選自0～4之整數}。 又，Y₁ 之結構可為1種，亦可為2種以上之組合。具有上述式(21)所表示之結構之Y₁ 基係就同時實現耐熱性及感光特性之觀點而言較佳。From the viewpoint of achieving both heat resistance and photosensitive properties, the divalent organic group represented by Y ₁ in the general formula (2) is preferably an aromatic group having 6 to 40 carbon atoms. For example, the following formula ( 21) The structure represented, but not limited to these: [化23]

{In the formula, R ₆ is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group with 1 to 10 carbons, and a fluorine-containing hydrocarbon group with 1 to 10 carbons, and n is selected from 0 An integer of ~4}. In addition, the structure of Y ₁ may be one type or a combination of two or more types. The Y ₁ group having the structure represented by the above formula (21) is preferable from the viewpoint of achieving both heat resistance and photosensitive characteristics.

[化25]

[化26]

， 尤佳為下述式(21b)或(21c)所表示之結構： [化27]

[化28]

。As the Y ₁ group, in the structure represented by the above formula (21), from the viewpoints of chemical resistance, resolution, and void suppression after a high temperature storage test, the following formulas (21A), (21B) The structure represented by) or (21C): [化24]

[化25]

[化26]

, Particularly preferably the structure represented by the following formula (21b) or (21c): [化27]

[化28]

.

L ₁ in the above general formula (3) is preferably a hydrogen atom or a methyl group, and from the viewpoint of photosensitive properties, L ₂ and L _{3 are} preferably hydrogen atoms. In addition, from the viewpoint of photosensitive characteristics, m ₁ is an integer of 2 or more and 10 or less, and preferably an integer of 2 or more and 4 or less.

{式中，R₁ 及R₂ 分別獨立地為氫原子或一價有機基，R₁ 及R₂ 之至少一者為一價有機基，而且，n₁ 為2～150之整數}。 於通式(4)中，R₁ 及R₂ 之至少一者更佳為上述通式(3)所表示之一價有機基。藉由(A)聚醯亞胺前驅物包含通式(4)所表示之聚醯亞胺前驅物，尤其是解像性之效果變高。In one embodiment, the (A) polyimine precursor is preferably a polyimine precursor having a structural unit represented by the following general formula (4): [化29]

{In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, at least one of R ₁ and R ₂ is a monovalent organic group, and n ₁ is an integer of 2 to 150}. In the general formula (4), at least one of R ₁ and R ₂ is more preferably a monovalent organic group represented by the general formula (3). When (A) the polyimide precursor includes the polyimide precursor represented by the general formula (4), the effect of particularly the resolution becomes higher.

{式中，R₁ 及R₂ 分別獨立地為氫原子或一價有機基，R₁ 及R₂ 之至少一者為一價有機基，而且，n₁ 為2～150之整數}。 於通式(5)中，R₁ 及R₂ 之至少一者更佳為上述通式(3)所表示之一價有機基。藉由(A)聚醯亞胺前驅物除通式(4)所表示之聚醯亞胺前驅物以外，亦包含通式(5)所表示之聚醯亞胺前驅物，尤其是解像性之效果變得更高。In one embodiment, the (A) polyimine precursor is preferably a polyimine precursor having a structural unit represented by the following general formula (5): [化30]

{In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, at least one of R ₁ and R ₂ is a monovalent organic group, and n ₁ is an integer of 2 to 150}. In the general formula (5), at least one of R ₁ and R ₂ is more preferably a monovalent organic group represented by the general formula (3). In addition to the polyimide precursor represented by the general formula (4), the polyimide precursor (A) also includes the polyimide precursor represented by the general formula (5), especially the resolution The effect becomes higher.

Among them, from the viewpoint of chemical resistance, resolution, and void suppression after high temperature storage test, it is particularly preferable that (A) the polyimide precursor contains both the above general formulas (4) and (5) The structural unit represented may be a copolymer of structural units represented by the general formulas (4) and (5). When (A) the polyimide precursor is a copolymer of structural units represented by the general formulas (4) and (5), R ₁ , R ₂ and n _{1 in} one formula may be the same as those in the other formula. R ₁ , R ₂ and n _{1 are the} same or different.

{式中，R₁ 及R₂ 分別獨立地為氫原子或一價有機基，R₁ 及R₂ 之至少一者為一價有機基，而且，n₁ 為2～150之整數}。 於通式(6)中，R₁ 及R₂ 之至少一者更佳為上述通式(3)所表示之一價有機基。藉由(A)聚醯亞胺前驅物包含通式(6)所表示之聚醯亞胺前驅物，尤其是耐化學品性之效果變高。In one embodiment, the (A) polyimine precursor is preferably a polyimine precursor having a structural unit represented by the following general formula (6): [化31]

{In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, at least one of R ₁ and R ₂ is a monovalent organic group, and n ₁ is an integer of 2 to 150}. In the general formula (6), at least one of R ₁ and R ₂ is more preferably a monovalent organic group represented by the general formula (3). When (A) the polyimide precursor includes the polyimide precursor represented by the general formula (6), the effect of especially the chemical resistance becomes higher.

(A) Preparation method of polyimide precursor (A) Polyimine precursor system is obtained by the following method: First, the tetracarboxylic acid containing the tetravalent organic group X _{1 in} the above general formula (2) The dianhydride reacts with alcohols with photopolymerizable unsaturated double bonds and alcohols without any unsaturated double bonds to prepare partially esterified tetracarboxylic acid (hereinafter also referred to as acid/ester body), and then It undergoes amide condensation polymerization with diamines containing the divalent organic group Y ₁ in the general formula (2).

(Preparation of acid/ester body) In this embodiment, the tetracarboxylic dianhydride containing the tetravalent organic group X _{1 as} the precursor of (A) polyimine is preferably used to have the above-mentioned general The tetracarboxylic dianhydride of the structure represented by the formula (20) is representative, for example, pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, diphenyl Methyl ketone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenyl sulfide-3,3',4, 4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2, 2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc., preferably, pyromellitic anhydride, diphenyl ether-3 ,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetra The carboxylic dianhydride is not limited to these. Moreover, of course, these can be used individually or in mixture of 2 or more types.

In this embodiment, as alcohols with photopolymerizable unsaturated double bonds that can be preferably used for preparing (A) polyimide precursors, for example, 2-propenyloxyethanol, 1 -Acrylic oxy-3-propanol, 2-acrylamide ethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-acrylic acid 2- Hydroxy-3-butoxypropyl, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-tert-butoxypropyl acrylate , 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloxyethanol, 1-methacryloxy-3-propanol, 2-methacrylamide ethanol, hydroxymethyl Vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy methacrylate -3-phenoxypropyl ester, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, 2-hydroxy-3-methacrylate Cyclohexyloxy propyl ester and so on.

It can also be used in the above-mentioned alcohols with photopolymerizable unsaturated double bonds, for example by mixing a part of alcohols without unsaturated double bonds, the alcohols without unsaturated double bonds are methanol, ethanol, n-propanol , Isopropanol, n-butanol, tertiary butanol, 1-pentanol, 2-pentanol, 3-pentanol, neopentanol, 1-heptanol, 2-heptanol, 3-heptanol, 1- Octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, benzyl alcohol Wait.

In addition, as a polyimide precursor, a non-photosensitive polyimide precursor prepared only from the above-mentioned alcohols without unsaturated double bonds and a photosensitive polyimide precursor may be mixed and used. . From the viewpoint of resolution, the non-photosensitive polyimide precursor is based on 100 parts by mass of the photosensitive polyimide precursor, and preferably 200 parts by mass or less.

In the presence of a basic catalyst such as pyridine, the above-mentioned preferred tetracarboxylic dianhydride and the above-mentioned alcohol are stirred at a temperature of 20-50℃ for 4-10 hours to dissolve them in the solvent described below , And mixed, so that the esterification reaction of acid anhydride can proceed to obtain the desired acid/ester body.

(Preparation of polyimide precursor) In the above acid/ester body (typically a solution in the following solvent), an appropriate dehydrating condensing agent, such as dicyclohexylcarbodiimide, is added under ice cooling , 1-Ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'- Dibutyl diamide carbonate, etc., are mixed to form the acid/ester body into a polyanhydride, and then the divalent organic group Y ₁ bis, which can be preferably used in this embodiment, is added dropwise to it The amine is separately dissolved or dispersed in a solvent, and the amine polycondensation is carried out to obtain the target polyimide precursor. As an alternative, after chlorination of the acid with sulfite chloride, etc., in the presence of a base such as pyridine, the above-mentioned acid/ester is reacted with a diamine compound to obtain the target polyimide precursor .

As the diamines containing the divalent organic group Y ₁ that can be preferably used in this embodiment, the diamines having the structure represented by the above general formula (21) are representative, for example: p-phenylenediamine , M-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether Phenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diamine Diphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl, 3,4'-diaminodiphenyl, 3,3'-diaminodiphenyl Benzene, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone Phenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3- Bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl] benzene, bis[4- (3-aminophenoxy)phenyl) sulfide, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[ 4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1 ,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis( 4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy) Phenyl) hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, bi-o-toluidine, 9,9-bis(4-aminophenyl)pyridine, and the Part of the hydrogen atoms on the benzene ring is substituted with methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen, etc., such as 3,3'-dimethyl-4,4'-diamino Biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'- Dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4' -Diaminobiphenyl and mixtures of these, but not limited to this.

After the amide polycondensation reaction is completed, if necessary, the water absorption by-products of the dehydration condensation agent coexisting in the reaction solution are filtered and separated, and poor solvents such as water, aliphatic lower alcohols, or a mixture of these are added to the obtained polymerization solution. Among the components, the polymer component is analyzed, and further re-dissolution and re-precipitation operations are repeated to refine the polymer, vacuum dry, and isolate the target polyimide precursor. In order to improve the refinement system, the polymer solution can be passed through a column filled with anion and/or cation exchange resin swelled by a suitable organic solvent to remove ionic impurities.

When measuring the weight average molecular weight in terms of polystyrene by gel permeation chromatography, the molecular weight of the polyimide precursor (A) is preferably 8,000 to 150,000, and more preferably 9,000 to 50,000. When the weight average molecular weight is above 8,000, the mechanical properties are good. When the weight average molecular weight is below 150,000, the dispersion in the developer is good, and the resolution of the relief pattern is good. As the developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. In addition, the weight average molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As standard monodisperse polystyrene, it is recommended to choose from STANDARD SM-105, an organic solvent standard sample manufactured by Showa Denko Corporation.

、2-甲基9-氧硫𠮿

、2-異丙基9-氧硫𠮿

、二乙基9-氧硫𠮿

等9-氧硫𠮿

衍生物；苯偶醯、苯偶醯二甲基縮酮、苯偶醯-β-甲氧基乙基縮醛等苯偶醯衍生物；安息香、安息香甲醚等安息香衍生物；1-苯基-1,2-丁二酮-2-(鄰甲氧基羰基)肟、1-苯基-1,2-丙二酮-2-(鄰甲氧基羰基)肟、1-苯基-1,2-丙二酮-2-(鄰乙氧基羰基)肟、1-苯基-1,2-丙二酮-2-(鄰苯甲醯基)肟、1,3-二苯基丙三酮-2-(鄰乙氧基羰基)肟、1-苯基-3-乙氧基丙三酮-2-(鄰苯甲醯基)肟等肟類；N-苯基甘胺酸等N-芳基甘胺酸類；過氯化苯甲醯等過氧化物類；芳香族聯咪唑類；二茂鈦類；α-(正辛磺醯氧基亞胺基)-4-甲氧基苯乙腈等光酸產生劑類等，但並不限定於該等。於上述光聚合起始劑中，尤其就光感度之觀點而言，更佳為肟類。(B) Photopolymerization initiator The (B) photopolymerization initiator used in this embodiment will be described. As the photopolymerization initiator, a photoradical polymerization initiator is preferable, and can be preferably exemplified: benzophenone, methyl phthalate, 4-benzyl-4'-methyl Benzophenone derivatives such as benzophenone, dibenzyl ketone, and quinone; 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl Acetophenone derivatives such as phenyl ketone; 9-oxysulfur

, 2-methyl 9-oxysulfur 𠮿

, 2-isopropyl 9-oxysulfur 𠮿

, Diethyl 9-oxysulfur 𠮿

Wait 9-oxysulfur 𠮿

Derivatives; benzil derivatives such as benzil, benzil dimethyl ketal, benzil-β-methoxyethyl acetal; benzoin derivatives such as benzoin and benzoin methyl ether; 1-phenyl -1,2-Butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1 ,2-Propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzyl)oxime, 1,3-diphenylpropane Trione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxyglycerol-2-(o-benzyl)oxime and other oximes; N-phenylglycine, etc. N-arylglycines; peroxides such as perchlorinated benzyl; aromatic biimidazoles; titanocene; α-(n-octylsulfonyloxyimino)-4-methoxy Photoacid generators such as phenylacetonitrile, etc. are not limited to these. Among the above-mentioned photopolymerization initiators, oximes are more preferable from the viewpoint of photosensitivity.

The compounding amount of (B) photopolymerization initiator in the negative photosensitive resin composition relative to 100 parts by mass of (A) polyimide precursor is preferably from 0.1 part by mass to 20 parts by mass, and more preferably 1 part by mass or more and 8 parts by mass or less. The above-mentioned compounding amount is 0.1 parts by mass or more from the viewpoint of photosensitivity or patterning properties, and 20 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative photosensitive resin composition .

{式中，a為1～3之整數，n為1～6之整數，R₂₁ 分別獨立地為碳數1～4之烷基，R₂₂ 為羥基或碳數1～4之烷基，而且，R₂₀ 係選自由包含環氧基、苯基胺基及脲基之取代基所組成之群中之至少1種} 於通式(1)中，a只要為1～3之整數即可，並無限定，就與金屬再配線層之接著性等觀點而言，較佳為2或3，更佳為3。 n只要為1～6之整數即可，並無限定，就與金屬再配線層之接著性之觀點而言，較佳為1以上4以下。就顯影性之觀點而言，較佳為2以上5以下。 R₂₁ 只要為碳數1～4之烷基即可，並無限定。可例示：甲基、乙基、丙基、異丙基、丁基、異丁基、第三丁基等。 R₂₂ 只要為羥基、或碳數1～4之烷基即可，並無限定。作為碳數1～4之烷基，可例示與R₂₁ 相同之烷基。 R₂₀ 只要為包含環氧基、苯基胺基、脲基、異氰酸基之取代基即可，並無限定。於該等中，就顯影性或金屬再配線層之接著性之觀點而言，較佳為選自由包含苯基胺基之取代基、及包含脲基之取代基所組成之群中之至少1種，更佳為包含苯基胺基之取代基。 作為含有環氧基之矽烷偶合劑，可例示：2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷等。 作為含有苯基胺基之矽烷偶合劑，可例示N-苯基-3-胺基丙基三甲氧基矽烷。 作為含有脲基之矽烷偶合劑，可例示3-脲基丙基三烷氧基矽烷。 作為含有異氰酸基之矽烷偶合劑，可例示3-異氰酸基丙基三乙氧基矽烷。(C) Silane coupling agent with specific structure (C) Silane coupling agent with specific structure used in this embodiment will be described. The (C) silane coupling agent having a specific structure in this embodiment has a structure represented by the following general formula (1). [化32]

{In the formula, a is an integer of 1 to 3, n is an integer of 1 to 6, R _{21 is} each independently an alkyl group with 1 to 4 carbons, R ₂₂ is a hydroxyl group or an alkyl group with 1 to 4 carbons, and , R ₂₀ is at least one selected from the group consisting of substituents including epoxy groups, phenylamino groups and ureido groups} In the general formula (1), a should just be an integer of 1 to 3, It is not limited, and it is preferably 2 or 3, more preferably 3 from the viewpoint of adhesion to the metal rewiring layer. n is not limited as long as it is an integer of 1 to 6, and it is preferably 1 or more and 4 or less from the viewpoint of adhesion to the metal rewiring layer. From the viewpoint of developability, it is preferably 2 or more and 5 or less. R ₂₁ is not limited as long as it is an alkyl group having 1 to 4 carbon atoms. Examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tertiary butyl. R ₂₂ is not limited as long as it is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms. As the C1-C4 alkyl group, the same alkyl group as R ₂₁ can be exemplified. R ₂₀ is not limited as long as it is a substituent containing an epoxy group, a phenylamino group, a urea group, and an isocyanate group. Among them, from the viewpoint of developability or adhesion of the metal rewiring layer, it is preferably at least 1 selected from the group consisting of a substituent containing a phenylamine group and a substituent containing a urea group It is more preferably a substituent containing a phenylamino group. Examples of epoxy-containing silane coupling agents include: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3- Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. As the silane coupling agent containing a phenylamino group, N-phenyl-3-aminopropyltrimethoxysilane can be exemplified. As the ureido group-containing silane coupling agent, 3-ureidopropyltrialkoxysilane can be exemplified. As the isocyanate group-containing silane coupling agent, 3-isocyanatopropyltriethoxysilane can be exemplified.

(D) Organic solvents with specific structure The organic solvent of this embodiment only needs to contain γ-butyrolactone, dimethyl sulfide, tetrahydrofurfuryl alcohol, ethyl acetate, dimethyl succinate, dimethyl malonate and ε-caprolactone. At least one of the group of esters is sufficient, and it is not limited. By containing the organic solvent, the adhesiveness with the sealing material can be sufficiently expressed. Among them, from the viewpoint of the solubility of the polyimide precursor (A), γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetate, and ε-caprolactone are preferred. From the viewpoint of suppressing voids on the copper surface, it is more preferable to include at least two organic solvents selected from the above group.

Although the reason for the good adhesion between the organic solvent having a specific structure and the sealing material in this embodiment is uncertain, the inventors of the present invention estimate as follows. Previously, the organic solvent to dissolve the photosensitive resin composition containing the polyimide precursor used N-methyl-2-pyrrolidone, or N,N-dimethylacetamide, N,N-dimethyl Amine-based solvents such as formamide. Although these solvents have a very high dissolving ability of polyimide precursors, in recent years when the heating and hardening temperature is required to be low (for example, less than 200 ℃), there is due to the affinity with the formed polyimide Tendency to remain high and large in the film. Therefore, due to the interaction with the above (C) silane coupling agent having a specific structure, etc., the performance is reduced. On the other hand, by containing the above-mentioned solvent, even if the heat-curing temperature is low, the solvent remaining in the film after heat-curing can be sufficiently reduced, so there is a tendency for the adhesion to the sealing material to be good.

In the negative photosensitive resin composition of the present embodiment, the amount of the organic solvent used is preferably 100 to 1000 parts by mass, more preferably 120 to 700 parts by mass relative to 100 parts by mass of the polyimide precursor (A) Parts, more preferably in the range of 125 to 500 parts by mass.

(E) Thermal alkali generator The negative photosensitive resin composition of the present embodiment may further contain components other than the aforementioned (A) to (D) components. In particular, in order to cope with the lowering of the heat hardening temperature, it is more preferable to include (E) a thermal alkali generator. The alkali generator refers to a compound that generates alkali by heating. By containing the thermal base generator, the imidization of the photosensitive resin composition can be further promoted.

The type of the thermal alkali generator is not particularly limited, and examples thereof include amine compounds protected by a tertiary butoxycarbonyl group, or thermal alkali generators disclosed in International Publication No. 2017/038598. However, it is not limited to these, in addition to this, a well-known thermal alkali generator can also be used.

As the amine compound protected by the tertiary butoxycarbonyl group, ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4 -Amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amine 2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, tyramine, norephedrine, 2-amino -1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol , N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino) Ethyl]benzyl alcohol, diethanolamine, diisopropanolamine, 3-pyrrolidol, 2-pyrrolidine methanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidine methanol, 3-piperidine methanol, 2-piperidine methanol, 4-piperidine ethanol, 2-piperidine ethanol, 2-(4-piperidinyl )-2-propanol, 1,4-butanol bis(3-aminopropyl) ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethyl Amine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown-5, diethylene glycol bis(3-aminopropyl Group) ether, 1,11-diamino-3,6,9-trioxaundecane, or a compound in which the amino acid and its derivatives are protected by the tertiary butoxycarbonyl group, but not Limited to these.

(E) The compounding amount of the thermal alkali generator is preferably 0.1 part by mass or more and 30 parts by mass or less, and more preferably 1 part by mass or more and 20 parts by mass or less relative to 100 parts by mass of the polyimide precursor (A). The above-mentioned compounding amount is preferably 0.1 parts by mass or more from the viewpoint of the effect of promoting the imidization, and 20 parts by mass from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative photosensitive resin composition the following.

The negative photosensitive resin composition of the present embodiment may further contain components other than the aforementioned (A) to (E) components. The components other than (A) to (E) are not limited. Examples include nitrogen-containing heterocyclic compounds, hindered phenol compounds, organic titanium compounds, sensitizers, photopolymerizable unsaturated monomers, thermal polymerization inhibitors剂 etc.

＜Nitrogen-containing heterocyclic compounds＞ When using the negative photosensitive resin composition of this embodiment to form a cured film on a substrate containing copper or copper alloy, in order to suppress discoloration on the copper, the negative photosensitive resin composition may optionally contain nitrogen Heterocyclic compounds. Specifically, an azole compound, a purine derivative, etc. can be mentioned.

Examples of the azole compound include: 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl -1H-triazole, 4-tert-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5- Phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-di Ethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α -Dimethylbenzyl)phenyl)-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl -5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-tertpentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxyl -5'-Third octylphenyl) benzotriazole, hydroxyphenyl benzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzo Triazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc.

Particularly preferred examples include tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. In addition, these azole compounds may be used singly or as a mixture of two or more kinds.

Specific examples of purine derivatives include: purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9- Methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9- (2-hydroxyethyl) adenine, guanine oxime, N-(2-hydroxyethyl) adenine, 8-amino adenine, 6-amino-8-phenyl-9H-purine, 1-ethyl Base adenine, 6-ethylaminopurine, 1-benzyl adenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaadenine Xanthine, 8-azahypoxanthine, etc. and their derivatives.

When the negative photosensitive resin composition contains the above-mentioned azole compound or purine derivative, the compounding amount is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the polyimide precursor (A), which is an improvement in the sensitivity characteristics From a viewpoint, 0.5-5 mass parts is more preferable. When the compounding amount of the azole compound relative to 100 parts by mass of the polyimide precursor of (A) is 0.1 parts by mass or more, the negative photosensitive resin composition of this embodiment is formed on copper or copper alloy At this time, the discoloration of the copper or copper alloy surface is suppressed. On the other hand, at 20 parts by mass or less, the light sensitivity is excellent.

＜Hindered phenol compounds＞ In addition, in order to suppress discoloration on the copper surface, the negative photosensitive resin composition may optionally contain a hindered phenol compound. Examples of hindered phenol compounds include 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, and octadecyl-3-( 3,5-di-tert-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4 ,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 4,4' -Butylene-bis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionic acid Ester], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylene bis [3-(3,5-Di-tert-butyl-4-hydroxyphenyl) propionate], N,N'-hexamethylene bis(3,5-di-tert-butyl-4- Hydroxy-phenylpropanamide), 2,2'-methylene-bis(4-methyl-6-tertiary butylphenol), 2,2'-methylene-bis(4-ethyl-6 -Tertiary butyl phenol), pentaerythritol-tetrakis[3-(3,5-di-tertiary butyl-4-hydroxyphenyl) propionate], tris-(3,5-di-tertiary butyl) 4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) Benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-tris-2,4,6-(1H,3H ,5H)-Triketone, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4, 6-(1H,3H,5H)-triketone, 1,3,5-tris(4-secondbutyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tri 𠯤-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl Yl]-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2 ,6-Dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2, 6-Dimethyl-4-phenylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-triketone, 1,3,5-tris(4- Tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1, 3,5-Tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H ,3H,5H)-Triketone, 1,3,5-tris(4-tertiarybutyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3 ,5-Tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tertiarybutyl-6-ethyl-3-hydroxy-2,5 -Dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tertiarybutyl-5) ,6-Diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5 -Tris(4-tertiary butyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1, 3,5-Tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H) -Triketone, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6 -(1H,3H,5H)-triketone etc., but not limited to this. Among these, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4 is particularly preferred ,6-(1H,3H,5H)-triketone etc.

The compounding amount of the hindered phenol compound is preferably 0.1-20 parts by mass relative to 100 parts by mass of the polyimide precursor (A), and more preferably 0.5-10 parts by mass from the viewpoint of photosensitivity characteristics. When the compounding amount of the hindered phenol compound with respect to 100 parts by mass of the polyimide precursor (A) is 0.1 parts by mass or more, for example, the negative photosensitive resin composition of this embodiment is formed on copper or copper alloy In this case, it prevents discoloration and corrosion of copper or copper alloy. On the other hand, in the case of 20 parts by mass or less, the light sensitivity is excellent.

＜Organic titanium compound＞ The negative photosensitive resin composition of this embodiment may contain an organic titanium compound. By containing an organic titanium compound, even when it is cured at a low temperature, a photosensitive resin layer with excellent chemical resistance can be formed.

As an organotitanium compound that can be used, an organic chemical substance is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organotitanium compounds are shown in I) to VII) below: I) Titanium chelate compound: Among them, in terms of obtaining the storage stability and good pattern of the negative photosensitive resin composition, it is more preferably a titanium chelate compound having two or more alkoxy groups. Specific examples are: bis(triethanolamine) titanium diisopropoxide, bis(2,4-glutaric acid) bis(n-butanol) titanium, bis(2,4-glutaric acid) titanium diisopropoxide, double (Tetramethylpimelic acid) titanium diisopropoxide, bis(ethylacetate) titanium diisopropoxide and the like.

II) Titanium tetraalkoxide compound: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexanol), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, Titanium tetramethoxypropoxide, titanium tetramethylphenoxide, tetra(n-nonanol) titanium, tetra(n-propanol) titanium, tetrastearyl titanium, tetra[bis{2,2-(allyloxymethyl基)Butanol}] Titanium, etc.

III) Titanocene compounds: for example (pentamethylcyclopentadienyl)titanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl) ) Titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc. IV) Monoalkoxide titanium compound: for example, tris(dioctylphosphate)titanium isopropoxide, tris(dodecylbenzenesulfonic acid)titanium isopropoxide and the like.

V) Titanium oxide compound: for example, titanyl bis(glutarate), titanyl bis(tetramethylpimelate), titanyl phthalocyanine, and the like. VI) Titanium tetraacetylpyruvate compound: for example, titanium tetraacetylpyruvate. VII) Titanate coupling agent: for example, isopropyl tris(dodecylbenzenesulfonyl) titanate and the like.

Among them, from the viewpoint of exerting better chemical resistance, the organic titanium compound is preferably selected from the group consisting of I) titanium chelate compound, II) tetraalkoxy titanium compound and III) titanocene compound. At least one compound in the group, especially bis(ethylacetate)titanium diisopropoxide, tetra(n-butoxide)titanium, and bis(η5-2,4-cyclopentadien-1-yl) ) Bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium.

When the organotitanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass relative to 100 parts by mass of the polyimide precursor (A). When the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited. On the other hand, when the amount is less than 10 parts by mass, the storage stability is excellent.

＜Sensitizer＞ In order to improve the photosensitivity, the negative photosensitive resin composition of this embodiment may optionally contain a sensitizer. As the sensitizer, for example, Michelone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylamino)benzylidene Yl)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methyl Cyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylidene dihydro Indanone, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenyl biphenyl)-benzothiazole, 2-(p-dimethylaminophenyl vinylidene ) Benzothiazole, 2-(p-dimethylaminophenyl vinylidene) isonaphththiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4 '-Diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin , 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylamine Coumarin, 3-ethoxycarbonyl-7-diethylamino coumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-Phenylethanolamine, 4-𠰌line benzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl- 5-Mercaptotetrazole, 2-Mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2- (P-dimethylamino styryl) naphtho(1,2-d)thiazole, 2-(p-dimethylamino styryl) styrene, etc. These can be used alone or, for example, in a combination of 2 to 5 types.

When the negative photosensitive resin composition contains a sensitizer for improving photosensitivity, the blending amount is preferably 0.1-25 parts by mass relative to 100 parts by mass of the (A) polyimide precursor.

＜Photopolymerizable unsaturated monomer＞ In order to improve the resolution of the relief pattern, the negative photosensitive resin composition may optionally contain a monomer having a photopolymerizable unsaturated bond. As such a monomer, a (meth)acrylic compound which undergoes a radical polymerization reaction by a photopolymerization initiator is preferred, and examples thereof include: diethylene glycol dimethacrylate, tetraethylene glycol dimethyl Mono- or diacrylate and methacrylate of ethylene glycol or polyethylene glycol such as base acrylate; mono- or diacrylate and methacrylate of propylene glycol or polypropylene glycol; mono-, di- or triacrylate of glycerin and Methacrylate; cyclohexane diacrylate and dimethacrylate; 1,4-butanediol diacrylate and dimethacrylate; 1,6-hexanediol diacrylate and dimethyl acrylate Acrylate; diacrylate and dimethacrylate of neopentyl glycol; mono or diacrylate and methacrylate of bisphenol A; benzene trimethacrylate, isopropyl acrylate and methacrylic acid Isopropyl ester; acrylamide and its derivatives; methacrylamide and its derivatives; trimethylolpropane triacrylate and methacrylate; glycerol di- or triacrylate and methacrylate; Di-, tri-, or tetra-acrylate and methacrylate of pentaerythritol; and compounds such as ethylene oxide or propylene oxide adducts of these compounds, but are not particularly limited to the above.

When the photosensitive resin composition contains the above-mentioned monomer having a photopolymerizable unsaturated bond for enhancing the resolution of the relief pattern, the blending amount of the monomer having a photopolymerizable unsaturated bond is relative to (A ) 100 parts by mass of the polyimide precursor, preferably 1-50 parts by mass.

＜Thermal polymerization inhibitor＞ In addition, the negative photosensitive resin composition of the present embodiment may optionally include thermal polymerization inhibition in order to improve the stability of the viscosity and photosensitivity of the negative photosensitive resin composition especially when stored in a solution containing a solvent. Agent. As the thermal polymerization inhibitor, for example, hydroquinone, N-nitrosodiphenylamine, p-tertiary butylcatechol, phenothionine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1 ,2-Cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso 2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N- Phenyl hydroxylamine ammonium salt, N-nitroso-N(1-naphthyl) hydroxylamine ammonium salt, etc.

<Method of manufacturing hardened relief pattern and semiconductor device> In addition, the present invention provides a method for manufacturing a hardened relief pattern, which includes the following steps: (1) Apply the negative photosensitive resin composition of this embodiment to a substrate to form a photosensitive resin layer on the substrate (2) Expose the photosensitive resin layer; (3) develop the photosensitive resin layer after exposure to form a relief pattern; and (4) heat the relief pattern to form a hardened relief pattern .

(1) Steps for forming photosensitive resin layer In this step, the negative photosensitive resin composition of the present invention is coated on a substrate, if necessary, and then dried to form a photosensitive resin layer. As the coating method, the method previously used for coating the photosensitive resin composition can be used, for example, by a spin coater, bar coater, knife coater, curtain coater, screen printer The method of spray coating by spray coating machine, etc.

The coating film containing the negative photosensitive resin composition can be dried if necessary. As a drying method, air drying, heating drying by an oven or hot plate, vacuum drying, etc. can be used. Specifically, in the case of air drying or heat drying, it can be dried at 20°C to 140°C for 1 minute to 1 hour. As described above, the photosensitive resin layer (negative photosensitive resin layer) can be formed on the substrate.

(2) Exposure step In this step, using an exposure device such as a contact aligner, a mirror projection aligner, a stepper, etc., through a patterned photomask or a reduction photomask, or directly by an ultraviolet light source, etc. The photosensitive resin layer is exposed.

Thereafter, based on the purpose of improving light sensitivity, post-exposure bake (PEB) and/or pre-development bake can be implemented by any combination of temperature and time as needed. Regarding the range of the baking conditions, the temperature is preferably from 40°C to 120°C, and the time is from 10 seconds to 240 seconds, but it is not limited to this as long as it does not hinder the characteristics of the negative photosensitive resin composition of the present invention range.

(3) Relief pattern formation step In this step, the unexposed part in the photosensitive resin layer after exposure is developed and removed. As a development method for developing the photosensitive resin layer after exposure (irradiation), any method can be selected from the previously known development methods of photoresist, such as rotary spray method, liquid coating method, dipping method accompanied by ultrasonic treatment, etc. And use. In addition, after development, for the purpose of adjusting the shape of the embossed pattern and other purposes, post-development baking can be performed with any combination of temperature and time as needed.

As the developer used for development, for example, a good solvent for a negative photosensitive resin composition or a combination of the good solvent and a poor solvent is preferable. As a good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, gamma -Butyrolactone, α-acetyl-γ-butyrolactone, etc. As a poor solvent, toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate, water, etc. are preferable, for example. When a good solvent and a poor solvent are mixed and used, it is preferable to adjust the ratio of the poor solvent to the good solvent based on the solubility of the polymer in the negative photosensitive resin composition. Moreover, each solvent can also be used in combination of 2 or more types, for example several types.

(4) Hardening relief pattern formation step In this step, the embossed pattern obtained by the above development is heated to disperse the photosensitive components, and (A) the polyimide precursor is imidized, thereby converting it into polyimide-containing Hardened relief pattern. As the heat curing method, various methods such as those using a hot plate, an oven, and a temperature-rising oven capable of setting a temperature program can be selected. Heating can be performed at 170°C to 400°C for 30 minutes to 5 hours, for example. As the atmosphere gas during heating and curing, air can be used, or inert gases such as nitrogen and argon can also be used.

{式中，X¹ 及Y¹ 與通式(2)中之X₁ 及Y₁ 相同，m為正整數} 通式(2)中之較佳之X₁ 及Y₁ 因相同之原因，而於通式(8)之聚醯亞胺中亦較佳。通式(8)之重複單元數m只要為正整數即可，並無特別限定，可為2～150之整數或3～140之整數。<Polyimine> The structure of the polyimine contained in the hardened relief pattern formed by the polyimine precursor composition is represented by the following general formula (8). [化33]

{In the formula, Y ₁ ^and X ¹ and Y ¹ in the general formula (2) and the X _1, m is a positive integer} general formula (2) in the same preferred because of reasons of X ₁ and Y _1, and in It is also preferable among the polyimines of general formula (8). The number m of repeating units of the general formula (8) is not particularly limited as long as it is a positive integer, and it may be an integer of 2 to 150 or an integer of 3 to 140.

In addition, the method for producing polyimide including the step of converting the negative photosensitive resin composition into polyimide described above is also an aspect of the present invention.

＜Semiconductor device＞ In this embodiment, a semiconductor device is also provided, which has a hardened relief pattern obtained by the above-mentioned hardened relief pattern manufacturing method. Therefore, it is possible to provide a semiconductor device having a substrate as a semiconductor element, and a cured relief pattern of polyimide formed on the substrate by the above-mentioned cured relief pattern manufacturing method. In addition, the present invention can also be applied to a method of manufacturing a semiconductor device that uses a semiconductor element as a base material and includes the method of manufacturing a hardened relief pattern as a part of the steps. The semiconductor device of the present invention can be manufactured by forming the hardened relief pattern formed by the above-mentioned hardened relief pattern manufacturing method into a surface protective film, an interlayer insulating film, an insulating film for rewiring, and a protection for flip chip devices A film, or a protective film for a semiconductor device having a bump structure, etc., are combined with a known manufacturing method of a semiconductor device.

＜Display device＞ In this embodiment, a display device is provided, which is provided with a display element and a cured film provided on the upper portion of the display element, and the cured film is the cured embossed pattern. Here, the hardened embossed pattern may be laminated directly in contact with the display element, or may be laminated with other layers in between. For example, as the cured film, there can be exemplified the surface protection film, insulating film, and planarizing film of thin film transistor (TFT) liquid crystal display elements and color filter elements, and multi-domain vertical alignment (MVA) type liquid crystal display devices. Use protrusions and partition walls for the cathode of organic electroluminescence (EL) elements.

In addition to being applied to semiconductor devices as described above, the negative photosensitive resin composition of the present invention is also useful for interlayer insulation of multilayer circuits, surface layers of flexible copper clad laminates, solder resist films and liquid crystal alignment films. [Example]

Hereinafter, the present embodiment will be specifically explained with examples, but the present invention is not limited to this. In the examples, comparative examples, and production examples, the physical properties of the polymer or negative photosensitive resin composition were measured and evaluated according to the following methods.

＜Measurement and evaluation method＞ (1) Weight average molecular weight The gel permeation chromatography method (standard polystyrene conversion) was used to measure the weight average molecular weight (Mw) of each resin under the following conditions. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Column: Shodex KD-806M manufactured by Showa Denko Co., Ltd. 2 in series, or Shodex 805M/806M series manufactured by Showa Denko Corporation Standard monodisperse polystyrene: Shodex STANDARD SM-105 manufactured by Showa Denko Corporation Mobile phase: 0.1 mol/L LiBr/N-methyl-2-pyrrolidone (NMP) Flow rate: 1 mL/min.

(2) The hardened embossed pattern on Cu is made on a 6-inch silicon wafer (manufactured by FUJIMI Electronics Co., Ltd., thickness 625±25 μm), using a sputtering device (L-440S-FHL type, CANON ANELVA) Made by the company), followed by sputtering Ti with a thickness of 200 nm and Cu with a thickness of 400 nm. Then, using a coating and developing machine (Model D-Spin60A, manufactured by SOKUDO), the negative photosensitive resin composition prepared by the following method was spin-coated on the wafer, and heated at 110°C. The board is pre-baked for 180 seconds to form a coating film with a thickness of about 7 μm. Using a mask with a test pattern, the coating film was irradiated with energy of 500 mJ/cm ² by Prisma GHI (manufactured by Ultratech). Next, cyclopentanone was used as a developer, and the coating film was spray-developed by a coating developer (D-Spin60A, manufactured by SOKUDO), and washed with propylene glycol methyl ether acetate, thereby obtaining a Cu surface. The embossed pattern. Using a temperature-increasing program curing furnace (VF-2000, manufactured by Koyo Lindberg), under a nitrogen atmosphere, the wafer with the embossed pattern formed on Cu was heated for 2 hours at the curing temperature described in Table 1. In this way, a hardened relief pattern containing resin with a thickness of about 4-5 μm is obtained on Cu.

(3) Evaluation of the resolution of the hardened relief pattern on Cu Observe the hardened relief pattern obtained by the above method under an optical microscope to find the size of the smallest opening pattern. At this time, if the area of the opening of the obtained pattern is more than 1/2 of the opening area of the corresponding pattern mask, it will be regarded as a resolution, and the mask with the smallest area among the resolution openings will be considered The length of the opening side is set to the resolution. Set the resolution less than 10 μm as "excellent", set the resolution greater than 10 μm and less than 14 μm as "good", set the resolution greater than 14 μm and less than 18 μm as "acceptable", and set 18 μm or more Set as "bad".

(4) The high temperature storage test of the hardened embossed pattern on Cu, and the evaluation of the void area thereafter, use a heating program curing oven (VF-2000 type, manufactured by Koyo Lindberg), in the air, The wafer with the hardened relief pattern formed on Cu was heated at 150°C for 168 hours. Then, using a plasma surface treatment device (EXAM type, manufactured by Shinko Seiki Co., Ltd.), the resin layer on the Cu was completely removed by plasma etching. The plasma etching conditions are as follows. Output: 133 W Gas type, flow rate: O ₂ : 40 mL/min + CF ₄ : 1 mL/min Air pressure: 50 Pa Mode: Hardening mode Etching time: 1800 seconds

Use FE-SEM (field emission scanning electron microscope, field emission scanning electron microscope) (S-4800, Hitachi High-Technology Co., Ltd.) to observe the Cu surface after the resin layer is completely removed, and use image analysis software (A Xiangjun, manufactured by Asahi Kasei Co., Ltd.), calculate the area of the surface of the Cu layer by the voids. When the total area of voids in the evaluation of the photosensitive resin composition described in Comparative Example 1 is set to 100%, the ratio of the total area of voids less than 50% is judged as "excellent", and 50% or more and less than 75% are judged as "good", those over 75% and less than 100% are judged as "acceptable", and those over 100% are judged as "bad".

(5) Evaluation of chemical resistance of hardened embossed pattern (polyimide coating) The hardened embossed pattern formed on Cu is immersed in the anti-corrosion stripping solution {manufactured by ATMI, product name ST-44, main components: 2-(2-aminoethoxy)ethanol and 1-cyclohexyl- 2-Pyrrolidone} was heated to 50°C for 5 minutes, washed with running water for 1 minute, and air dried. Thereafter, the film surface was visually observed with an optical microscope, and the chemical resistance was evaluated based on the presence or absence of damage caused by the chemical solution such as cracks, and/or the rate of change of the film thickness after the chemical solution treatment. As an evaluation criterion, those with no damage such as cracks and a film thickness change rate of less than 10% based on the film thickness before chemical immersion were set as "excellent", and those with 10-15% were set as "good". 15-20% is set as "acceptable", and those with cracks or film thickness change rate exceeding 20% are set as "bad".

(6) The adhesion test with the sealing material prepares R4000 series manufactured by Nagase chemteX as the epoxy-based sealing material. Then, the sealing material is spin-coated on the aluminum sputtered silicon wafer so that the thickness becomes about 150 microns, and the epoxy-based sealing material is cured by thermal curing at 130°C. On the above-mentioned epoxy-based cured film, the photosensitive resin composition produced in the examples and comparative examples was applied so that the final film thickness became 10 micrometers. After the entire surface of the coated photosensitive resin composition is exposed under 500 mJ/cm ² exposure conditions, it is thermally cured at 180° C. for 2 hours to form a first cured film with a thickness of 10 microns. The photosensitive resin composition used for forming the first layer of the cured film is coated on the first layer of the cured film, and the entire surface is exposed under the same conditions as the first layer of cured film, and then thermally cured to produce a thickness 10 micron second layer of hardened film. Epoxy resin was coated on the photosensitive resin cured film of the above sample, and then the pins were erected, and the adhesiveness test was performed using a coiling tester (manufactured by Quad Group, Sebastian Type 5). Evaluation is based on the following criteria. Evaluation: Adhesive strength 70 MPa or more: Adhesive strength is excellent 50 MPa or more and less than 70 MPa: Good adhesion is 30 MPa or more and less than 50 MPa: Acceptable adhesion is less than 30 MPa: Poor adhesion

Production Example 1: Synthesis of polymer A-1 as a precursor of (A) polyimine Put 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) into a separable flask with a volume of 2 L, add 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and γ-butane 400 mL of lactone was stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the exotherm caused by the reaction ended, the reaction mixture was cooled to room temperature and left for 16 hours. Secondly, under ice-bath cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 mL of γ-butyrolactone while stirring was added to the reaction mixture over 40 minutes, and then added to the reaction mixture. Stirring to suspend 93.0 g of 4,4'-oxydiphenylamine (ODA) in 350 mL of γ-butyrolactone and add it over 60 minutes. After further stirring for 2 hours at room temperature, 30 mL of ethanol was added, stirred for 1 hour, and then 400 mL of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction liquid.

The obtained reaction solution was added to 3 L of ethanol to generate a precipitate containing crude polymer. The produced crude polymer was separated by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 L of water to precipitate the polymer, and the obtained precipitate was separated by filtration and vacuum dried to obtain a powdery polymer (polymer A-1). The molecular weight of the polymer (A-1) was measured by gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 20,000.

Production Example 2: Synthesis of polymer A-2 as the precursor of (A) polyimine Use 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) of Production Example 1, except that The reaction was carried out in the same manner as the method described in Production Example 1 above to obtain a polymer (A-2). The molecular weight of the polymer (A-2) was measured by gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 22,000.

Production Example 3: Synthesis of polymer A-3 as a precursor of (A) polyimine Except that 50.2 g of p-phenylenediamine was used instead of 93.0 g of 4,4'-oxydiphenylamine (ODA) in Production Example 1, the reaction was carried out in the same manner as described in Production Example 1 above to obtain a polymer ( A-3). The molecular weight of the polymer (A-3) was measured by gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 19,000.

Production Example 4: Synthesis of polymer A-4 as the precursor of (A) polyimine The 4,4'-oxydiphthalic dianhydride in Production Example 1 was changed to stellate dianhydride (229.2 g), and 4,4'-oxydiphenylamine was changed to 2,2'-bis(trifluoromethyl) Except for the above, the reaction was carried out in the same manner as the method described in Production Example 1 above to obtain a polymer (A-4). The molecular weight of the polymer (A-4) was measured by gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 12,000.

Production Example 5: Synthesis of polymer A-5 as the precursor of (A) polyimine Use 98.6 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) instead of 93.0 g of 4,4'-oxydiphenylamine (ODA) in Production Example 1, except for The reaction was carried out in the same manner as the method described in Production Example 1 above to obtain a polymer (A-5). The molecular weight of the polymer (A-5) was measured by gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 21,000.

Production Example 6: (E) Synthesis of Thermal Alkali Generator E-1 Add 100 g of diethylene glycol bis(3-aminopropyl) ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 g of ethanol to a 1 L eggplant flask, and mix and stir them with a stirrer It is a homogeneous solution and is cooled to below 5°C with ice water. Dissolve 215 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) in 120 g of ethanol by dropping a dropping funnel into it. At this time, the dripping was performed while adjusting the dripping speed so that the temperature of the reaction liquid was maintained at 50°C or less. After 2 hours from the end of the dropping, the reaction solution was concentrated under reduced pressure at 50°C for 3 hours to obtain the target compound E-1.

<Example 1> Using the polymer A-1, a negative photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. (A) Polyimide precursor polymer A-1: 100 g, (B) photopolymerization initiator, 1-phenyl-1,2-propanedione-2-(O-ethyl) Oxycarbonyl)-oxime (equivalent to photopolymerization initiator B-1): 3 g dissolved in (C) KBM-403 (1.5 g), (D) organic solvent γ-butyrolactone (hereinafter referred to as GBL) ：150 g in. By further adding a small amount of GBL, the viscosity of the obtained solution was adjusted to about 30 poises to prepare a negative photosensitive resin composition. The composition was evaluated according to the above method. The results are shown in Table 1.

<Examples 2 to 13, Comparative Examples 1 to 3> Except for preparing the components and blending ratios shown in Table 1, the same negative photosensitive resin composition as in Example 1 was prepared, and the same evaluation as in Example 1 was performed. The results are shown in Table 1. The compounds described in Table 1 are as follows.

B-1: 1-Phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime C-1: 3-Glycidoxypropyl trimethoxysilane (KBM-403) C-2: N-phenyl-3-aminopropyl trimethoxysilane (KBM-573) C-3: 3-ureidopropyl triethoxysilane (KBE-585) C-4: 3-Isocyanatopropyltriethoxysilane (KBE-9007) C-5: 3-Aminopropyltrimethoxysilane (KBM-903) D-1: γ-butyrolactone (hereinafter referred to as GBL) D-2: Dimethyl sulfide (DMSO) E-1: The compound shown in Production Example 5 E-2: 1-(tertiary butoxycarbonyl)-4-hydroxypiperidine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Comparative example 1 Comparative example 2 Comparative example 3 (A) Polyimide precursor A-1 100 100 100 100 50 100 100 100 100 100 A-2 100 50 A-3 100 A-4 100 100 A-5 100 100 (B) Photopolymerization initiator B-1 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 (C) Silane coupling agent C-1 1.5 1.5 1.5 1.5 1.5 C-2 1.5 1.5 1.5 1.5 1.5 1.5 C-3 1.5 C-4 1.5 C-5 1.5 (D) Organic solvent D-1 150 150 150 150 150 150 150 150 150 150 150 120 150 150 150 150 D-2 30 (E) Thermal alkali generator E-1 1 E-2 20 Curing temperature (℃) 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 Resolution good good Acceptable Acceptable Acceptable good Acceptable good excellent good good good good bad bad bad Copper void evaluation Acceptable good good Acceptable Acceptable Acceptable Acceptable Acceptable excellent good good good good bad bad bad Chemical resistance evaluation Acceptable good good Acceptable Acceptable Acceptable Acceptable good good excellent excellent good excellent bad bad bad Evaluation of adhesion to sealing material good good good good good good Acceptable good good good good excellent good Acceptable Acceptable bad (Unit: g)

According to Table 1, it can be seen that Examples 1-13 containing the (C) silane coupling agent having the specific structure represented by the above general formula (1) and the (C) not containing the specific structure represented by the above general formula (1) Compared with Comparative Examples 1 to 3 of the silane coupling agent, higher chemical resistance and resolution were obtained. Furthermore, it is possible to suppress the generation of voids at the interface between the Cu layer and the resin layer after the high temperature storage test, and the adhesion to the sealing material is also good. [Industrial availability]

By using the negative photosensitive resin composition of the present invention, a cured embossed pattern with high chemical resistance and resolution can be obtained, and the generation of voids on the Cu surface can be suppressed. The present invention can be suitably used in the field of photosensitive materials useful for the production of electrical and electronic materials such as semiconductor devices and multilayer wiring boards, for example.

Claims (20)

A negative photosensitive resin composition comprising the following components: (A) a polyimide precursor; (B) a photopolymerization initiator; (C) a silane coupling agent, which is represented by the following general formula (1) ) Means: [化1]

{In the formula, a is an integer of 1 to 3, n is an integer of 1 to 6, R _{21 is} each independently an alkyl group with 1 to 4 carbons, R ₂₂ is a hydroxyl group or an alkyl group with 1 to 4 carbons, and , R ₂₀ is at least one selected from the group consisting of substituents including epoxy groups, phenylamino groups, urea groups and isocyanate groups}; and (D) organic solvents, which contain γ- At least one of the group consisting of butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetamide, dimethyl succinate, dimethyl malonate and ε-caprolactone. The negative photosensitive resin composition according to claim 1, wherein in the general formula (1), R ₂₀ is at least one selected from the group consisting of substituents containing a phenylamino group and a urea group. The negative photosensitive resin composition of claim 1 or 2, wherein in the general formula (1), R ₂₀ is a substituent containing a phenylamino group. The negative photosensitive resin composition according to any one of claims 1 to 3, which further contains (E) a thermal alkali generator. The negative photosensitive resin composition according to any one of claims 1 to 4, wherein the above-mentioned (D) organic solvent contains selected from the group consisting of γ-butyrolactone, dimethyl sulfenylene, tetrahydrofurfuryl alcohol, and ethyl acetylacetate , Dimethyl succinate, dimethyl malonate and ε-caprolactone at least 2 species. The negative photosensitive resin composition according to any one of claims 1 to 5, wherein the polyimide precursor (A) has a structural unit represented by the following general formula (2): [化2]

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, and R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, and, At least one of R ₁ and R ₂ is a monovalent organic group}. The negative photosensitive resin composition of claim 6, wherein in the above general formula (2), at least one of R ₁ and R ₂ is a monovalent organic group represented by the following general formula (3): [化] 3]

{In the formula, L ₁ , L ₂ and L ₃ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10}. The negative photosensitive resin composition of claim 6 or 7, wherein in the above general formula (2), X ₁ has a structure represented by the following general formula (20a): [化4]

. The negative photosensitive resin composition of claim 6 or 7, wherein in the above general formula (2), X ₁ has a structure represented by the following general formula (20b): [化5]

. The negative photosensitive resin composition of claim 6 or 7, wherein in the above general formula (2), X ₁ has a structure represented by the following general formula (20c): [化6]

. The negative photosensitive resin composition according to any one of claims 6 to 10, wherein in the above general formula (2), Y ₁ includes a structure represented by the following general formula (21b): [化7]

. The negative photosensitive resin composition according to any one of claims 6 to 10, wherein in the above general formula (2), Y ₁ includes a structure represented by the following general formula (21c): [化 8]

{In the formula, R ₆ is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group with 1 to 10 carbons, and a fluorine-containing hydrocarbon group with 1 to 10 carbons, and n is selected from 0 An integer of ~4}. The negative photosensitive resin composition of claim 6 or 7, wherein the polyimide precursor (A) has a structural unit represented by the following general formula (4): [化9]

{In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, at least one of R ₁ and R ₂ is a monovalent organic group, and n ₁ is an integer of 2 to 150}. The negative photosensitive resin composition according to claim 6 or 7, wherein the polyimide precursor (A) has a structural unit represented by the following general formula (5): [化10]

{In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, at least one of R ₁ and R ₂ is a monovalent organic group, and n ₁ is an integer of 2 to 150}. The negative photosensitive resin composition according to claim 6 or 7, wherein the polyimide precursor (A) also contains a structural unit represented by the following general formula (4): [化11]

{Wherein, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, at least one of R ₁ and R ₂ is a monovalent organic group, and n ₁ is an integer from 2 to 150}; and The structural unit represented by the general formula (5): [化12]

{In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, at least one of R ₁ and R ₂ is a monovalent organic group, and n ₁ is an integer from 2 to 150; these may They are the same as R ₁ , R ₂ and n ₁ in the general formula (4), or may be different}. The negative photosensitive resin composition according to claim 15, wherein the polyimide precursor (A) is a copolymer of structural units represented by the general formulas (4) and (5). The negative photosensitive resin composition of claim 6 or 7, wherein the polyimide precursor (A) has a structural unit represented by the following general formula (6): [化13]

{In the formula, R ₁ and R ₂ are each independently a hydrogen atom or a monovalent organic group, at least one of R ₁ and R ₂ is a monovalent organic group, and n ₁ is an integer of 2 to 150}. The negative photosensitive resin composition according to any one of claims 1 to 17, which comprises 100 parts by mass of the (A) polyimide precursor, 0.1-20 parts by mass of the above-mentioned (B) photopolymerization initiator based on 100 parts by mass of the above-mentioned (A) polyimide precursor, and 0.1-20 parts by mass of the above-mentioned (C) silane coupling agent based on 100 parts by mass of the above-mentioned (A) polyimide precursor. A manufacturing method of polyimide, which includes the step of converting the negative photosensitive resin composition according to any one of claims 1 to 18 into polyimide. A method for manufacturing hardened relief patterns, which includes the following steps: (1) Apply the negative photosensitive resin composition according to any one of claims 1 to 18 on a substrate to form a photosensitive resin layer on the substrate; (2) Expose the above-mentioned photosensitive resin layer; (3) Developing the above-mentioned photosensitive resin layer after exposure to form a relief pattern; and (4) The above-mentioned relief pattern is heated to form a hardened relief pattern.