TWI753387B - Negative photosensitive resin composition, method for producing polyimide, and method for producing hardened relief pattern - Google Patents

Abstract

{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}The present invention provides a negative photosensitive resin composition which can obtain higher chemical resistance and resolution, and can suppress the generation of voids at the interface between the Cu layer and the resin layer after a high temperature storage test. The negative photosensitive resin composition of the present invention comprises (A) a polyimide precursor, (B) a photopolymerization initiator, (C) a silane coupling agent, which is represented by the general formula (1); and (D) ) organic solvent, which contains selected from γ-butyrolactone, dimethylsulfoxide, tetrahydrofurfuryl alcohol, ethyl acetate, dimethyl succinate, dimethyl malonate and ε-caprolactone At least 1 species in the group formed.

{In the formula, a is an integer of 1-3, n is an integer of 1-6, R ₂₁ is each independently an alkyl group having 1-4 carbon atoms, R ₂₂ is a hydroxyl group or an alkyl group having 1-4 carbon atoms, and , R ₂₀ is at least one selected from the group consisting of substituents including epoxy group, phenylamine group, urea group and isocyanato group}

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 method for producing polyimide, and a method for producing a hardened relief pattern.

In the past, polyimide resins, polybenzoxazole resins, etc., which have excellent heat resistance, electrical properties, and mechanical properties, have been used as insulating materials for electronic parts, passivation films, surface protection films, and interlayer insulating films for semiconductor devices. Phenolic resin, etc. Among these resins, those provided in the form of photosensitive resin compositions can easily form heat-resistant floats by coating, exposing, developing, and curing thermal imidization of the composition. Convex pattern film. Such a photosensitive resin composition has a feature that the steps can be greatly shortened compared with the conventional non-photosensitive material.

In addition, a semiconductor device (hereinafter, also referred to as "element") is mounted on a printed circuit board by various methods depending on the purpose. Previous devices were generally fabricated by wire bonding using thin wires to connect external terminals (bonds) 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 installation wiring must be accurately controlled, and wire bonding is difficult to meet this requirement.

Therefore, flip chip mounting has been proposed in which a rewiring layer is formed on the surface of a semiconductor wafer, bumps (electrodes) are formed thereon, and the wafer is turned over and directly mounted on a printed circuit board (for example, see Patent Document 1). In this flip-chip mounting, since the wiring distance can be accurately controlled, the demand for high-end components for processing high-speed signals, or for mobile phones due to the small mounting size, is rapidly expanding. In the case of using materials such as polyimide, polybenzoxazole, and phenol resin for flip-chip mounting, after the pattern of the resin layer is formed, the metal wiring layer is formed. The metal wiring layer is usually subjected to plasma etching on the surface of the resin layer to roughen the surface, and then sputtering to a thickness of 1 μm or less to form a metal layer to be a plated seed layer, and then use the metal layer as an electrode. , formed by electroplating. At this time, titanium (Ti) is generally used as a metal for a seed layer, and copper (Cu) is used as a metal for a rewiring layer formed by electroplating.

In addition, in recent years, fan-out semiconductor packages have attracted attention. In the fan-out type semiconductor package, by covering the semiconductor chip with a sealing material (resin layer), a chip seal body larger than the chip size of the semiconductor chip is formed. Further, a rewiring layer reaching the regions of the semiconductor wafer and the sealing material is formed. The rewiring layer is formed with a relatively thin film thickness. In addition, the rewiring layer can be formed to the region of the sealing material, so that the number of external connection terminals can be increased.

This metal rewiring layer requires high adhesion between the metal layer and the resin layer to be wired after the reliability test. In particular, in recent years, the temperature for heat-hardening the rewiring layer is required to be lower. As a reliability test, for example, the following test can be exemplified: a high-temperature storage test of storing at a high temperature of 125° C. or more in the air for 100 hours or more; while assembling an assembly line and applying a voltage, it is confirmed that the temperature is about 125° C. in the air. High-temperature operation test for actions stored for more than 100 hours; temperature cycle test in which a low temperature state of about -65°C to -40°C and a high temperature state of about 125°C to 150°C are cycled back and forth in the air; temperature above 85°C High-temperature and high-humidity storage test in which the temperature is stored in a water vapor atmosphere with a humidity of 85% or more; a high-temperature and high-humidity bias voltage test, which is the same test as the high-temperature and high-humidity storage test, while assembling an assembly line and applying a voltage; and in the air Or pass the solder reflow test at 260°C for several times under nitrogen. [Prior Art Literature] [Patent Literature]

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

[Problems to be Solved by Invention]

However, conventionally, in the above-mentioned reliability test, in the case of a high-temperature storage test, there was a problem that a void was formed at the interface where the Cu layer of the rewiring and the resin layer were connected after the test. Especially when the temperature of heating and hardening is low temperature, there is a more obvious tendency. When voids are formed at the interface between the Cu layer and the resin layer, the adhesiveness between the two is lowered.

In addition to the problem of voids, chemical resistance is also required for the metal redistribution layer, and the requirement for miniaturization is also increased. Therefore, especially the photosensitive resin composition for forming the rewiring layer of a semiconductor is required to suppress the generation of voids and to exhibit high chemical resistance and resolution.

The present invention has been conceived in view of the previous practical situation, and one object of the present invention is to provide a method that can obtain higher chemical resistance and resolution, and can suppress the Cu layer and the resin after a high temperature storage test. A negative-type photosensitive resin composition (hereinafter, in this specification, it is also abbreviated as "photosensitive resin composition") which generate|occur|produces a void at the interface which a layer contact|connects. Moreover, the one objective is also to provide the formation method of the hardening relief pattern using the negative photosensitive resin composition of this invention. [Technical means to solve problems]

{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 present inventors have found that the above problems can be solved by combining a specific polyimide precursor, a silane coupling agent having 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 composed of the following general Formula (1) represents: [Formula 1]

{In the formula, a is an integer of 1-3, n is an integer of 1-6, R ₂₁ is each independently an alkyl group having 1-4 carbon atoms, R ₂₂ is a hydroxyl group or an alkyl group having 1-4 carbon atoms, and , R ₂₀ is at least one selected from the group consisting of substituents comprising epoxy, phenylamine, urea and isocyanato groups}; and (D) an organic solvent containing a compound selected from γ- At least one kind selected from the group consisting of butyrolactone, dimethylsulfoxide, tetrahydrofurfuryl alcohol, ethyl acetate, dimethyl succinate, dimethyl malonate and ε-caprolactone. [2] The negative photosensitive resin composition according to [1], wherein in the general formula (1), R ₂₀ is selected from the group consisting of substituents including a phenylamine group and a ureido group At least 1 species. [3] The negative photosensitive resin composition according to [1] or [2], wherein in the general formula (1), R ₂₀ is a substituent containing a phenylamino group. [4] The negative photosensitive resin composition according to any one of [1] to [3], further comprising (E) a thermal base generator. [5] The negative photosensitive resin composition according to any one of [1] to [4], wherein the (D) organic solvent contains a compound selected from the group consisting of γ-butyrolactone, dimethylsulfoxide, tetrahydro At least two kinds selected from the group consisting of furfuryl alcohol, ethyl acetate, dimethyl succinate, dimethyl malonate and ε-caprolactone. [6] The negative photosensitive resin composition according to any one of [1] to [5], wherein the (A) polyimide precursor has a structural unit represented by the following general formula (2) : [Change 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 according to [6], wherein in the general formula (2), at least one of R ₁ and R ₂ is a valence represented by the following general formula (3) Organic base: [Chemical 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 according to [6] or [7], wherein in the above general formula (2), X ₁ has a structure represented by the following general formula (20a): ]

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

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

. [11] The negative photosensitive resin composition according to 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) : [Chemical 7]

. [12] The negative photosensitive resin composition according to 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) : [hua 8]

{In the formula, R ₆ is a valent group selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and n is selected from 0 an integer of ~4}. [13] The negative photosensitive resin composition according to [6] or [7], wherein the (A) polyimide precursor has a structural unit represented by the following general formula (4): ]

{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 according to [6] or [7], wherein the (A) polyimide precursor has a structural unit represented by the following general formula (5): ]

{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 according to [6] or [7], wherein the (A) polyimide precursor simultaneously contains a structural unit represented by the following general formula (4): 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 of 2 to 150}; and the following The structural unit represented by the general formula (5): [Chemical 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 2-150. 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 the structural units represented by the general formulae (4) and (5). [17] The negative photosensitive resin composition according to [6] or [7], wherein the (A) polyimide precursor has a structural unit represented by the following general formula (6): ]

{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 according to any one of [1] to [17], comprising 100 parts by mass of the above-mentioned (A) polyimide precursor, the above-mentioned (A) polyimide precursor 0.1-20 parts by mass of the above-mentioned (B) photopolymerization initiator based on 100 parts by mass of the imine precursor, and 0.1-20 parts by mass based on 100 parts by mass of the above-mentioned (A) polyimide precursor The above-mentioned (C) silane coupling agent. [19] A method for producing polyimide, comprising the step of converting the negative photosensitive resin composition as described in any one of [1] to [18] into polyimide. [20] A method for producing a hardened relief pattern, comprising 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) exposing the relief pattern A heat treatment is performed to form a hardened relief pattern. [Effect 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 the formation method of the hardening relief pattern using this negative photosensitive resin composition can be provided.

Hereinafter, an embodiment for implementing the present invention (hereinafter, simply referred to as an "embodiment") will be described in detail. In addition, this invention is not limited to the following embodiment, Various changes can be carried out within the range of the summary. In addition, according to this specification, the structures represented by the same symbol in the general formula may be the same or different from each other when there is a plurality of structures in the molecule.

<Negative photosensitive resin composition> The negative photosensitive resin composition of this embodiment includes the following components: (A) polyimide precursor; (B) photopolymerization initiator; (C) a silane coupling agent having a specific structure; and (D) A specific organic solvent.

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 0.1-20 parts by mass of (B) photopolymerization initiator and 0.1-20 parts by mass of (A) 100 parts by mass of polyimide precursor as a reference (C) silane coupler having 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) polyimide precursor in this embodiment is a resin component contained in the negative photosensitive resin composition, and is converted into a polymer by thermal cyclization treatment imide. The polyimide precursor is preferably a polyimide having a structural unit represented by the following general formula (2): [Chem. 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):

{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}.

In general formula (2), n ₁ is not limited as long as it is an integer of 2 to 150, but 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 5-70.

{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 simultaneously achieving heat resistance and photosensitivity, the tetravalent organic group represented by X ₁ in the general formula (2) is preferably an organic group having 6 to 40 carbon atoms, more preferably a -COOR ₁ group and -COOR An aromatic group or an alicyclic aliphatic group in which the ₂ group and the -CONH- group are in ortho positions to each other. As the tetravalent organic group represented by X ₁ , specifically, an organic group containing an aromatic ring and having a carbon number of 6 to 40 can be mentioned, for example, a group having a structure represented by the following general formula (20) can be exemplified. basis, but not limited to: [Chem. 16]

{In the formula, R ₆ is a valent group selected from the group consisting of hydrogen atoms, fluorine atoms, hydrocarbon groups with 1-10 carbon atoms, and fluorine-containing hydrocarbon groups with 1-10 carbon atoms, and l is selected from 0-2 The integer of , m is an integer selected from 0-3, and n is an integer selected from 0-4}. 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 photosensitivity.

[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), from the viewpoints of chemical resistance, resolution, and void suppression after a high-temperature storage test, the following formulae (20A) and (20B) are more preferable. ) or the structure represented by (20C): [Chemical 17]

[Chemical 18]

[Chemical 19]

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

[Chemical 21]

[Chemical 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 heat resistance and photosensitivity at the same time, 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 structures represented, but not limited to these: [化23]

{In the formula, R ₆ is a valent group selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and n is selected from 0 an integer of ~4}. In addition, the structure of Y ₁ may be 1 type or a combination of 2 or more types may be sufficient as it. The Y ₁ group having the structure represented by the above formula (21) is preferable from the viewpoint of achieving both heat resistance and photosensitivity.

[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 formulae (21A) and (21B) are preferred ) or the structure represented by (21C): [Chemical 24]

[Chemical 25]

[Chemical 26]

, preferably a structure represented by the following formula (21b) or (21c):

[Chemical 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 a hydrogen atom. Moreover, 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, from the viewpoint of photosensitive characteristics.

{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) polyimide precursor is preferably a polyimide precursor having a structural unit represented by the following general formula (4): [Chem. 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 valent organic group represented by the above-mentioned general formula (3). When the polyimide precursor represented by the general formula (4) is contained in the (A) polyimide precursor, the resolution effect becomes high in particular.

{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) polyimide precursor is preferably a polyimide precursor having a structural unit represented by the following general formula (5): [Chemical 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 valent organic group represented by the above-mentioned 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. effect becomes higher.

Among these, from the viewpoints of chemical resistance, resolution, and void suppression after a high-temperature storage test, it is particularly preferable that the (A) polyimide precursor contains both the above-mentioned general formulae (4) and (5) The represented structural unit, or a copolymer of the structural units represented by the general formulae (4) and (5). When the (A) polyimide precursor is a copolymer of the structural units represented by the general formulae (4) and (5), R ₁ , R ₂ and n ₁ in one formula can be respectively combined with 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) polyimide precursor is preferably a polyimide precursor having a structural unit represented by the following general formula (6):

{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 valent organic group represented by the above-mentioned general formula (3). When (A) the polyimide precursor contains the polyimide precursor represented by the general formula (6), the effect of especially chemical resistance becomes high.

(A) Preparation method of polyimide precursor (A) The polyimide precursor is obtained by the following method: _First , the tetracarboxylic acid containing the tetravalent organic group X in the above general formula (2) is made Dianhydride reacts with alcohols having photopolymerizable unsaturated double bonds and alcohols without any unsaturated double bonds to prepare partially esterified tetracarboxylic acids (hereinafter, also referred to as acid/ester bodies), and then make It is subjected to amide polycondensation with diamines containing the divalent organic group Y ₁ in the above-mentioned general formula (2).

(Preparation of acid/ester body) In this embodiment, as a tetracarboxylic dianhydride containing a tetravalent organic group X ₁ , which can be preferably used for preparing the (A) polyimide precursor, it has the above-mentioned general The tetracarboxylic dianhydride of the structure represented by the formula (20) is represented, for example, pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, diphenyl ether Methanone-3,3',4,4'-tetracarboxylic dianhydride, Biphenyl-3,3',4,4'-tetracarboxylic dianhydride, Diphenyl-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 Carboxylic dianhydride is not limited to these. Moreover, of course, these may be used individually, and may mix and use 2 or more types.

In this embodiment, as alcohols having photopolymerizable unsaturated double bonds that can be preferably used for preparing the (A) polyimide precursor, for example, 2-propenyloxyethanol, 1 - Acryloyloxy-3-propanol, 2-acrylamidoethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2- Hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-tert-butoxypropyl acrylate , 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethanol, 1-methacryloyloxy-3-propanol, 2-methacrylamidoethanol, methylol Ethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy methacrylate -3-Phenoxypropyl, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, 2-hydroxy-3-methacrylate Cyclohexyloxypropyl ester, etc.

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, 3-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 and a photosensitive polyimide precursor prepared only from the above-mentioned alcohols not having an unsaturated double bond may be mixed and used. . From the viewpoint of resolution, the non-photosensitive polyimide precursor is preferably 200 parts by mass or less based on 100 parts by mass of the photosensitive polyimide precursor.

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

(Preparation of Polyimide Precursor) In the above acid/ester body (typically a solution in the following solvent), add a suitable dehydration condensing agent, such as dicyclohexylcarbodiimide, under ice cooling , 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'- Dibutadiimide carbonate, etc., are mixed to form an acid/ester body into a polyacid anhydride, and then added dropwise to it, the divalent organic group Y ₁ bis that can be preferably used in this embodiment The amines are separately dissolved or dispersed in a solvent, and polyimide polycondensation is carried out, whereby the target polyimide precursor can be obtained. Alternatively, after chlorinating the acid moiety with thionine chloride or the like, in the presence of a base such as pyridine, the above acid/ester body can be reacted with a diamine compound, thereby obtaining the target polyimide precursor .

The diamines containing the divalent organic group Y ₁ that can be preferably used in this embodiment are represented by diamines having a structure represented by the above general formula (21), 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 bismuth, 3,3'-diaminodiphenyl bismuth, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl 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] bismuth, 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)propane 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, di-o-toluidine, 9,9-bis(4-aminophenyl)benzene, and the A part of the hydrogen atoms on the benzene ring, such as benzene, 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 thereof, etc., but not limited thereto.

After the amide polycondensation reaction is completed, if necessary, the water-absorbing by-product of the dehydration condensing agent coexisting in the reaction solution is filtered and separated, and a poor solvent such as water, aliphatic lower alcohol, or a mixed solution of these is added to the obtained polymerization. The polymer components are separated out, and further, redissolving, reprecipitation and precipitation operations are repeated, whereby the polymer is purified and vacuum-dried to isolate the target polyimide precursor. To improve the degree of refinement, the polymer solution can be passed through a column packed with anion and/or cation exchange resin swelled with a suitable organic solvent to remove ionic impurities.

When measured by the polystyrene conversion weight average molecular weight by gel permeation chromatography, the molecular weight of the said (A) polyimide precursor becomes like this. Preferably it is 8,000-150,000, More preferably, it is 9,000-50,000. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, and when the weight average molecular weight is 150,000 or less, the dispersibility in the developing solution is good, and the resolution of the relief pattern is good. As developing solvents for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. In addition, the weight average molecular weight was calculated|required from the calibration curve produced using the standard monodisperse polystyrene. As a standard monodisperse polystyrene, it is recommended to select from the organic solvent-based standard sample STANDARD SM-105 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 the present embodiment will be described. The photopolymerization initiator is preferably a photoradical polymerization initiator, and examples include benzophenone, methyl o-benzoic acid benzoate, and 4-benzyl-4'-methyl. Benzophenone derivatives such as benzophenone, dibenzyl ketone, and fenone; 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl Acetophenone derivatives such as phenyl ketone; 9-oxosulfur

, 2-methyl 9-oxothio

, 2-isopropyl 9-oxothio

, diethyl 9-oxothio

Wait for 9-oxysulfur 𠮿

Derivatives; benzil derivatives such as benzil, benzil dimethyl ketal, benzil-β-methoxyethyl acetal, etc.; 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 Oximes such as triketo-2-(o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxyglycerol-2-(o-benzyl) oxime; N-phenylglycine, etc. N-arylglycines; peroxides such as benzalkonium chloride; aromatic biimidazoles; titanocenes; α-(n-octanesulfonyloxyimino)-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 the (B) photopolymerization initiator in the negative photosensitive resin composition is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 100 parts by mass of the (A) polyimide precursor. 1 mass part or more and 8 mass parts or less. The said compounding quantity is 0.1 mass part or more from the viewpoint of photosensitivity or patternability, and 20 mass parts or less from the viewpoint of the physical properties of the photosensitive resin layer after hardening 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 which has a specific structure The silane coupling agent which has a specific structure (C) used in this embodiment is demonstrated. (C) The silane coupling agent which has a specific structure which concerns on this embodiment has the structure represented by following general formula (1). [Chemical 32]

{In the formula, a is an integer of 1-3, n is an integer of 1-6, R ₂₁ is each independently an alkyl group having 1-4 carbon atoms, R ₂₂ is a hydroxyl group or an alkyl group having 1-4 carbon atoms, and , R ₂₀ is at least one selected from the group consisting of substituents including epoxy group, phenylamine group and urea group} In general formula (1), a can be an integer from 1 to 3, Although not limited, 2 or 3 are preferable, and 3 is more preferable from the viewpoint of the adhesiveness with the metal rewiring layer. n is not limited as long as it is an integer of 1 to 6, but it is preferably 1 or more and 4 or less from the viewpoint of the adhesiveness with 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. A methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, etc. can be illustrated. 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 alkyl group having 1 to 4 carbon atoms, the same alkyl group as that of R ₂₁ can be exemplified. R ₂₀ is not limited as long as it is a substituent including an epoxy group, a phenylamino group, a urea group, and an isocyanato group. Among these, at least one selected from the group consisting of a substituent containing a phenylamino group and a substituent containing a urea group is preferred from the viewpoint of developability or adhesiveness of the metal redistribution layer. species, more preferably a substituent containing a phenylamino group. As an epoxy group-containing silane coupling agent, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3- Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. As a phenylamino group-containing silane coupling agent, N-phenyl-3-aminopropyltrimethoxysilane can be exemplified. As a urea group-containing silane coupling agent, 3-ureidopropyltrialkoxysilane can be exemplified. As an isocyanato group-containing silane coupling agent, 3-isocyanatopropyltriethoxysilane can be exemplified.

(D) Organic solvent with specific structure As long as the organic solvent of this embodiment contains γ-butyrolactone, dimethylsulfoxide, tetrahydrofurfuryl alcohol, ethyl acetate, dimethyl succinate, dimethyl malonate and ε-caprolactone At least one of the group consisting of esters may be used, and is not limited. By including the above-mentioned organic solvent, the adhesiveness with the sealing material can be sufficiently expressed. Among them, from the viewpoint of the solubility of the (A) polyimide precursor, γ-butyrolactone, dimethylsulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, and ε-caprolactone are preferred , from the viewpoint of suppressing voids on the copper surface, it is more preferable to contain at least two kinds of organic solvents selected from the above-mentioned groups.

Although the reason why the adhesiveness between the organic solvent having the specific structure of the present embodiment and the sealing material is good is uncertain, the present inventors estimate as follows. Previously, as the organic solvent for dissolving the photosensitive resin composition containing the polyimide precursor, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylacetone were used. Carboxamide-based solvents such as carboxamide. Although these solvents have extremely high dissolving ability of polyimide precursors, when the required heating and hardening temperature in recent years is low (for example, less than 200°C), due to the affinity with the generated polyimide The tendency to remain high and large in the membrane. Therefore, the performance is lowered due to the interaction with the silane coupling agent having a specific structure (C) above. On the other hand, by including the above-mentioned solvent, even if the heat-hardening temperature is low, the solvent remaining in the film after heat-hardening can be sufficiently reduced, so that the adhesiveness with the sealing material tends 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 (A) polyimide precursor. parts, more preferably in the range of 125 to 500 parts by mass.

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

The type of the thermal base generator is not particularly limited, and examples thereof include an amine compound protected by a tertiary butoxycarbonyl group, the thermal base generator disclosed in International Publication No. WO 2017/038598, and the like. 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 third butoxycarbonyl group, ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-propanol, 4 -Amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amine Alkyl-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-pyrrolidinol, 2-pyrrolidinol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-Hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 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-aminopropane) group) ether, 1,11-diamino-3,6,9-trioxaundecane, or a compound that protects the amine group of an amino acid and its derivatives by a tertiary butoxycarbonyl group, but does not limited to these.

The blending amount of the (E) thermal base generator is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the (A) polyimide precursor. The above-mentioned compounding amount is preferably 0.1 part by mass or more from the viewpoint of the imidization promoting effect, 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 this embodiment may further contain components other than the above-mentioned (A) to (E) components. The components other than the components (A) to (E) are not limited, and examples thereof include nitrogen-containing heterocyclic compounds, hindered phenol compounds, organic titanium compounds, sensitizers, photopolymerizable unsaturated monomers, and thermal polymerization inhibitors. agent, etc.

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

As the azole compound, 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-diazole 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-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxyl -5'-Third-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolutriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole 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 preferable examples include tolutriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. In addition, these azole compounds may be used 1 type, and may be used as a mixture of 2 or more types.

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-aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyl adenine, 6-ethylaminopurine, 1-benzyladenine, 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 (A) polyimide precursor. From a viewpoint, it is more preferably 0.5 to 5 parts by mass. When the compounding amount of the azole compound with respect to 100 parts by mass of the polyimide precursor (A) is 0.1 part by mass or more, the case where the negative photosensitive resin composition of the present embodiment is formed on copper or a copper alloy When it is, the discoloration of the copper or copper alloy surface is suppressed, and on the other hand, when it is 20 mass parts or less, it is excellent in photosensitivity.

<Hindered phenolic compound> Moreover, in order to suppress discoloration on the copper surface, the negative photosensitive resin composition may optionally contain a hindered phenol compound. As the hindered phenol compound, 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, 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-dieneethylbis [3-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4- Hydroxy-phenylpropanamide), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6 - tert-butylphenol), pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-tert-butyl) yl-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𠯤-2,4, 6-(1H,3H,5H)-trione, 1,3,5-tris(4-second-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris 𠯤-2,4,6-(1H,3H,5H)-trione, 1,3,5-tri[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl base]-1,3,5-tris𠯤-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2 ,6-Dimethylbenzyl]-1,3,5-tris𠯤-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)-trione, 1,3,5-tris(4- tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-tri𠯤-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-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3 ,5-Tris𠯤-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5 -Dimethylbenzyl)-1,3,5-tri(2,4,6-(1H,3H,5H)-trione, 1,3,5-tri(4-tert-butyl-5) ,6-Diethyl-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-methylbenzyl)-1,3,5-tris𠯤-2,4,6-(1H,3H,5H)-trione, 1, 3,5-Tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris𠯤-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 thereto. Among them, especially preferred is 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris𠯤-2,4 , 6-(1H,3H,5H)-triketone, etc.

The blending amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the (A) polyimide precursor. When the blending amount of the hindered phenol compound with respect to 100 parts by mass of the polyimide precursor (A) is 0.1 part by mass or more, for example, the negative photosensitive resin composition of the present embodiment is formed on copper or a copper alloy. In this case, discoloration and corrosion of copper or copper alloy are prevented, and on the other hand, in the case of 20 parts by mass or less, the photosensitivity is excellent.

＜Organo-titanium compound＞ The negative photosensitive resin composition of this embodiment may contain an organic titanium compound. By containing an organic titanium compound, even in the case of hardening at a low temperature, a photosensitive resin layer excellent in chemical resistance can be formed.

As the organotitanium compound that can be used, an organic chemical substance bonded to a titanium atom via a covalent bond or an ionic bond can be exemplified. Specific examples of organotitanium compounds are shown in the following I) to VII): I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable in that the storage stability of the negative photosensitive resin composition and a favorable pattern can be obtained. Specific examples are: titanium bis(triethanolamine) diisopropoxide, titanium bis(2,4-glutaric acid) di(n-butoxide), titanium bis(2,4-glutaric acid) diisopropoxide, bis(2,4-glutaric acid) titanium (Tetramethylpimelate) titanium diisopropoxide, bis(ethylacetate) titanium diisopropoxide, etc.

II) Titanium tetraalkoxide compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetrakis(2-ethylhexanoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, Titanium tetramethoxypropoxide, titanium tetramethylphenolate, titanium tetrakis (n-nonoxide), titanium tetrakis (n-propoxide), titanium tetrastearyloxide, tetrakis[bis{2,2-(allyloxymethyl) base) butanol}] titanium and so on.

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) Monoalkoxytitanium compounds: for example, titanium tris(dioctylphosphoric acid) isopropoxide, tris(dodecylbenzenesulfonic acid) titanium isopropoxide, and the like.

V) Oxytitanium compounds: for example, bis(glutaric acid) oxytitanium, bis(tetramethylpimelate) oxytitanium, phthalocyanine oxytitanium, and the like. VI) Titanium tetraacetylacetonate compound: for example, titanium tetraacetylacetonate and the like. VII) Titanate coupling agent: for example, isopropyl tris(dodecylbenzenesulfonyl) titanate and the like.

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

When the organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, with respect to 100 parts by mass of the (A) polyimide precursor. When this compounding quantity is 0.05 mass part or more, favorable heat resistance and chemical resistance are exhibited, and on the other hand, when it is 10 mass parts or less, it is excellent in storage stability.

＜Sensitizer＞ The negative photosensitive resin composition of the present embodiment may optionally contain a sensitizer in order to improve the photosensitivity. As the sensitizer, for example, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene) may be mentioned. 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-dimethylaminocinnamic dihydrogen Indanone, p-dimethylaminobenzylidene dihydroindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylidene) ) benzothiazole, 2-(p-dimethylaminophenylvinylidene)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olinyl benzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl- 5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2- (p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, and the like. These can be used alone or in combination of, for example, 2 to 5 types.

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

<Photopolymerizable unsaturated monomer> The negative photosensitive resin composition may optionally contain a monomer having a photopolymerizable unsaturated bond in order to improve the resolution of the relief pattern. As such a monomer, a (meth)acrylic compound which undergoes a radical polymerization reaction with a photopolymerization initiator is preferable, and examples thereof include diethylene glycol dimethacrylate, tetraethylene glycol dimethyl acrylate. Mono- or di-acrylates and methacrylates of ethylene glycol or polyethylene glycol such as base acrylates; mono- or di-acrylates and methacrylates of propylene glycol or polypropylene glycol; mono-, di- or triacrylates of glycerol and Methacrylate; Cyclohexane Diacrylate and Dimethacrylate; Diacrylate and Dimethacrylate of 1,4-Butanediol; Diacrylate and Dimethacrylate of 1,6-Hexanediol Diacrylates and Dimethacrylates of Neopentyl Glycol; Mono- or Diacrylates and Methacrylates of Bisphenol A; Isopropyl esters; acrylamide and its derivatives; methacrylamide and its derivatives; trimethylolpropane triacrylate and methacrylate; glycerol di- or triacrylates and methacrylates; Di-, tri- or tetra-acrylates and methacrylates 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 improving the resolution of the relief pattern, the compounding amount of the monomer having a photopolymerizable unsaturated bond is relative to (A ) 100 parts by mass of the polyimide precursor, preferably 1 to 50 parts by mass.

<Thermal polymerization inhibitor> In addition, the negative photosensitive resin composition of the present embodiment may optionally contain a thermal polymerization inhibitor in order to enhance the stability of the viscosity and photosensitivity of the negative photosensitive resin composition when stored in a state containing a solvent in particular. agent. As the thermal polymerization inhibitor, for example, hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1 ,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-cresol, 5-nitroso-8-hydroxyquinoline, 1-nitroso yl-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N- Phenylhydroxylamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, etc.

<Manufacturing method of hardened relief pattern and semiconductor device> In addition, the present invention provides a method for producing a hardened relief pattern, which includes the following steps: (1) coating the negative photosensitive resin composition of the present embodiment on a substrate, and 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) subjecting the relief pattern to heat treatment to form a hardened relief pattern .

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

The coating film containing the negative photosensitive resin composition can be dried as needed. As the drying method, methods such as air drying, heating drying by an oven or a hot plate, and vacuum drying can be used. Specifically, in the case of air-drying or heat-drying, drying can be carried out at 20° C. to 140° C. under the conditions of 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, exposure devices such as contact aligners, mirror projection aligners, steppers, etc. are used, and the negative-type formed above is irradiated through a patterned mask or a reticle or directly by an ultraviolet light source, etc. The photosensitive resin layer is exposed.

Thereafter, for the purpose of improving the photosensitivity, the post-exposure bake (PEB) and/or the 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 40°C to 120°C, and the time is 10 seconds to 240 seconds. However, as long as the properties of the negative-type photosensitive resin composition of the present invention are not inhibited, it is not limited to this range. Scope.

(3) Embossed pattern forming step In this step, the unexposed portion in the exposed photosensitive resin layer is developed and removed. As a development method for developing the photosensitive resin layer after exposure (irradiation), any method can be selected from the development methods of photoresist known in the past, such as spin spray method, liquid coating method, immersion method with ultrasonic treatment, etc. and use. Moreover, after development, for the purpose of adjusting the shape of the relief pattern, etc., the post-development baking can be performed by any combination of temperature and time as needed.

As a developer used for development, for example, a good solvent for the 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, γ -Butyrolactone, α-Acetyl-γ-Butyrolactone, etc. As a poor solvent, for example, toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate, water, etc. are preferable. When a good solvent and a poor solvent are used in combination, it is preferable to adjust the ratio of the poor solvent to the good solvent in consideration of the solubility of the polymer in the negative photosensitive resin composition. Moreover, you may use each solvent in combination of 2 or more types, for example, several types.

(4) Hardening relief pattern forming step In this step, the embossed pattern obtained by the above-mentioned development is heated to disperse the photosensitive components, and (A) the polyimide precursor is imidized, thereby converting into a polyimide-containing compound. Hardened embossed pattern. As a heat-hardening method, various methods, such as those using a hot plate, those using an oven, and those using a temperature-programmable temperature-raising type oven, can be selected, for example. Heating can be performed, for example, at 170°C to 400°C for 30 minutes to 5 hours. As the atmospheric gas at the time of heat-hardening, air can be used, and inert gas, such as nitrogen gas and argon gas, 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。<Polyimide> The structure of the polyimide contained in the cured relief pattern formed from the above-mentioned polyimide precursor composition is represented by the following general formula (8). [Chemical 33]

{In the formula, X ¹ and Y ¹ are the same as X ₁ and Y ₁ in the general formula (2), and m is a positive integer} The preferred X ₁ and Y ₁ in the general formula (2) are for the same reason, and are in Among the polyimides of the general formula (8) are also preferred. The repeating unit number m of the general formula (8) is not particularly limited as long as it is a positive integer, and may be an integer of 2 to 150 or an integer of 3 to 140.

Moreover, the manufacturing method of the polyimide including the step of converting the negative photosensitive resin composition into the polyimide described above is also an aspect of the present invention.

<Semiconductor device> This embodiment also provides a semiconductor device having a hardened relief pattern obtained by the above-described method for producing a hardened relief pattern. Therefore, it is possible to provide a semiconductor device having a substrate serving as a semiconductor element, and a cured relief pattern of polyimide formed on the substrate by the above-described method for producing a cured relief pattern. In addition, the present invention can also be applied to a method of manufacturing a semiconductor device using a semiconductor element as a base material and including the method of manufacturing the above-described 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-described hardened relief pattern manufacturing method into a surface protection 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, there is provided a display device including a display element and a cured film provided on the upper part of the display element, and the cured film is the cured relief pattern described above. Here, the hardened relief pattern can be directly connected to the display element and laminated, or can be laminated with other layers in between. For example, as this cured film, a thin film transistor (TFT) liquid crystal display element and a surface protection film of a color filter element, an insulating film, a planarizing film, and a multi-domain vertical alignment (MVA) type liquid crystal display device can be mentioned. Use protrusions and spacers for cathodes of organic electroluminescence (EL) elements.

The negative photosensitive resin composition of the present invention is useful not only for semiconductor devices as described above, but also 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 described by way of examples, but the present invention is not limited thereto. In Examples, Comparative Examples, and Production Examples, the physical properties of the polymer or the negative photosensitive resin composition were measured and evaluated according to the following methods.

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

(2) The hardened relief pattern on Cu was fabricated on a 6-inch silicon wafer (manufactured by FUJIMI Electronics Industry Co., Ltd., thickness 625±25 μm), using a sputtering device (L-440S-FHL type, CANON ANELVA Company), and sequentially sputtered Ti with a thickness of 200 nm and Cu with a thickness of 400 nm. Then, using a coating developer (D-Spin60A type, 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 was pre-baked for 180 seconds to form a coating film with a thickness of about 7 μm. Using the mask with the test pattern, the coating film was irradiated with an energy of 500 mJ/cm ² by Prisma GHI (manufactured by Ultratech). Next, using cyclopentanone as a developing solution, the coating film was spray developed by a coating developer (D-Spin60A type, manufactured by SOKUDO), and rinsed by propylene glycol methyl ether acetate, thereby obtaining a Cu coating. The embossed pattern. Using a heating program curing furnace (Model VF-2000, manufactured by Koyo Lindberg Co., Ltd.), under a nitrogen atmosphere, the wafer with the relief pattern formed on the Cu was heated at the curing temperature recorded in Table 1 for 2 hours. This results in a hardened relief pattern containing resin with a thickness of about 4-5 μm on Cu.

(3) Evaluation of resolution of hardened relief pattern on Cu The hardened relief pattern obtained by the above method was observed under an optical microscope, and the size of the smallest opening pattern was obtained. At this time, if the area of the opening part of the obtained pattern is more than 1/2 of the opening area of the corresponding pattern mask, it is regarded as a solution, and the mask corresponding to the opening part of the solution with the smallest area will be The length of the opening edge is set as the resolution. Resolutions below 10 μm were set as “Excellent”, those above 10 μm and below 14 μm were set as “Good”, those above 14 μm and below 18 μm were set as “Acceptable”, and those above 18 μm were set as “Acceptable” set as "bad".

(4) High temperature storage test of hardened relief pattern on Cu, and evaluation of void area after that. Using a heating program curing furnace (Model VF-2000, manufactured by Koyo Lindberg Co., Ltd.), in the air, The wafer with the hardened relief pattern formed on the Cu was heated at 150° C. for 168 hours. Then, using a plasma surface treatment apparatus (EXAM type, manufactured by Shinko Seiki Co., Ltd.), all the resin layers on the Cu were 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

The Cu surface after the resin layer was completely removed was observed by FE-SEM (field emission scanning electron microscope) (Model S-4800, manufactured by Hitachi High-Tech Co., Ltd.), and image analysis software (A Like Jun, manufactured by Asahi Kasei Co., Ltd.), the area of the surface of the Cu layer occupied by the voids was calculated. When the total area of the voids in the evaluation of the photosensitive resin composition described in Comparative Example 1 was taken as 100%, those with a total area ratio of voids less than 50% were judged as "excellent", and those with a total area ratio of 50% or more and less than 50% were judged as "excellent". 75% were judged as "good", those with more than 75% and less than 100% were judged as "acceptable", and those with more than 100% were judged as "bad".

(5) Chemical resistance evaluation of hardened relief pattern (polyimide coating film) The hardened relief pattern formed on Cu was immersed in a resist stripping solution {made 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. Then, 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 change rate of the film thickness after the chemical solution treatment. As the evaluation criteria, those with no damage such as cracks and the film thickness change rate being within 10% of the film thickness before chemical immersion as a standard were regarded as "excellent", those with 10 to 15% were regarded as "good", and Those with 15 to 20% were set as "acceptable", and those with cracks or the film thickness change rate exceeding 20% were set as "defective".

(6) Adhesion test with sealing material R4000 series manufactured by Nagase ChemteX was prepared as an epoxy-based sealing material. Next, the sealing material was spin-coated on the silicon wafer by aluminum sputtering so as to have a thickness of about 150 microns, and the epoxy-based sealing material was cured by thermal curing at 130°C. On the said epoxy-type cured film, the photosensitive resin composition produced in an Example and a comparative example was apply|coated so that a final film thickness might become 10 micrometers. The coated photosensitive resin composition was exposed to the entire surface under the exposure condition of 500 mJ/cm ² , and then thermally cured at 180° C. for 2 hours to prepare a first-layer cured film with a thickness of 10 μm. The photosensitive resin composition used for the formation of the first layer of cured film was coated on the cured film of the first layer, and the entire surface was exposed to light under the same conditions as in the production of the first layer of cured film, and then thermally cured to produce a thickness of 10 micron second layer of cured film. The epoxy resin was apply|coated to the photosensitive resin cured film of the said sample, the pin was then erected, and the adhesiveness test was performed using the coil tester (Quad Group company make, Sebastian 5 type). Evaluation was performed according to the following criteria. Evaluation: Adhesion strength 70 MPa or more: Adhesion strength is excellent 50 MPa or more and less than 70 MPa: Adhesive strength is good 30 MPa or more and less than 50 MPa: Adhesive strength is acceptable, less than 30 MPa: Adhesion strength is poor

Production Example 1: Synthesis of Polymer A-1 as (A) Polyimide Precursor Put 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) into a separable flask with a volume of 2 L, and add 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and γ-butylene 400 mL of lactone was stirred at room temperature, and while stirring, 81.5 g of pyridine was added 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. Next, under ice-cooling, a solution obtained by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 mL of γ-butyrolactone was added to the reaction mixture for 40 minutes while stirring. It was added over 60 minutes while stirring to suspend 93.0 g of 4,4'-oxydianiline (ODA) in 350 mL of γ-butyrolactone. Furthermore, after stirring at room temperature for 2 hours, 30 mL of ethanol was added, followed by stirring for 1 hour, and then, 400 mL of γ-butyrolactone was added. The resulting precipitate in the reaction mixture was removed by filtration to obtain a reaction solution.

The obtained reaction solution was added to 3 L of ethanol to form a precipitate containing crude polymer. The resulting 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 a polymer, and the obtained precipitate was separated by filtration, and then 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), and as a result, the weight average molecular weight (Mw) was 20,000.

Production Example 2: Synthesis of Polymer A-2 as (A) Polyimide Precursor Except that 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 1 , and reacted 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), and as a result, the weight average molecular weight (Mw) was 22,000.

Production Example 3: Synthesis of Polymer A-3 as (A) Polyimide Precursor A polymer ( A-3). The molecular weight of the polymer (A-3) was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, the weight average molecular weight (Mw) was 19,000.

Production Example 4: Synthesis of Polymer A-4 as (A) Polyimide Precursor The 4,4'-oxydiphthalic dianhydride of Production Example 1 was changed to perylene dianhydride (229.2 g), and the 4,4'-oxydianiline was changed to 2,2'-bis(trifluoromethyl) A polymer (A-4) was obtained by reacting in the same manner as in the method described in the above-mentioned Production Example 1, except for the addition of phenyl)benzidine (TFMB) (148.5 g). The molecular weight of the polymer (A-4) was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, the weight average molecular weight (Mw) was 12,000.

Production Example 5: Synthesis of Polymer A-5 as (A) Polyimide Precursor In addition to using 98.6 g of 2,2'-dimethylbiphenyl-4,4'-diamine (m-TB) in place of 93.0 g of 4,4'-oxydiphenylamine (ODA) in Production Example 1, use The reaction was carried out in the same manner as the method described in the above-mentioned Production Example 1 to obtain a polymer (A-5). The molecular weight of the polymer (A-5) was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, the weight average molecular weight (Mw) was 21,000.

Production Example 6: (E) Synthesis of Thermal Alkali Generator E-1 100 g of diethylene glycol bis(3-aminopropyl) ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 g of ethanol were added to an eggplant-shaped flask with a volume of 1 L, and the mixture was mixed with a stirrer to make it. For a homogeneous solution, cool to below 5°C with ice water. A solution prepared by dissolving 215 g of di-tertiary butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) in 120 g of ethanol was dropped therefrom through a dropping funnel. At this time, dropping was performed while adjusting the dropping speed so that the temperature of the reaction liquid was kept at 50° C. or lower. The target compound E-1 was obtained by concentrating the reaction solution under reduced pressure at 50° C. for 3 hours after 2 hours from the completion of the dropping.

<Example 1> Using the polymer A-1, a negative photosensitive resin composition was prepared by the following method, and the evaluation of the prepared composition was performed. Polymer A-1 as (A) polyimide precursor: 100 g, 1-phenyl-1,2-propanedione-2-(O-ethyl as (B) photopolymerization initiator 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) : In 150 g. By further adding a small amount of GBL, the viscosity of the obtained solution was adjusted to about 30 poise, and the negative photosensitive resin composition was produced. The compositions were evaluated according to the methods described above. The results are shown in Table 1.

<Examples 2 to 13, Comparative Examples 1 to 3> The same negative photosensitive resin composition as in Example 1 was prepared, except that the composition and the mixing ratio shown in Table 1 were 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, respectively.

B-1: 1-Phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime C-1: 3-glycidyloxypropyltrimethoxysilane (KBM-403) C-2: N-Phenyl-3-aminopropyltrimethoxysilane (KBM-573) C-3: 3-Ureidopropyltriethoxysilane (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 sulfoxide (DMSO) E-1: Compound shown in Production Example 5 E-2: 1-(3rd-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 with Sealing Materials good good good good good good acceptable good good good good excellent good acceptable acceptable bad (unit: g)

As can be seen from Table 1, Examples 1 to 13 including (C) silane coupling agent having the specific structure represented by the above general formula (1) and Examples 1 to 13 not including (C) having 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, the generation of voids at the interface between the Cu layer and the resin layer after the high-temperature storage test can be suppressed, and the adhesiveness with the sealing material is also good. [Industrial Availability]

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

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) )Express:

{In the formula, a is an integer of 1 to 3, n is an integer of 1 to 6, R ₂₁ is independently an alkyl group with 1 to 4 carbon atoms, R ₂₂ is a hydroxyl group or an alkyl group with 1 to 4 carbon atoms, and , R ₂₀ is at least one selected from the group consisting of substituents comprising epoxy, phenylamine, urea and isocyanate}; and (D) an organic solvent containing a compound selected from γ- At least one kind selected from the group consisting of butyrolactone, dimethylsulfoxide, tetrahydrofurfuryl alcohol, ethyl acetate, 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 including a phenylamino group and a ureido group. The negative photosensitive resin composition according to claim 1 or 2, wherein in the general formula (1), R ₂₀ is a substituent containing a phenylamino group. The negative photosensitive resin composition of claim 1 or 2, further comprising (E) a thermal base generator. The negative photosensitive resin composition according to claim 1 or 2, wherein the above-mentioned (D) organic solvent contains a compound selected from the group consisting of γ-butyrolactone, dimethylsulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, and succinic acid. At least two of the group consisting of dimethyl malonate, dimethyl malonate and ε-caprolactone. The negative photosensitive resin composition of claim 1 or 2, wherein the (A) polyimide precursor has a structural unit represented by the following general formula (2):

{In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer from 2 to 150, and R ₁ and R ₂ are 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 according to claim 6, wherein in the general formula (2), at least one of R ₁ and R ₂ is a valent organic group represented by the following general formula (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, wherein in the above general formula (2), X ₁ has a structure represented by the following general formula (20a):

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

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

The negative photosensitive resin composition of claim 6, wherein in the above general formula (2), Y ₁ comprises a structure represented by the following general formula (21b):

The negative photosensitive resin composition of claim 6, wherein in the above general formula (2), Y ₁ comprises a structure represented by the following general formula (21c):

{In the formula, R ₆ is a valent group selected from the group consisting of hydrogen atoms, fluorine atoms, hydrocarbon groups with 1 to 10 carbon atoms, and fluorine-containing hydrocarbon groups with 1 to 10 carbon atoms, and n is selected from 0 an integer of ~4}. The negative photosensitive resin composition of claim 6, wherein the (A) polyimide precursor has a structural unit represented by the following general formula (4):

{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}. The negative photosensitive resin composition according to claim 6, wherein the (A) polyimide precursor has a structural unit represented by the following general formula (5): [Chemical 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 from 2 to 150}. The negative photosensitive resin composition of claim 6, wherein the (A) polyimide precursor simultaneously includes a structural unit represented by the following general formula (4):

{wherein, R ₁ and R ₂ are 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 following The structural unit represented by the general formula (5):

{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; 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 (A) polyimide precursor is a copolymer of the structural units represented by the general formulae (4) and (5). The negative photosensitive resin composition of claim 6, wherein the (A) polyimide precursor has a structural unit represented by the following general formula (6):

{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}. The negative photosensitive resin composition according to claim 1 or 2, comprising 100 parts by mass of the above-mentioned (A) polyimide precursor, and 0.1 based on 100 parts by mass of the above-mentioned (A) polyimide precursor. -20 parts by mass of the above-mentioned (B) photopolymerization initiator, 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 method for producing polyimide, comprising the step of converting the negative photosensitive resin composition according to any one of claims 1 to 18 into polyimide. A method for manufacturing a hardened relief pattern, comprising the following steps: (1) coating 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) exposing the photosensitive resin layer; (3) developing the photosensitive resin layer after exposure to form a relief pattern; and (4) subjecting the relief pattern to heat treatment to form a cured relief pattern.