TW201945439A

TW201945439A - Negative photosensitive resin composition, and method for producing said composition having good tightness and high temperature storage between the copper layer and the resin layer

Info

Publication number: TW201945439A
Application number: TW108114450A
Authority: TW
Inventors: 塩崎秀二郎; 小倉知士; 平田竜也
Original assignee: 日商旭化成股份有限公司
Priority date: 2018-04-27
Filing date: 2019-04-25
Publication date: 2019-12-01
Also published as: JP2020091464A; JP7407518B2; JP2024019341A; TW202334283A; TWI803627B; JP2023171788A

Abstract

An object of the present invention is to provide a negative photosensitive resin composition which can obtain higher chemical resistance and resolution, and can suppress the generation of voids at the interface between a Cu layer and a resin layer after a high temperature storage test. Further, an object of the present invention is to provide a method of forming a hardened concave-convex pattern using a negative photosensitive resin composition of the present invention. Also, the fan-out wafer-level packaging have attracted attention in recent years. In a fan-out wafer-level packaging, a wafer sealing body larger than the wafer size of a semiconductor wafer is formed by covering the semiconductor wafer with a sealing material. Then a wire redistribution layer is further formed to reach the area of the semiconductor wafer and the sealing material. The wire redistribution layer is formed from a thinner film. Since the wire redistribution layer can be formed to the area of the sealing material, the number of external connection terminals can be increased. The negative photosensitive resin composition of the present invention comprises: (A) a polyimide precursor; a specific compound (for example, (B1) an active esterifying agent, (B2) a thermal hardening agent, and (B3) a tertiary amine compound and/or a guanidine compound, (B4) an acidic compound, or (B5) a nitrogen-containing compound); and (C) a photopolymerization initiator.

Description

Negative photosensitive resin composition and manufacturing method thereof

本發明係關於一種負型感光性樹脂組合物及其製造方法。The present invention relates to a negative photosensitive resin composition and a method for producing the same.

先前，電子零件之絕緣材料、及半導體裝置之鈍化膜、表面保護膜、層間絕緣膜等中使用同時具有優異之耐熱性、電氣特性及機械特性之聚醯亞胺樹脂、聚苯并㗁唑樹脂、酚系樹脂等。該等樹脂之中，以感光性樹脂組合物之形態提供者可藉由該組合物之塗佈、曝光、顯影、及利用固化之熱醯亞胺化處理而容易地形成耐熱性之凹凸圖案皮膜。此種感光性樹脂組合物具有與先前之非感光型材料相比能夠大幅縮短步驟之特徵。Previously, polyimide resins and polybenzoxazole resins, which had excellent heat resistance, electrical characteristics, and mechanical properties, were used for insulating materials of electronic parts, and passivation films, surface protective films, and interlayer insulating films of semiconductor devices. , Phenolic resin, etc. Among these resins, the supplier in the form of a photosensitive resin composition can easily form a heat-resistant uneven pattern film by applying the composition, exposing, developing, and curing a thermally-imidized process. . Such a photosensitive resin composition has a feature that the steps can be significantly shortened compared with the conventional non-photosensitive material.

另外，半導體裝置(以下亦稱為「元件」)對應於目的而以各種方法安裝於印刷基板。先前之元件通常係藉由以較細之金屬線自元件之外部端子(焊墊)連接至引線框架之打線接合法而製作。然而，於元件之高速化推進而動作頻率達到GHz之今日，安裝中之各端子之配線長度之差異對元件之動作產生影響。因此，於高端用途之元件之安裝中，產生正確控制安裝配線之長度之必要，於打線接合中難以滿足該要求。In addition, a semiconductor device (hereinafter also referred to as a “device”) is mounted on a printed circuit board by various methods according to the purpose. Previous devices were usually made by wire bonding using thin metal wires connected from the external terminals (pads) of the device to the lead frame. However, in today's high-speed components, and the operating frequency reaches GHz, the difference in the wiring length of each terminal during installation has an impact on the component's operation. Therefore, in the installation of high-end components, it is necessary to correctly control the length of the installation wiring, and it is difficult to meet this requirement in wire bonding.

因此，提出有於半導體晶片之表面形成再配線層，並於其上形成凸塊(電極)後，將該晶片反過來直接安裝於印刷基板之覆晶安裝(例如參照日本專利文獻1)。於該覆晶安裝中，可正確控制配線距離，故而被處理高速之信號之高端用途之元件或安裝尺寸較小之行動電話等分別採用而需求急速擴大。於覆晶安裝中使用聚醯亞胺、聚苯并㗁唑、酚系樹脂等材料之情形時，形成該樹脂層之圖案後，經過金屬配線層形成步驟。金屬配線層通常係對樹脂層表面進行電漿蝕刻將表面粗化後，藉由濺鍍以1 μm以下之厚度形成成為鍍覆之晶種層之金屬層後，將該金屬層作為電極，藉由電解鍍覆而形成。此時，一般作為成為晶種層之金屬，使用鈦(Ti)，作為藉由電解鍍覆所形成之再配線層之金屬，使用銅(Cu)。Therefore, a flip-chip mounting method is proposed in which a redistribution layer is formed on the surface of a semiconductor wafer and bumps (electrodes) are formed thereon, and then the wafer is directly mounted on a printed circuit board in reverse (for example, refer to Japanese Patent Document 1). In this flip-chip installation, the wiring distance can be controlled correctly, so the components used for high-end applications that process high-speed signals or mobile phones with smaller installation sizes are used separately and the demand is rapidly expanding. In the case where materials such as polyimide, polybenzoxazole, and phenol-based resin are used for flip-chip mounting, a pattern of the resin layer is formed and then a metal wiring layer forming step is performed. The metal wiring layer is generally formed by plasma-etching the surface of the resin layer to roughen the surface, and then forming a metal layer as a seed layer for plating by sputtering to a thickness of 1 μm or less, and then using the metal layer as an electrode. It is formed by electrolytic plating. At this time, titanium (Ti) is generally used as a metal to be a seed layer, and copper (Cu) is used as a metal of a redistribution layer formed by electrolytic plating.

對於此種金屬再配線層，要求於可靠性試驗後再配線之金屬層與樹脂層之密接性較高。作為可靠性試驗，例如可列舉：於空氣中以125℃以上之高溫保存100小時以上之高溫保存試驗；一面組入配線施加電壓一面確認於空氣中以125℃左右之溫度經過100小時以上之保存下之動作之高溫動作試驗；於空氣中循環往復-65℃～-40℃左右之低溫狀態與125℃～150℃左右之高溫狀態之溫度循環試驗；以85℃以上之溫度於濕度85%以上之水蒸氣環境下保存之高溫高濕保存試驗；一面組入配線施加電壓一面進行與高溫高濕保存試驗相同之試驗之高溫高濕偏壓試驗；以及於空氣中或氮氣下複數次通過260℃之回焊爐之回焊試驗等。
[先前技術文獻]
[專利文獻]For such a metal redistribution layer, the adhesion between the metal layer and the resin layer that are to be redistributed after the reliability test is required is high. Examples of the reliability test include: a high-temperature storage test in which air is stored at a high temperature of 125 ° C or higher for more than 100 hours; while the voltage is applied to the wiring, it is confirmed that it has been stored in the air at a temperature of about 125 ° C for more than 100 hours High-temperature operation test of the following actions; Temperature cycling test of low-temperature state of -65 ℃ ～ -40 ℃ and high-temperature state of about 125 ℃ ～ 150 ℃ in air cycle; temperature above 85 ℃ and humidity above 85% High-temperature and high-humidity storage test stored under water vapor environment; The high-temperature and high-humidity bias test is performed under the same test as the high-temperature and high-humidity storage test while the voltage is applied to the wiring; and it passes 260 ° C several times in air or nitrogen. Reflow test of reflow furnace.
[Prior technical literature]
[Patent Literature]

[專利文獻1]日本專利特開2001-338947號公報[Patent Document 1] Japanese Patent Laid-Open No. 2001-338947

[發明所欲解決之問題][Problems to be solved by the invention]

然而，先前於上述可靠性試驗中之高溫保存試驗之情形時，存在試驗後於再配線之Cu層之與樹脂層相接之界面產生孔隙之問題。若於Cu層與樹脂層之界面產生孔隙，則兩者之密接性降低。However, in the case of the high-temperature storage test in the reliability test described above, there was a problem that voids were generated at the interface between the Cu layer and the resin layer that were rewired after the test. If pores are generated at the interface between the Cu layer and the resin layer, the adhesion between the two will decrease.

又，除了孔隙之問題以外，還對金屬再配線層要求耐化學品性，又，微細化要求亦增加。因此，尤其對用於形成半導體之再配線層之感光性樹脂組合物要求抑制孔隙之產生並且顯示較高之耐化學品性與解像性。In addition to the problem of porosity, chemical resistance is required for the metal redistribution layer, and the requirement for miniaturization has also increased. Therefore, in particular, the photosensitive resin composition for forming a redistribution layer of a semiconductor is required to suppress generation of pores and exhibit high chemical resistance and resolution.

本發明係鑒於此種先前之實際情況而想出者，其目的之一在於提供一種可獲得較高之耐化學品性及解像度，且於高溫保存(high temperature storage)試驗後可抑制Cu層之與樹脂層相接之界面產生孔隙之負型感光性樹脂組合物(以下，於本說明書中亦簡稱為「感光性樹脂組合物」)。又，其目的之一亦在於提供一種使用本發明之負型感光性樹脂組合物之硬化凹凸圖案之形成方法。
又，近年來扇出型半導體封裝體受到關注。於扇出型之半導體封裝體中，藉由以密封材覆蓋半導體晶片而形成大於半導體晶片之晶片尺寸之晶片密封體。進而，形成達至半導體晶片及密封材之區域之再配線層。再配線層以較薄之膜厚形成。又，由於再配線層可形成至密封材之區域，故而可增多外部連接端子之個數。
[解決問題之技術手段]The present invention was conceived in view of such a previous actual situation, and one of the objects thereof is to provide a chemical resistance and resolution that can be obtained, and that the Cu layer can be suppressed after a high temperature storage test. A negative-type photosensitive resin composition (hereinafter, also referred to simply as a "photosensitive resin composition") in the interface between the resin layer and the pores. It is also an object of the present invention to provide a method for forming a cured uneven pattern using the negative photosensitive resin composition of the present invention.
In addition, in recent years, fan-out semiconductor packages have attracted attention. In a fan-out type semiconductor package, a wafer sealing body larger than the wafer size of the semiconductor wafer is formed by covering the semiconductor wafer with a sealing material. Further, a redistribution layer is formed in a region reaching the semiconductor wafer and the sealing material. The redistribution layer is formed with a thin film thickness. In addition, since the redistribution layer can be formed to the area of the sealing material, the number of external connection terminals can be increased.
[Technical means to solve the problem]

本發明者等人發現，藉由組合特定之感光性樹脂、特定之化合物(例如，(B1)活性酯化劑、(B2)熱硬化劑、(B3)三級胺化合物及/或胍化合物、(B4)酸性化合物或(B5)含氮化合物)、及光聚合起始劑，可解決上述課題，從而完成本發明。即，本發明如下所述。
[1]
一種負型感光性樹脂組合物，其包含：
(A)聚醯亞胺前驅物；
(B)活性酯化劑；及
(C)光聚合起始劑。
[2]
如[1]中記載之負型感光性樹脂組合物，其中上述(B)活性酯化劑為選自由碳酸雙(五氟苯基)酯、碳酸雙(4-硝基苯基)酯、二(N-丁二醯亞胺基)碳酸酯、五氟苯酚、1-羥基-7-氮雜苯并三唑及三氟乙酸4-硝基苯酯所組成之群中之至少1種。
[3]
如[1]或[2]中記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物包含具有下述通式(2)所表示之結構單元之聚醯亞胺前驅物：
[化1]

{式中，X₁ 為4價之有機基，Y₁ 為2價之有機基，n₁ 為2～150之整數，並且R₁ 及R₂ 分別獨立為氫原子或1價之有機基，R₁ 及R₂ 之至少一者為1價之有機基}。
[4]
如[3]中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1價之有機基：
[化2]

{式中，L₁ 、L₂ 及L₃ 分別獨立為氫原子或碳數1～3之有機基，並且m₁ 為2～10之整數}。
[5]
如[3]或[4]中記載之負型感光性樹脂組合物，其中於上述通式(2)中，X₁ 包含下述通式(20a)所表示之結構：
[化3]
。
[6]
如[3]或[4]中記載之負型感光性樹脂組合物，其中於上述通式(2)中，X₁ 包含下述通式(20b)所表示之結構：
[化4]
。
[7]
如[3]至[6]中任一項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5]
。
[8]
如[3]或[4]中記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物包含具有下述通式(4)所表示之結構單元之聚醯亞胺前驅物：
[化6]

{式中，R₁ 、R₂ 、及n₁ 係上述所定義者}。
[9]
如[3]或[4]中記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物包含具有下述通式(5)所表示之結構單元之聚醯亞胺前驅物：
[化7]

{式中，R₁ 、R₂ 、及n₁ 係上述所定義者}。
[10]
如[3]至[9]中任一項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)及(5)所表示之結構單元：
[化8]

{式中，R₁ 、R₂ 、及n₁ 分別為上述所定義者，與通式(5)中之R₁ 、R₂ 、及n₁ 相同，或可不同}
[化9]

{式中，R₁ 、R₂ 、及n₁ 分別為上述所定義者，與通式(4)中之R₁ 、R₂ 、及n₁ 相同，或可不同}。
[11]
如[10]中記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物為上述通式(4)與(5)所表示之結構單元之共聚物。
[12]
如[1]至[11]中任一項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質量份為基準之0.1～30質量份之上述(B)活性酯化劑、及
以上述(A)聚醯亞胺前驅物100質量份為基準之0.1～20質量份之上述(C)光聚合起始劑。
[13]
一種聚醯亞胺之製造方法，其包含將如[1]至[12]中任一項記載之負型感光性樹脂組合物轉換為聚醯亞胺之步驟。
[14]
一種硬化凹凸圖案之製造方法，其包含：
(1)將如[1]至[12]中任一項記載之負型感光性樹脂組合物塗佈於基板上而於上述基板上形成感光性樹脂層之步驟、
(2)對上述感光性樹脂層進行曝光之步驟、
(3)對曝光後之上述感光性樹脂層進行顯影而形成凹凸圖案之步驟、及
(4)對上述凹凸圖案進行加熱處理而形成硬化凹凸圖案之步驟。
[15]
一種負型感光性樹脂組合物，其包含：
(A)聚醯亞胺前驅物；
(B)熱硬化劑；及
(C)光聚合起始劑。
[16]
如[15]中記載之負型感光性樹脂組合物，其中上述(B)熱硬化劑為選自由苯并㗁、環氧樹脂及氧雜環丁烷樹脂所組成之群中之至少1種。
[17]
如[15]或[16]中記載之負型感光性樹脂組合物，其中上述(B)熱硬化劑為苯并㗁。
[18]
如[15]至[17]中任一項記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物包含具有下述通式(2)所表示之結構單元之聚醯亞胺前驅物：
[化10]

{式中，X₁ 為4價之有機基，Y₁ 為2價之有機基，n₁ 為2～150之整數，並且R₁ 及R₂ 分別獨立為氫原子或1價之有機基，R₁ 及R₂ 之至少一者為1價之有機基}。
[19]
如[18]中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1價之有機基：
[化11]

{式中，L₁ 、L₂ 及L₃ 分別獨立為氫原子或碳數1～3之有機基，並且m₁ 為2～10之整數}。
[20]
如[18]或[19]中記載之負型感光性樹脂組合物，其中於上述通式(2)中，X₁ 包含下述通式(20a)所表示之結構：
[化12]
。
[21]
如[18]或[19]中記載之負型感光性樹脂組合物，其中於上述通式(2)中，X₁ 包含下述通式(20b)所表示之結構：
[化13]
。
[22]
如[18]至[21]中任一項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14]
。
[23]
如[18]或[19]中記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物包含具有下述通式(4)所表示之結構單元之聚醯亞胺前驅物：
[化15]

{式中，R₁ 、R₂ 、及n₁ 係上述所定義者}。
[24]
如[18]或[19]中記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物包含具有下述通式(5)所表示之結構單元之聚醯亞胺前驅物：
[化16]

{式中，R₁ 、R₂ 、及n₁ 係上述所定義者}。
[25]
如[18]至[24]中任一項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)及(5)所表示之結構單元：
[化17]

{式中，R₁ 、R₂ 、及n₁ 分別為上述所定義者，與通式(5)中之R₁ 、R₂ 、及n₁ 相同，或可不同}
[化18]

{式中，R₁ 、R₂ 、及n₁ 分別為上述所定義者，與通式(4)中之R₁ 、R₂ 、及n₁ 相同，或可不同}。
[26]
如[25]中記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物為上述通式(4)與(5)所表示之結構單元之共聚物。
[27]
如[15]至[26]中任一項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質量份為基準之0.1～30質量份之上述(B)熱硬化劑、及
以上述(A)聚醯亞胺前驅物100質量份為基準之0.1～20質量份之上述(C)光聚合起始劑。
[28]
一種聚醯亞胺之製造方法，其包含將如[15]至[27]中任一項記載之負型感光性樹脂組合物轉換為聚醯亞胺之步驟。
[29]
一種硬化凹凸圖案之製造方法，其包括：
(1)將如[15]至[27]中任一項記載之負型感光性樹脂組合物塗佈於基板上而於上述基板上形成感光性樹脂層之步驟、
(2)對上述感光性樹脂層進行曝光之步驟、
(3)對曝光後之上述感光性樹脂層進行顯影而形成凹凸圖案之步驟、及
(4)對上述凹凸圖案進行加熱處理而形成硬化凹凸圖案之步驟。
[30]
一種負型感光性樹脂組合物，其包含：
(A)聚醯亞胺前驅物；
(B)選自由下述通式(B-1)：
[化19]

{式中，Ra及Rb分別獨立為可包含雜原子之碳數1～10之1價之有機基，Rc分別獨立為可包含雜原子之1價之有機基，且m表示0～5之整數}
所表示之三級胺化合物、及胍化合物所組成之群中之至少1種；及
(C)光聚合起始劑。
[31]
如[30]中記載之負型感光性樹脂組合物，其中於上述通式(B-1)中，Ra及Rb為選自由甲基、乙基、正丙基、及異丙基所組成之群中之至少1種。
[32]
如[30]中記載之負型感光性樹脂組合物，其中上述胍化合物為下述通式(B-2)所表示之化合物：
[化20]

{式中，Rd表示氫原子、或可包含雜原子之碳數1～10之1價之有機基}。
[33]
如[30]至[32]中任一項記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物包含具有下述通式(2)所表示之結構單元之聚醯亞胺前驅物：
[化21]

{式中，X₁ 為4價之有機基，Y₁ 為2價之有機基，n₁ 為2～150之整數，並且R₁ 及R₂ 分別獨立為氫原子或1價之有機基，R₁ 及R₂ 之至少一者為1價之有機基}。
[34]
如[33]中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1價之有機基：
[化22]

{式中，L₁ 、L₂ 及L₃ 分別獨立為氫原子或碳數1～3之有機基，並且m₁ 為2～10之整數}。
[35]
如[33]或[34]中記載之負型感光性樹脂組合物，其中於上述通式(2)中，X₁ 包含下述通式(20a)所表示之結構：
[化23]
。
[36]
如[33]或[34]中記載之負型感光性樹脂組合物，其中於上述通式(2)中，X₁ 包含下述通式(20b)所表示之結構：
[化24]
。
[37]
如[33]至[36]中任一項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25]
。
[38]
如[33]或[34]中記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物包含具有下述通式(4)所表示之結構單元之聚醯亞胺前驅物：
[化26]

{式中，R₁ 、R₂ 、及n₁ 係上述所定義者}。
[39]
如[33]或[34]中記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物包含具有下述通式(5)所表示之結構單元之聚醯亞胺前驅物：
[化27]

{式中，R₁ 、R₂ 、及n₁ 係上述所定義者}。
[40]
如[33]至[39]中任一項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)及(5)所表示之結構單元：
[化28]

{式中，R₁ 、R₂ 、及n₁ 分別為上述所定義者，與通式(5)中之R₁ 、R₂ 、及n₁ 相同，或可不同}
[化29]

{式中，R₁ 、R₂ 、及n₁ 分別為上述所定義者，與通式(4)中之R₁ 、R₂ 、及n₁ 相同，或可不同}。
[41]
如[40]中記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物為上述通式(4)與(5)所表示之結構單元之共聚物。
[42]
如[30]至[41]中任一項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質量份為基準之0.1～30質量份之上述(B)三級胺化合物及/或胍化合物、及
以上述(A)聚醯亞胺前驅物100質量份為基準之0.1～20質量份之上述(C)光聚合起始劑。
[43]
一種聚醯亞胺之製造方法，其包括將如[30]至[42]中任一項記載之負型感光性樹脂組合物轉換為聚醯亞胺之步驟。
[44]
一種硬化凹凸圖案之製造方法，其包括：
(1)將如[30]至[42]中任一項記載之負型感光性樹脂組合物塗佈於基板上而於上述基板上形成感光性樹脂層之步驟、
(2)對上述感光性樹脂層進行曝光之步驟、
(3)對曝光後之上述感光性樹脂層進行顯影而形成凹凸圖案之步驟、及
(4)對上述凹凸圖案進行加熱處理而形成硬化凹凸圖案之步驟。
[45]
一種負型感光性樹脂組合物，其包含以下之成分：
(A)聚醯亞胺前驅物；
(B-1)於結構中具有2個以上之酚性羥基或羧基之酸性化合物；及
(C)光聚合起始劑。
[46]
如[45]中記載之負型感光性樹脂組合物，其中上述(B-1)酸性化合物為選自由沒食子酸甲酯、亞甲基二水楊酸、鄰香豆酸、鄰苯二甲酸所組成之群中之至少1種酸性化合物。
[47]
如[45]或[46]中記載之負型感光性樹脂組合物，其中上述(B-1)酸性化合物為亞甲基二水楊酸或鄰香豆酸。
[48]
一種負型感光性樹脂組合物，其包含以下之成分：
(A)聚醯亞胺前驅物；
(B-2)於結構中具有1個選自酚性羥基或羧基中之基，且具有1個以上之選自-NH-CO-A₁ 、或-CO-NH₂ 中之基之酸性化合物(A₁ 為碳數1～4之有機基)；及
(C)光聚合起始劑。
[49]
如[48]中記載之負型感光性樹脂組合物，其中上述(B-2)酸性化合物以下述通式(1)表示：
[化30]

{式(1)中，A₂ 為羥基、或羧基，A₃ 為選自-NH-CO-A₁ 、或-CO-NH₂ 中之基，A₁ 為碳數1～4之有機基，A₄ 為1價之基，m₂ 為1或2，m₃ 為0～4之整數}。
[50]
如[45]至[49]中任一項記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物包含具有下述通式(2)所表示之結構單元之聚醯亞胺前驅物：
[化31]

{式中，X₁ 為4價之有機基，Y₁ 為2價之有機基，n₁ 為2～150之整數，並且R₁ 及R₂ 分別獨立為氫原子或1價之有機基，R₁ 及R₂ 之至少一者為1價之有機基}。
[51]
如[50]中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1價之有機基：
[化32]

{式中，L₁ 、L₂ 及L₃ 分別獨立為氫原子或碳數1～3之有機基，並且m₁ 為2～10之整數}。
[52]
如[50]或[51]中記載之負型感光性樹脂組合物，其中於上述通式(2)中，X₁ 包含下述通式(20a)所表示之結構：
[化33]
。
[53]
如[50]或[51]中記載之負型感光性樹脂組合物，其中於上述通式(2)中，X₁ 包含下述通式(20b)所表示之結構：
[化34]
。
[54]
如[50]至[53]中任一項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)或通式(7)所表示之結構：
[化35]

[化36]

(式中，R₉ ～R₁₂ 為氫原子或碳數1～4之1價之脂肪族基，可相互相同，亦可不同)。
[55]
如[50]或[51]中記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物包含具有下述通式(4)所表示之結構單元之聚醯亞胺前驅物：
[化37]

{式中，R₁ 、R₂ 、及n₁ 係上述所定義者}。
[56]
如[50]或[51]中記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物包含具有下述通式(5)所表示之結構單元之聚醯亞胺前驅物：
[化38]

{式中，R₁ 、R₂ 、及n₁ 係上述所定義者}。
[57]
如[50]至[56]中任一項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)及下述通式(5)所表示之結構單元：
[化39]

{式中，R₁ 、R₂ 、及n₁ 分別為上述所定義者，與通式(5)中之R₁ 、R₂ 、及n₁ 相同，或可不同}
[化40]

{式中，R₁ 、R₂ 、及n₁ 分別為上述所定義者，與通式(4)中之R₁ 、R₂ 、及n₁ 相同，或可不同}。
[58]
如[57]中記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物為上述通式(4)與(5)所表示之結構單元之共聚物。
[59]
如[45]至[47]中任一項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質量份為基準之0.1～30質量份之上述(B-1)酸性化合物、及
以上述(A)聚醯亞胺前驅物100質量份為基準之0.1～20質量份之上述(C)光聚合起始劑。
[60]
如[48]或[49]中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質量份為基準之0.1～30質量份之上述(B-2)酸性化合物)、及
以上述(A)聚醯亞胺前驅物100質量份為基準之0.1～20質量份之上述(C)光聚合起始劑。
[61]
一種聚醯亞胺之製造方法，其包含將如[45]至[60]中任一項記載之負型感光性樹脂組合物轉換為聚醯亞胺之步驟。
[62]
一種硬化凹凸圖案之製造方法，其包含：
(1)將如[45]至[60]中任一項記載之負型感光性樹脂組合物塗佈於基板上而於上述基板上形成感光性樹脂層之步驟、
(2)對上述感光性樹脂層進行曝光之步驟、
(3)對曝光後之上述感光性樹脂層進行顯影而形成凹凸圖案之步驟、及
(4)對上述凹凸圖案進行加熱處理而形成硬化凹凸圖案之步驟。
[63]
一種負型感光性樹脂組合物，其包含：
(A)聚醯亞胺前驅物；
(B)選自由縮二脲化合物、咔唑化合物、吲哚化合物、乙內醯脲化合物、尿嘧啶衍生物及巴比妥酸化合物所組成之群中之至少1種含氮化合物；及
(C)光聚合起始劑。
[64]
如[63]中記載之負型感光性樹脂組合物，其中上述(B)含氮化合物為選自由縮二脲化合物、咔唑化合物、及吲哚化合物所組成之群中之至少1種。
[65]
如[63]或[64]中記載之負型感光性樹脂組合物，其中上述(B)含氮化合物為縮二脲化合物。
[66]
如[63]至[65]中任一項記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物包含具有下述通式(2)所表示之結構單元之聚醯亞胺前驅物：
[化41]

{式中，X₁ 為4價之有機基，Y₁ 為2價之有機基，n₁ 為2～150之整數，並且R₁ 及R₂ 分別獨立為氫原子或1價之有機基，R₁ 及R₂ 之至少一者為1價之有機基}。
[67]
如[66]中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1價之有機基：
[化42]

{式中，L₁ 、L₂ 及L₃ 分別獨立為氫原子、或碳數1～3之有機基，並且m₁ 為2～10之整數}。
[68]
如[66]或[67]中記載之負型感光性樹脂組合物，其中於上述通式(2)中，X₁ 包含下述通式(20a)所表示之結構：
[化43]
。
[69]
如[66]或[67]中記載之負型感光性樹脂組合物，其中於上述通式(2)中，X₁ 包含下述通式(20b)所表示之結構：
[化44]
。
[70]
如[66]至[69]中任一項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45]
。
[71]
如[66]或[67]中記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物包含具有下述通式(4)所表示之結構單元之聚醯亞胺前驅物：
[化46]

{式中，R₁ 、R₂ 、及n₁ 係上述所定義者}。
[72]
如[66]或[67]中記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物包含具有下述通式(5)所表示之結構單元之聚醯亞胺前驅物：
[化47]

{式中，R₁ 、R₂ 、及n₁ 係上述所定義者}。
[73]
如[66]至[72]中任一項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)及(5)所表示之結構單元：
[化48]

{式中，R₁ 、R₂ 、及n₁ 分別為上述所定義者，與通式(5)中之R₁ 、R₂ 、及n₁ 相同，或可不同}
[化49]

{式中，R₁ 、R₂ 、及n₁ 分別為上述所定義者，與通式(4)中之R₁ 、R₂ 、及n₁ 相同，或可不同}。
[74]
如[73]中記載之負型感光性樹脂組合物，其中上述(A)聚醯亞胺前驅物為上述通式(4)與(5)所表示之結構單元之共聚物。
[75]
如[63]至[74]中任一項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質量份為基準之0.1～30質量份之上述(B)含氮化合物、及
以上述(A)聚醯亞胺前驅物100質量份為基準之0.1～20質量份之上述(C)光聚合起始劑。
[76]
一種聚醯亞胺之製造方法，其包括將如[63]至[75]中任一項記載之負型感光性樹脂組合物轉換為聚醯亞胺之步驟。
[77]
一種硬化凹凸圖案之製造方法，其包括：
(1)將如[63]至[75]中任一項記載之負型感光性樹脂組合物塗佈於基板上而於上述基板上形成感光性樹脂層之步驟、
(2)對上述感光性樹脂層進行曝光之步驟、
(3)對曝光後之上述感光性樹脂層進行顯影而形成凹凸圖案之步驟、及
(4)對上述凹凸圖案進行加熱處理而形成硬化凹凸圖案之步驟。
[發明之效果]The inventors have found that by combining a specific photosensitive resin, a specific compound (for example, (B1) an active esterifying agent, (B2) a thermosetting agent, (B3) a tertiary amine compound and / or a guanidine compound, (B4) an acidic compound or (B5) a nitrogen-containing compound) and a photopolymerization initiator can solve the above-mentioned problems and complete the present invention. That is, the present invention is as follows.
[1]
A negative photosensitive resin composition comprising:
(A) a polyimide precursor;
(B) an active esterifying agent; and
(C) Photopolymerization initiator.
[2]
The negative photosensitive resin composition according to [1], wherein the (B) active esterifying agent is selected from the group consisting of bis (pentafluorophenyl) carbonate, bis (4-nitrophenyl) carbonate, and (N-butanediimino) carbonate, pentafluorophenol, 1-hydroxy-7-azabenzotriazole, and 4-nitrophenyl trifluoroacetate.
[3]
The negative-type photosensitive resin composition according to [1] or [2], wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (2) Things:
[Chemical 1]

{Wherein 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, R At least one of ₁ and R ₂ is a monovalent organic group}.
[4]
The negative-type photosensitive resin composition according to [3], wherein in the general formula (2), at least one of R ₁ and R ₂ is a monovalent organic group represented by the following general formula (3) :
[Chemical 2]

{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}.
[5]
The negative photosensitive resin composition as described in [3] or [4], wherein in the general formula (2), X ₁ includes a structure represented by the following general formula (20a):
[Chemical 3]
.
[6]
The negative photosensitive resin composition as described in [3] or [4], wherein in the general formula (2), X ₁ includes a structure represented by the following general formula (20b):
[Chemical 4]
.
[7]
The negative photosensitive resin composition according to any one of [3] to [6], wherein in the general formula (2), Y ₁ includes a structure represented by the following general formula (21b):
[Chemical 5]
.
[8]
The negative photosensitive resin composition according to [3] or [4], wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (4) Things:
[Chemical 6]

{Wherein R ₁ , R ₂ , and n ₁ are as defined above}.
[9]
The negative-type photosensitive resin composition according to [3] or [4], wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (5) Things:
[Chemical 7]

{Wherein R ₁ , R ₂ , and n ₁ are as defined above}.
[10]
The negative-type photosensitive resin composition according to any one of [3] to [9], wherein the (A) polyimide precursor includes a structure represented by the following general formulae (4) and (5) unit:
[Chemical 8]

{In the formula, R ₁ , R ₂ , and n ₁ are respectively as defined above, and are the same as R ₁ , R ₂ , and n ₁ in the general formula (5), or may be different}
[Chemical 9]

{In the formula, R ₁ , R ₂ , and n ₁ are respectively defined above, and are the same as R ₁ , R ₂ , and n ₁ in the general formula (4), or may be different}.
[11]
The negative photosensitive resin composition according to [10], wherein the (A) polyimide precursor is a copolymer of a structural unit represented by the general formulae (4) and (5).
[12]
The negative photosensitive resin composition according to any one of [1] to [11], which comprises:
100 parts by mass of the aforementioned (A) polyimide precursor,
0.1 to 30 parts by mass of the above (B) active esterifying agent based on 100 parts by mass of the aforementioned (A) polyimide precursor, and based on 100 parts by mass of the (A) polyimide precursor 0.1 to 20 parts by mass of the (C) photopolymerization initiator.
[13]
A method for producing polyimide, comprising the step of converting the negative photosensitive resin composition according to any one of [1] to [12] into polyimide.
[14]
A method for manufacturing a hardened uneven pattern, comprising:
(1) a step of applying the negative photosensitive resin composition according to any one of [1] to [12] on a substrate to form a photosensitive resin layer on the substrate,
(2) a step of exposing the photosensitive resin layer,
(3) a step of developing the photosensitive resin layer after exposure to form a concave-convex pattern, and
(4) A step of heating the aforementioned uneven pattern to form a hardened uneven pattern.
[15]
A negative photosensitive resin composition comprising:
(A) a polyimide precursor;
(B) a thermosetting agent; and
(C) Photopolymerization initiator.
[16]
The negative photosensitive resin composition according to [15], wherein the (B) thermosetting agent is at least one selected from the group consisting of a benzofluorene, an epoxy resin, and an oxetane resin.
[17]
The negative photosensitive resin composition according to [15] or [16], wherein the (B) thermosetting agent is benzopyrene.
[18]
The negative-type photosensitive resin composition according to any one of [15] to [17], wherein the (A) polyimide precursor includes a polyfluorene having a structural unit represented by the following general formula (2) Imine precursor:
[Chemical 10]

{Wherein 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, R At least one of ₁ and R ₂ is a monovalent organic group}.
[19]
The negative-type photosensitive resin composition according to [18], wherein in the general formula (2), at least one of R ₁ and R ₂ is a monovalent organic group represented by the following general formula (3) :
[Chemical 11]

{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}.
[20]
The negative photosensitive resin composition according to [18] or [19], wherein in the general formula (2), X ₁ includes a structure represented by the following general formula (20a):
[Chemical 12]
.
[twenty one]
The negative photosensitive resin composition as described in [18] or [19], wherein in the general formula (2), X ₁ includes a structure represented by the following general formula (20b):
[Chemical 13]
.
[twenty two]
The negative photosensitive resin composition according to any one of [18] to [21], wherein in the general formula (2), Y ₁ includes a structure represented by the following general formula (21b):
[Chemical 14]
.
[twenty three]
The negative-type photosensitive resin composition according to [18] or [19], wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (4) Things:
[Chemical 15]

{Wherein R ₁ , R ₂ , and n ₁ are as defined above}.
[twenty four]
The negative-type photosensitive resin composition according to [18] or [19], wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (5) Things:
[Chemical 16]

{Wherein R ₁ , R ₂ , and n ₁ are as defined above}.
[25]
The negative photosensitive resin composition according to any one of [18] to [24], wherein the (A) polyimide precursor includes a structure represented by the following general formulae (4) and (5) unit:
[Chemical 17]

{In the formula, R ₁ , R ₂ , and n ₁ are respectively as defined above, and are the same as R ₁ , R ₂ , and n ₁ in the general formula (5), or may be different}
[Chemical 18]

{In the formula, R ₁ , R ₂ , and n ₁ are respectively defined above, and are the same as R ₁ , R ₂ , and n ₁ in the general formula (4), or may be different}.
[26]
The negative-type photosensitive resin composition according to [25], wherein the (A) polyimide precursor is a copolymer of a structural unit represented by the general formulae (4) and (5).
[27]
The negative photosensitive resin composition according to any one of [15] to [26], which comprises:
100 parts by mass of the aforementioned (A) polyimide precursor,
0.1 to 30 parts by mass of the above (B) thermosetting agent based on 100 parts by mass of the (A) polyimide precursor, and 0.1 based on 100 parts by mass of the (A) polyimide precursor -20 parts by mass of the above (C) photopolymerization initiator.
[28]
A method for producing polyimide, comprising the step of converting the negative-type photosensitive resin composition according to any one of [15] to [27] into polyimide.
[29]
A method for manufacturing a hardened uneven pattern includes:
(1) a step of applying the negative photosensitive resin composition according to any one of [15] to [27] on a substrate to form a photosensitive resin layer on the substrate,
(2) a step of exposing the photosensitive resin layer,
(3) a step of developing the photosensitive resin layer after exposure to form a concave-convex pattern, and
(4) A step of heating the aforementioned uneven pattern to form a hardened uneven pattern.
[30]
A negative photosensitive resin composition comprising:
(A) a polyimide precursor;
(B) is selected from the following general formula (B-1):
[Chemical 19]

{In the formula, Ra and Rb are each independently a monovalent organic group having 1 to 10 carbon atoms that may contain a hetero atom, Rc is each independently a monovalent organic group that may include a hetero atom, and m represents an integer of 0 to 5 }
At least one selected from the group consisting of a tertiary amine compound and a guanidine compound; and
(C) Photopolymerization initiator.
[31]
The negative photosensitive resin composition as described in [30], wherein in the general formula (B-1), Ra and Rb are selected from the group consisting of methyl, ethyl, n-propyl, and isopropyl At least one species in the group.
[32]
The negative photosensitive resin composition according to [30], wherein the guanidine compound is a compound represented by the following general formula (B-2):
[Chemical 20]

{In the formula, Rd represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms which may include a hetero atom}.
[33]
The negative-type photosensitive resin composition according to any one of [30] to [32], wherein the (A) polyimide precursor includes a polyfluorene having a structural unit represented by the following general formula (2) Imine precursor:
[Chemical 21]

{Wherein 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, R At least one of ₁ and R ₂ is a monovalent organic group}.
[34]
The negative photosensitive resin composition as described in [33], wherein in the general formula (2), at least one of R ₁ and R ₂ is a monovalent organic group represented by the following general formula (3) :
[Chemical 22]

{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}.
[35]
The negative photosensitive resin composition as described in [33] or [34], wherein in the general formula (2), X ₁ includes a structure represented by the following general formula (20a):
[Chemical 23]
.
[36]
The negative photosensitive resin composition as described in [33] or [34], wherein in the general formula (2), X ₁ includes a structure represented by the following general formula (20b):
[Chemical 24]
.
[37]
The negative photosensitive resin composition according to any one of [33] to [36], wherein in the general formula (2), Y ₁ includes a structure represented by the following general formula (21b):
[Chemical 25]
.
[38]
The negative-type photosensitive resin composition according to [33] or [34], wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (4) Things:
[Chemical 26]

{Wherein R ₁ , R ₂ , and n ₁ are as defined above}.
[39]
The negative-type photosensitive resin composition according to [33] or [34], wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (5) Things:
[Chemical 27]

{Wherein R ₁ , R ₂ , and n ₁ are as defined above}.
[40]
The negative-type photosensitive resin composition according to any one of [33] to [39], wherein the (A) polyimide precursor includes a structure represented by the following general formulae (4) and (5) unit:
[Chemical 28]

{In the formula, R ₁ , R ₂ , and n ₁ are respectively as defined above, and are the same as R ₁ , R ₂ , and n ₁ in the general formula (5), or may be different}
[Chemical 29]

{In the formula, R ₁ , R ₂ , and n ₁ are respectively defined above, and are the same as R ₁ , R ₂ , and n ₁ in the general formula (4), or may be different}.
[41]
The negative-type photosensitive resin composition according to [40], wherein the (A) polyimide precursor is a copolymer of a structural unit represented by the general formulae (4) and (5).
[42]
The negative photosensitive resin composition according to any one of [30] to [41], comprising:
100 parts by mass of the aforementioned (A) polyimide precursor,
0.1 to 30 parts by mass of the above (B) tertiary amine compound and / or guanidine compound based on 100 parts by mass of the (A) polyimide precursor, and 100 (A) the polyimide precursor The above (C) photopolymerization initiator is 0.1 to 20 parts by mass based on the parts by mass.
[43]
A method for producing polyimide, comprising the step of converting the negative-type photosensitive resin composition according to any one of [30] to [42] into polyimide.
[44]
A method for manufacturing a hardened uneven pattern includes:
(1) a step of applying the negative photosensitive resin composition according to any one of [30] to [42] on a substrate to form a photosensitive resin layer on the substrate,
(2) a step of exposing the photosensitive resin layer,
(3) a step of developing the photosensitive resin layer after exposure to form a concave-convex pattern, and
(4) A step of heating the aforementioned uneven pattern to form a hardened uneven pattern.
[45]
A negative photosensitive resin composition containing the following components:
(A) a polyimide precursor;
(B-1) an acidic compound having two or more phenolic hydroxyl or carboxyl groups in the structure; and
(C) Photopolymerization initiator.
[46]
The negative-type photosensitive resin composition according to [45], wherein the (B-1) acidic compound is selected from the group consisting of methyl gallate, methylene disalicylic acid, o-coumaric acid, and phthalic acid At least one acidic compound in a group consisting of formic acid.
[47]
The negative photosensitive resin composition according to [45] or [46], wherein the (B-1) acidic compound is methylene disalicylic acid or o-coumaric acid.
[48]
A negative photosensitive resin composition containing the following components:
(A) a polyimide precursor;
(B-2) An acidic compound having one group selected from phenolic hydroxyl or carboxyl groups in the structure and one or more groups selected from -NH-CO-A ₁ or -CO-NH ₂ (A ₁ is an organic group having 1 to 4 carbon atoms); and
(C) Photopolymerization initiator.
[49]
The negative-type photosensitive resin composition as described in [48], wherein the (B-2) acidic compound is represented by the following general formula (1):
[Chemical 30]

{In formula (1), A ₂ is a hydroxyl group or a carboxyl group, A ₃ is a group selected from -NH-CO-A ₁ or -CO-NH ₂ , and A ₁ is an organic group having 1 to 4 carbon atoms. A ₄ is a monovalent base, m ₂ is 1 or 2, and m ₃ is an integer of 0 to 4}.
[50]
The negative photosensitive resin composition according to any one of [45] to [49], wherein the (A) polyimide precursor includes a polyfluorene having a structural unit represented by the following general formula (2) Imine precursor:
[Chemical 31]

{Wherein 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, R At least one of ₁ and R ₂ is a monovalent organic group}.
[51]
The negative photosensitive resin composition according to [50], wherein in the general formula (2), at least one of R ₁ and R ₂ is a monovalent organic group represented by the following general formula (3) :
[Chemical 32]

{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}.
[52]
The negative photosensitive resin composition according to [50] or [51], wherein in the general formula (2), X ₁ includes a structure represented by the following general formula (20a):
[Chemical 33]
.
[53]
The negative photosensitive resin composition as described in [50] or [51], wherein in the general formula (2), X ₁ includes a structure represented by the following general formula (20b):
[Chem 34]
.
[54]
The negative photosensitive resin composition according to any one of [50] to [53], wherein in the general formula (2), Y ₁ includes the following general formula (21b) or (7) The structure:
[Chemical 35]

[Chemical 36]

(Wherein R ₉ to R ₁₂ are a hydrogen atom or a monovalent aliphatic group having 1 to 4 carbon atoms, and may be the same as or different from each other).
[55]
The negative photosensitive resin composition according to [50] or [51], wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (4) Things:
[Chemical 37]

{Wherein R ₁ , R ₂ , and n ₁ are as defined above}.
[56]
The negative photosensitive resin composition according to [50] or [51], wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (5) Things:
[Chemical 38]

{Wherein R ₁ , R ₂ , and n ₁ are as defined above}.
[57]
The negative-type photosensitive resin composition according to any one of [50] to [56], wherein the (A) polyimide precursor includes both the following general formula (4) and the following general formula (5) Represented structural unit:
[Chemical 39]

{In the formula, R ₁ , R ₂ , and n ₁ are respectively as defined above, and are the same as R ₁ , R ₂ , and n ₁ in the general formula (5), or may be different}
[Chemical 40]

{In the formula, R ₁ , R ₂ , and n ₁ are respectively defined above, and are the same as R ₁ , R ₂ , and n ₁ in the general formula (4), or may be different}.
[58]
The negative-type photosensitive resin composition according to [57], wherein the (A) polyimide precursor is a copolymer of a structural unit represented by the general formulae (4) and (5).
[59]
The negative photosensitive resin composition according to any one of [45] to [47], comprising:
100 parts by mass of the aforementioned (A) polyimide precursor,
0.1 to 30 parts by mass of the aforementioned (B-1) acidic compound based on 100 parts by mass of the aforementioned (A) polyimide precursor, and based on 100 parts by mass of the (A) polyimide precursor 0.1 to 20 parts by mass of the (C) photopolymerization initiator.
[60]
The negative photosensitive resin composition as described in [48] or [49], comprising:
100 parts by mass of the aforementioned (A) polyimide precursor,
0.1 to 30 parts by mass of the aforementioned (B-2) acidic compound based on 100 parts by mass of the aforementioned (A) polyimide precursor, and 100 parts by mass of the aforementioned (A) polyimide precursor 0.1 to 20 parts by mass of the above (C) photopolymerization initiator.
[61]
A method for producing polyimide, comprising the step of converting the negative photosensitive resin composition according to any one of [45] to [60] into polyimide.
[62]
A method for manufacturing a hardened uneven pattern, comprising:
(1) a step of applying the negative photosensitive resin composition according to any one of [45] to [60] on a substrate to form a photosensitive resin layer on the substrate,
(2) a step of exposing the photosensitive resin layer,
(3) a step of developing the photosensitive resin layer after exposure to form a concave-convex pattern, and
(4) A step of heating the aforementioned uneven pattern to form a hardened uneven pattern.
[63]
A negative photosensitive resin composition comprising:
(A) a polyimide precursor;
(B) at least one nitrogen-containing compound selected from the group consisting of a biuret compound, a carbazole compound, an indole compound, a hydantoin compound, a uracil derivative, and a barbituric acid compound; and
(C) Photopolymerization initiator.
[64]
The negative-type photosensitive resin composition according to [63], wherein the nitrogen-containing compound (B) is at least one selected from the group consisting of a biuret compound, a carbazole compound, and an indole compound.
[65]
The negative-type photosensitive resin composition according to [63] or [64], wherein the nitrogen-containing compound (B) is a biuret compound.
[66]
The negative-type photosensitive resin composition according to any one of [63] to [65], wherein the (A) polyimide precursor includes a polyfluorene having a structural unit represented by the following general formula (2) Imine precursor:
[Chemical 41]

{Wherein 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, R At least one of ₁ and R ₂ is a monovalent organic group}.
[67]
The negative-type photosensitive resin composition according to [66], wherein in the general formula (2), at least one of R ₁ and R ₂ is a monovalent organic group represented by the following general formula (3) :
[Chemical 42]

{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}.
[68]
The negative photosensitive resin composition according to [66] or [67], wherein in the general formula (2), X ₁ includes a structure represented by the following general formula (20a):
[Chemical 43]
.
[69]
The negative photosensitive resin composition as described in [66] or [67], wherein in the general formula (2), X ₁ includes a structure represented by the following general formula (20b):
[Chemical 44]
.
[70]
The negative photosensitive resin composition according to any one of [66] to [69], wherein in the general formula (2), Y ₁ includes a structure represented by the following general formula (21b):
[Chemical 45]
.
[71]
The negative-type photosensitive resin composition according to [66] or [67], wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (4) Things:
[Chemical 46]

{Wherein R ₁ , R ₂ , and n ₁ are as defined above}.
[72]
The negative-type photosensitive resin composition according to [66] or [67], wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (5) Things:
[Chemical 47]

{Wherein R ₁ , R ₂ , and n ₁ are as defined above}.
[73]
The negative-type photosensitive resin composition according to any one of [66] to [72], wherein the (A) polyimide precursor includes a structure represented by the following general formulae (4) and (5) unit:
[Chemical 48]

{In the formula, R ₁ , R ₂ , and n ₁ are respectively as defined above, and are the same as R ₁ , R ₂ , and n ₁ in the general formula (5), or may be different}
[Chemical 49]

{In the formula, R ₁ , R ₂ , and n ₁ are respectively defined above, and are the same as R ₁ , R ₂ , and n ₁ in the general formula (4), or may be different}.
[74]
The negative photosensitive resin composition according to [73], wherein the (A) polyfluorene imine precursor is a copolymer of a structural unit represented by the general formulae (4) and (5).
[75]
The negative photosensitive resin composition according to any one of [63] to [74], comprising:
100 parts by mass of the aforementioned (A) polyimide precursor,
0.1 to 30 parts by mass of the above (B) nitrogen-containing compound based on 100 parts by mass of the aforementioned (A) polyfluorene imide precursor, and 0.1 based on 100 parts by mass of the aforementioned (A) polyamido precursor -20 parts by mass of the above (C) photopolymerization initiator.
[76]
A method for producing polyimide, comprising the step of converting the negative-type photosensitive resin composition according to any one of [63] to [75] into polyimide.
[77]
A method for manufacturing a hardened uneven pattern includes:
(1) a step of applying the negative photosensitive resin composition according to any one of [63] to [75] on a substrate to form a photosensitive resin layer on the substrate,
(2) a step of exposing the photosensitive resin layer,
(3) a step of developing the photosensitive resin layer after exposure to form a concave-convex pattern, and
(4) A step of heating the aforementioned uneven pattern to form a hardened uneven pattern.
[Effect of the invention]

根據本發明，可提供一種能夠獲得較高之耐化學品性與解像度，且於高溫保存(high temperature storage)試驗後抑制Cu層之與樹脂層相接之界面產生孔隙之負型感光性樹脂組合物，又，可提供一種使用該負型感光性樹脂組合物之硬化凹凸圖案之形成方法。According to the present invention, it is possible to provide a negative-type photosensitive resin combination capable of obtaining higher chemical resistance and resolution and suppressing pore generation at the interface between the Cu layer and the resin layer after a high temperature storage test. In addition, it is possible to provide a method for forming a hardened uneven pattern using the negative photosensitive resin composition.

以下，對用以實施本發明之形態(以下，簡稱為「實施形態」)進行詳細說明。再者，本發明並不限定於以下之實施形態，可於其主旨之範圍內進行各種變化而實施。
再者，於本說明書全文中，通式中由相同符號所表示之結構於在分子中存在複數個之情形時，可相互相同，或亦可不同。Hereinafter, the form (hereinafter, abbreviated as "embodiment") for implementing this invention is demonstrated in detail. The present invention is not limited to the following embodiments, and can be implemented with various changes within the scope of the gist thereof.
In addition, throughout the specification, the structures represented by the same symbols in the general formula may be the same as or different from each other when there are a plurality of structures in the molecule.

[第一態樣]
對本實施形態之第一態樣進行說明。
＜負型感光性樹脂組合物＞
本實施形態之負型感光性樹脂組合物包含：
(A)聚醯亞胺前驅物；
(B1)活性酯化劑；及
(C)光聚合起始劑。[First aspect]
A first aspect of this embodiment will be described.
<Negative photosensitive resin composition>
The negative photosensitive resin composition of this embodiment includes:
(A) a polyimide precursor;
(B1) an active esterifying agent; and
(C) Photopolymerization initiator.

就獲得較高之解像度之觀點而言，負型感光性樹脂組合物較佳為包含100質量份之(A)聚醯亞胺前驅物、以(A)聚醯亞胺前驅物100質量份為基準之0.1～30質量份之(B1)活性酯化劑、及以(A)聚醯亞胺前驅物100質量份為基準之0.1～20質量份之(C)光聚合起始劑。From the viewpoint of obtaining a 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. 0.1 to 30 parts by mass of the active esterifying agent (B1) and 0.1 to 20 parts by mass of the (C) photopolymerization initiator based on 100 parts by mass of the polyimide precursor (A).

(A)聚醯亞胺前驅物
本實施形態中之(A)聚醯亞胺前驅物為負型感光性樹脂組合物中所含之樹脂成分，藉由實施加熱環化處理而轉換為聚醯亞胺。
聚醯亞胺前驅物較佳為具有下述通式(2)：
[化50]

{式中，X₁ 為4價之有機基，Y₁ 為2價之有機基，n₁ 為2～150之整數，並且R₁ 及R₂ 分別獨立為氫原子、或1價之有機基}
所表示之結構之聚醯胺。(A) Polyfluorene imide precursor (A) The polyfluorene imide precursor in this embodiment is a resin component contained in a negative photosensitive resin composition, and is converted into a polyfluorene by performing a thermal cyclization treatment. Imine.
The polyfluorene imide precursor preferably has the following general formula (2):
[Chemical 50]

{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}
Polyamines of the indicated structure.

R₁ 及R₂ 之至少一者較佳為下述通式(3)：
[化51]

{式中，L₁ 、L₂ 及L₃ 分別獨立為氫原子、或碳數1～3之有機基，並且m₁ 為2～10之整數}所表示之1價之有機基。At least one of R ₁ and R ₂ is preferably the following general formula (3):
[Chemical 51]

[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] represented by a monovalent organic group.

通式(2)中之n₁ 只要為2～150之整數則並無限定，就負型感光性樹脂組合物之感光特性及機械特性之觀點而言，較佳為3～100之整數，更佳為5～70之整數。
就兼顧耐熱性與感光特性之觀點而言，於通式(2)中，X₁ 所表示之4價之有機基較佳為碳數6～40之有機基，更佳為-COOR₁ 基及-COOR₂ 基與-CONH-基互相位於鄰位之芳香族基、或脂環式脂肪族基。作為X₁ 所表示之4價之有機基，具體而言，可列舉含有芳香族環之碳原子數6～40之有機基、例如具有下述通式(20)：
[化52]

{式中，R6為選自由氫原子、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1價之基，l為選自0～2中之整數，m為選自0～3中之整數，並且n為選自0～4中之整數}
所表示之結構之基，但並不限定於該等。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 基就兼顧耐熱性與感光特性之觀點而言較佳。
作為X₁ 基，於上述式(20)所表示之結構之中，下述式(20A)或(20B)：
[化53]

所表示之結構就耐化學品性、解像度、及高溫保存試驗後之孔隙抑制之觀點而言更佳，尤佳為下述式(20a)或(20b)：
[化54]

[化55]

所表示之結構。N ₁ in the general formula (2) is not limited as long as it is an integer of 2 to 150. In terms of the photosensitive characteristics and mechanical characteristics of the negative photosensitive resin composition, it is preferably an integer of 3 to 100, more preferably It is preferably an integer from 5 to 70.
From the viewpoint of considering both heat resistance and photosensitivity, in the general formula (2), the tetravalent organic group represented by X ₁ is preferably an organic group having 6 to 40 carbon atoms, more preferably a -COOR ₁ group and An aromatic group or an alicyclic aliphatic group in which the -COOR ₂ group and the -CONH- group are adjacent to each other. Specific examples of the tetravalent organic group represented by X ₁ include an organic group having 6 to 40 carbon atoms, which contains an aromatic ring, and has, for example, the following general formula (20):
[Chemical 52]

{Wherein R6 is a monovalent 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 l is selected from 0 to 2 An integer in which m is an integer selected from 0 to 3 and n is an integer selected from 0 to 4}
The basis of the structure shown is not limited to these. 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 formula (20) is preferable from the viewpoint of considering both heat resistance and light-sensitive properties.
As the X ₁ group, among the structures represented by the above formula (20), the following formula (20A) or (20B):
[Chem 53]

The structure represented is more preferable from the viewpoints of chemical resistance, resolution, and pore suppression after a high-temperature storage test, and particularly preferably the following formula (20a) or (20b):
[Chemical 54]

[Chem 55]

The structure represented.

就兼顧耐熱性與感光特性之觀點而言，於上述通式(2)中，Y₁ 所表示之2價之有機基較佳為碳數6～40之芳香族基，例如可列舉下述式(21)：
[化56]

{式中，R6為選自由氫原子、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1價之基，並且n為選自0～4中之整數}
所表示之結構，但並不限定於該等。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 基就兼顧耐熱性及感光特性之觀點而言較佳。
作為Y₁ 基，於上述式(21)所表示之結構之中，下述式(21A)或(21B)：
[化57]

所表示之結構就耐化學品性、解像度、及高溫保存試驗後之孔隙抑制之觀點而言較佳，尤佳為下述式(21b)或下述式(7)：
[化58]

[化59]

(式中，R₉ ～R₁₂ 為氫原子或碳數1～4之1價之脂肪族基，可相互相同，亦可不同)
所表示之結構。From the viewpoint of considering both heat resistance and photosensitivity, in the general formula (2), the divalent organic group represented by Y ₁ is preferably an aromatic group having 6 to 40 carbon atoms. For example, the following formula can be given: (twenty one):
[Chemical 56]

{Wherein R6 is a monovalent 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 to Integer in 4}
The structures indicated are not limited to these. The structure of Y ₁ may be one type or a combination of two or more types. The Y ₁ group having the structure represented by the formula (21) is preferable from the viewpoint of considering both heat resistance and light-sensitive properties.
As the Y ₁ group, among the structures represented by the above formula (21), the following formula (21A) or (21B):
[Chemical 57]

The structure represented is preferable from the viewpoints of chemical resistance, resolution, and pore suppression after a high-temperature storage test, and particularly preferably the following formula (21b) or the following formula (7):
[Chem 58]

[Chemical 59]

(Wherein R ₉ to R ₁₂ are a hydrogen atom or a monovalent aliphatic group having 1 to 4 carbon atoms, and may be the same as or different from each other)
The structure represented.

上述通式(3)中之L₁ 較佳為氫原子或甲基，就感光特性之觀點而言，L₂ 及L₃ 較佳為氫原子。又，就感光特性之觀點而言，m₁ 為2以上且10以下之整數，較佳為2以上且4以下之整數。In the general formula (3), L _{1 is} preferably a hydrogen atom or a methyl group, and from the viewpoint of photosensitivity, L ₂ and L _{3 are} preferably a hydrogen atom. Moreover, m ₁ is an integer of 2 or more and 10 or less from a viewpoint of a photosensitive characteristic, Preferably it is an integer of 2 or more and 4 or less.

於一實施形態中，(A)聚醯亞胺前驅物較佳為具有下述通式(4)：
[化60]

{式中，R₁ 、R₂ 、及n₁ 係上述所定義者}
所表示之結構單元之聚醯亞胺前驅物。
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1價之有機基。藉由使(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提高。In one embodiment, (A) the polyfluorene imide precursor preferably has the following general formula (4):
[Chemical 60]

{Wherein R ₁ , R ₂ , and n ₁ are as defined above}
Polyimide precursors of the indicated structural units.
In the general formula (4), at least one of R ₁ and R ₂ is more preferably a monovalent organic group represented by the general formula (3). When the (A) polyfluorene imide precursor includes the polyfluorene imide precursor represented by the general formula (4), the effect of resolving power is improved in particular.

於一實施形態中，(A)聚醯亞胺前驅物較佳為具有下述通式(5)：
[化61]

{式中，R₁ 、R₂ 、及n₁ 係上述所定義者}
所表示之結構單元之聚醯亞胺前驅物。
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1價之有機基。藉由使(A)聚醯亞胺前驅物除了通式(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進一步提高。
該等之中，就耐化學品性、解像度、及高溫保存試驗後之孔隙抑制之觀點而言，尤佳為(A)聚醯亞胺前驅物同時包含上述通式(4)與(5)所表示之結構單元，或者為上述通式(4)與(5)所表示之結構單元之共聚物。於(A)聚醯亞胺前驅物為通式(4)與(5)所表示之結構單元之共聚物之情形時，一者之式中之R₁ 、R₂ 、及n₁ 分別可與另一者之式中之R₁ 、R₂ 、及n₁ 相同，亦可不同。In one embodiment, (A) the polyfluorene imide precursor preferably has the following general formula (5):
[Chem 61]

{Wherein R ₁ , R ₂ , and n ₁ are as defined above}
Polyimide precursors of the indicated structural units.
In the general formula (5), at least one of R ₁ and R ₂ is more preferably a monovalent organic group represented by the general formula (3). By making the (A) polyfluorene imide precursor in addition to the polyfluorene imide precursor represented by the general formula (4), the polyfluorene imide precursor represented by the general formula (5) is also included, especially the resolution The effect of sex is further enhanced.
Among these, from the viewpoints of chemical resistance, resolution, and porosity suppression after a high-temperature storage test, it is particularly preferred that the (A) polyimide precursor includes both the general formulae (4) and (5). The structural unit represented may be a copolymer of the structural units represented by the general formulae (4) and (5). In the case where (A) the polyimide precursor is a copolymer of a structural unit represented by the general formulae (4) and (5), R ₁ , R ₂ , and n _{1 in} one formula may be respectively R ₁ , R ₂ , and n ₁ in the other formula are the same or different.

(A)聚醯亞胺前驅物之製備方法
聚醯亞胺前驅物可藉由如下方式獲得：首先使包含上述通式(2)中之4價之有機基X₁ 之四羧酸二酐、與具有光聚合性之不飽和雙鍵之醇類及任意不具有不飽和雙鍵之醇類進行反應，製備部分酯化之四羧酸(以下，亦稱為酸/酯體)後，使其與包含上述通式(2)中之2價之有機基Y₁ 之二胺類進行醯胺縮聚。(A) Preparation method of polyimide precursor The polyimide precursor can be obtained by firstly making a tetracarboxylic dianhydride containing the tetravalent organic group X _{1 in} the above general formula (2), It reacts with alcohols having photopolymerizable unsaturated double bonds and any alcohols having unsaturated double bonds to prepare a partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid / ester), and then Ammonium polycondensation is carried out with diamines containing the divalent organic group Y ₁ in the general formula (2).

(酸/酯體之製備)
於本實施形態中，作為適宜用於製備(A)聚醯亞胺前驅物之包含4價之有機基X₁ 之四羧酸二酐，以上述通式(20)所示之四羧酸二酐為代表，例如可列舉：均苯四甲酸二酐、二苯醚-3,3',4,4'-四羧酸二酐、二苯甲酮-3,3',4,4'-四羧酸二酐、聯苯-3,3',4,4'-四羧酸二酐、二苯基碸-3,3',4,4'-四羧酸二酐、二苯基甲烷-3,3',4,4'-四羧酸二酐、2,2-雙(3,4-鄰苯二甲酸酐)丙烷、2,2-雙(3,4-鄰苯二甲酸酐)-1,1,1,3,3,3-六氟丙烷等，較佳為可列舉：均苯四甲酸二酐、二苯醚-3,3',4,4'-四羧酸二酐、二苯甲酮-3,3',4,4'-四羧酸二酐、聯苯-3,3',4,4'-四羧酸二酐，但並不限定於該等。又，該等當然可單獨使用，亦可混合2種以上使用。(Preparation of acid / ester)
In this embodiment, as a tetracarboxylic dianhydride containing a tetravalent organic group X ₁ suitable for preparing (A) a polyimide precursor, the tetracarboxylic acid dianhydride represented by the above general formula (20) Anhydride is representative, for example, pyromellitic dianhydride, diphenyl ether-3,3 ', 4,4'-tetracarboxylic dianhydride, benzophenone-3,3', 4,4'- Tetracarboxylic dianhydride, biphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, diphenylfluorene-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 and the like, preferably, they can include: pyromellitic dianhydride, diphenyl ether-3,3 ', 4,4'-tetracarboxylic acid di Anhydride, benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride, biphenyl-3,3', 4,4'-tetracarboxylic dianhydride, but it is not limited to these. These can be used alone or in combination of two or more.

於本實施形態中，作為適宜用於製備(A)聚醯亞胺前驅物之具有光聚合性之不飽和雙鍵之醇類，例如可列舉：2-丙烯醯氧基乙醇、1-丙烯醯氧基-3-丙醇、2-丙烯醯胺乙醇、羥甲基乙烯基酮、2-羥基乙基乙烯基酮、丙烯酸2-羥基-3-甲氧基丙酯、丙烯酸2-羥基-3-丁氧基丙酯、丙烯酸2-羥基-3-苯氧基丙酯、丙烯酸2-羥基-3-丁氧基丙酯、丙烯酸2-羥基-3-第三丁氧基丙酯、丙烯酸2-羥基-3-環己氧基丙酯、2-甲基丙烯醯氧基乙醇、1-甲基丙烯醯氧基-3-丙醇、2-甲基丙烯醯胺乙醇、羥甲基乙烯基酮、2-羥基乙基乙烯基酮、甲基丙烯酸2-羥基-3-甲氧基丙酯、甲基丙烯酸2-羥基-3-丁氧基丙酯、甲基丙烯酸2-羥基-3-苯氧基丙酯、甲基丙烯酸2-羥基-3-丁氧基丙酯、甲基丙烯酸2-羥基-3-第三丁氧基丙酯、甲基丙烯酸2-羥基-3-環己氧基丙酯等。In this embodiment, as the alcohol having an unsaturated double bond having photopolymerization suitable for preparing the (A) polyfluorene imide precursor, for example, 2-propenyloxyethanol and 1-propenefluorene Oxy-3-propanol, 2-propenylamine ethanol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3 acrylate -Butoxypropyl, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-third butoxypropyl acrylate, acrylic acid 2 -Hydroxy-3-cyclohexyloxypropyl, 2-methacryloxyethanol, 1-methacryloxy-3-propanol, 2-methacrylamine ethanol, methylol vinyl Ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-methacrylate Phenoxypropyl, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-third butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyl methacrylate Propyl ester, etc.

亦可向上述具有光聚合性之不飽和雙鍵之醇類中混合一部分例如甲醇、乙醇、正丙醇、異丙醇、正丁醇、第三丁醇、1-戊醇、2-戊醇、3-戊醇、新戊醇、1-庚醇、2-庚醇、3-庚醇、1-辛醇、2-辛醇、3-辛醇、1-壬醇、三乙二醇單甲醚、三乙二醇單乙醚、四乙二醇單甲醚、四乙二醇單乙醚、苄醇等不具有不飽和雙鍵之醇類而使用。A part of the photopolymerizable unsaturated double bond alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, third butanol, 1-pentanol, and 2-pentanol can also be mixed. , 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol mono Methyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, and benzyl alcohol are used without having an unsaturated double bond.

又，作為聚醯亞胺前驅物，亦可將僅以上述不具有不飽和雙鍵之醇類製備之非感光性聚醯亞胺前驅物與感光性聚醯亞胺前驅物混合而使用。就解像性之觀點而言，非感光性聚醯亞胺前驅物較佳為以感光性聚醯亞胺前驅物100質量份為基準為200質量份以下。Further, as the polyimide precursor, a non-photosensitive polyimide precursor prepared using only the above-mentioned alcohol having no unsaturated double bond and a photosensitive polyimide precursor may be mixed and used. From the viewpoint of resolvability, the non-photosensitive polyfluorene imide precursor is preferably 200 parts by mass or less based on 100 parts by mass of the photosensitive polyfluorene imide precursor.

將上述較佳之四羧酸二酐與上述醇類於吡啶等鹼性觸媒之存在下，於如下所述之溶劑中，以溫度20～50℃攪拌溶解4～10小時進行混合，藉此可進行酸酐之酯化反應，獲得所需之酸/酯體。The above-mentioned preferred tetracarboxylic dianhydride and the above-mentioned alcohols are mixed in a solvent described below under stirring at a temperature of 20 to 50 ° C for 4 to 10 hours for mixing, thereby enabling the mixing An esterification reaction of an acid anhydride is performed to obtain a desired acid / ester body.

(聚醯亞胺前驅物之製備)
於冰浴冷卻下向上述酸/酯體(典型而言為下述溶劑中之溶液)中投入混合適當之脫水縮合劑、例如二環己基碳二醯亞胺、1-乙氧基羰基-2-乙氧基-1,2-二氫喹啉、1,1-羰基二氧基-二-1,2,3-苯并三唑、N,N'-二丁二醯亞胺基碳酸酯等而將酸/酯體製成聚酸酐後，向其中滴加投入使本實施形態中較佳地使用之包含2價之有機基Y₁ 之二胺類另外溶解或分散於溶劑而成者，進行醯胺縮聚，藉此可獲得目標之聚醯亞胺前驅物。作為代替方案，針對上述酸/酯體，使用亞硫醯氯等將酸部分進行醯氯化後，於吡啶等鹼存在下與二胺化合物反應，藉此可獲得目標之聚醯亞胺前驅物。(Preparation of polyimide precursor)
Add the appropriate dehydration condensing agent, such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2, to the above-mentioned acid / ester body (typically, the solution in the solvent below) under cooling in an ice bath. -Ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N'-dibutyldifluorenimide carbonate After the acid / ester body is made into a polyanhydride, the diamines containing the divalent organic group Y ₁ which is preferably used in this embodiment are added dropwise thereto, and then dissolved or dispersed in a solvent, The fluorene polycondensation is performed, whereby the target polyfluorene imine is obtained. As an alternative, for the above acid / ester, the acid part is chlorinated with thionyl chloride, etc., and then reacted with a diamine compound in the presence of a base such as pyridine, thereby obtaining the target polyimide precursor .

作為於本實施形態中較佳地使用之包含2價之有機基Y₁ 之二胺類，以具有上述通式(21)所示之結構之二胺為代表，例如可列舉：對苯二胺、間苯二胺、4,4-二胺基二苯醚、3,4'-二胺基二苯醚、3,3'-二胺基二苯醚、4,4'-二胺基二苯硫醚、3,4'-二胺基二苯硫醚、3,3'-二胺基二苯硫醚、4,4'-二胺基二苯基碸、3,4'-二胺基二苯基碸、3,3'-二胺基二苯基碸、4,4'-二胺基聯苯、3,4'-二胺基聯苯、3,3'-二胺基聯苯、4,4'-二胺基二苯甲酮、3,4'-二胺基二苯甲酮、3,3'-二胺基二苯甲酮、4,4'-二胺基二苯基甲烷、3,4'-二胺基二苯基甲烷、3,3'-二胺基二苯基甲烷、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(3-胺基苯氧基)苯基]碸、4,4-雙(4-胺基苯氧基)聯苯、4,4-雙(3-胺基苯氧基)聯苯、雙[4-(4-胺基苯氧基)苯基]醚、雙[4-(3-胺基苯氧基)苯基]醚、1,4-雙(4-胺基苯基)苯、1,3-雙(4-胺基苯基)苯、9,10-雙(4-胺基苯基)蒽、2,2-雙(4-胺基苯基)丙烷、2,2-雙(4-胺基苯基)六氟丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷、1,4-雙(3-胺基丙基二甲基矽烷基)苯、鄰聯甲苯胺碸、9,9-雙(4-胺基苯基)茀、及該等之苯環上之氫原子之一部分經甲基、乙基、羥基甲基、羥基乙基、鹵素等取代而成者、例如3,3'-二甲基-4,4'-二胺基聯苯、2,2'-二甲基-4,4'-二胺基聯苯、3,3'-二甲基-4,4'-二胺基二苯基甲烷、2,2'-二甲基-4,4'-二胺基二苯基甲烷、3,3'-二甲氧基-4,4'-二胺基聯苯、3,3'-二氯-4,4'-二胺基聯苯、及其等之混合物等，但並不限定於其。As the diamines containing a divalent organic group Y ₁ which is preferably used in this embodiment, diamines having a structure represented by the general formula (21) are represented, and examples thereof include p-phenylenediamine , M-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminediphenyl Phenylsulfide, 3,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 4,4'-diaminodiphenylphosphonium, 3,4'-diamine Diphenylphosphonium, 3,3'-diaminodiphenylphosphonium, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl Benzene, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminedione 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] fluorene, bis [4- (3-aminophenoxy) phenyl] pyrene, 4,4-bis (4-aminophenoxy) biphenyl, 4,4-bis (3-aminophenoxy) biphenyl, bis [ 4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy ) Phenyl] ether, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 9,10-bis (4-aminophenyl) anthracene , 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) Phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1,4-bis (3-aminopropyldimethylsilyl) benzene, o- Part of the hydrogen atoms on the benzylamine hydrazone, 9,9-bis (4-aminophenyl) fluorene, and benzene ring are replaced by methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen, etc. For example, 3,3'-dimethyl-4,4'-diaminobiphenyl, 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, and the like are not limited thereto.

於醯胺縮聚反應結束後，將該反應液中共存之脫水縮合劑之吸水副產物視需要過濾分離後，將水、脂肪族低級醇、或其等之混合液等不良溶劑投入至所得之聚合物成分中，析出聚合物成分，進而反覆進行再溶解、再沈澱析出操作等，藉此將聚合物純化，並進行真空乾燥，單離目標之聚醯亞胺前驅物。為了提高純化度，亦可使該聚合物之溶液通過將陰離子及/或陽離子交換樹脂以適當之有機溶劑膨潤後進行填充之管柱而去除離子性雜質。After the ammonium polycondensation reaction is completed, the water absorption by-products of the dehydration condensation agent coexisting in the reaction solution are filtered and separated as necessary, and poor solvents such as water, aliphatic lower alcohol, or a mixed solution thereof are added to the obtained polymerization Among the chemical components, the polymer component is precipitated, and the polymer is then repeatedly dissolved, re-precipitated, and the like, thereby purifying the polymer and vacuum-drying it to separate the target polyimide precursor. In order to improve the degree of purification, the solution of the polymer may be passed through a column filled with an anion and / or cation exchange resin with an appropriate organic solvent and then filled to remove ionic impurities.

上述(A)聚醯亞胺前驅物之分子量於以利用凝膠滲透層析法之聚苯乙烯換算重量平均分子量進行測定之情形時，較佳為8,000～150,000，更佳為9,000～50,000。於重量平均分子量為8,000以上之情形時，機械物性良好，於為150,000以下之情形時，於顯影液中之分散性良好，凹凸圖案之解像性能良好。作為凝膠滲透層析法之展開溶劑，推薦四氫呋喃、及N-甲基-2-吡咯啶酮。又，重量平均分子量係由使用標準單分散聚苯乙烯所製成之校準曲線求出。作為標準單分散聚苯乙烯，推薦自昭和電工公司製造之有機溶劑系標準試樣STANDARD SM-105中進行選擇。When the molecular weight of the polyamidoimide precursor (A) is measured by a polystyrene-equivalent weight average molecular weight by gel permeation chromatography, the molecular weight is preferably 8,000 to 150,000, more preferably 9,000 to 50,000. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, and when it is 150,000 or less, the dispersibility in the developer is good, and the resolution performance of the uneven pattern is good. As a developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. The weight average molecular weight was determined from a calibration curve using a standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from the organic solvent series standard sample STANDARD SM-105 manufactured by Showa Denko Corporation.

(B1)活性酯化劑
本實施形態中之(B1)活性酯化劑只要為可將羧酸或羧酸酯等轉換為活性較高之酯化合物之化合物則並無限定。具體而言，可例示：碳酸雙(五氟苯基)酯、碳酸雙(4-硝基苯基)酯、二(N-丁二醯亞胺基)碳酸酯、五氟苯酚、三氟乙酸4-硝基苯酯、1-羥基-7-氮雜苯并三唑等。
其中，就Cu孔隙抑制之觀點而言，較佳為1-羥基-7-氮雜苯并三唑、及五氟苯酚。
若使用上述活性酯化劑，則可獲得良好之耐化學品性與解像性、及Cu孔隙抑制效果。雖受理論約束，但關於可獲得良好之耐化學品性之理由，認為藉由使用活性酯化劑，於加熱中以更低溫進行醯亞胺化，藉此容易進行聚醯亞胺之堆積，而使耐化學品性提高。
又，可獲得良好之解像性之理由雖不明確，但認為其原因在於：加熱前之活性酯化劑藉由與聚醯亞胺前驅物進行調配，更容易溶解於顯影時之顯影液而抑制殘渣。此外，顯示Cu孔隙抑制效果之理由雖未確定，但認為活性酯化劑於加熱中產生極性官能基(羥基等)等，該羥基與Cu離子強烈相互作用，抑制Cu之擴散，結果抑制Cu孔隙。(B1) Active esterifying agent The (B1) active esterifying agent in this embodiment is not limited as long as it is a compound capable of converting a carboxylic acid or a carboxylic acid ester into an ester compound having a higher activity. Specific examples include bis (pentafluorophenyl) carbonate, bis (4-nitrophenyl) carbonate, bis (N-butanefluorenedimino) carbonate, pentafluorophenol, and trifluoroacetic acid. 4-nitrophenyl ester, 1-hydroxy-7-azabenzotriazole and the like.
Among these, from the viewpoint of Cu pore suppression, 1-hydroxy-7-azabenzotriazole and pentafluorophenol are preferred.
When the above active esterifying agent is used, good chemical resistance and resolution, and Cu pore suppression effect can be obtained. Although bound by theory, for the reason that good chemical resistance can be obtained, it is believed that by using an active esterifying agent, the fluorene imidization can be performed at a lower temperature during heating, thereby facilitating the accumulation of polyfluorene. This improves chemical resistance.
Although the reason for obtaining good resolution is not clear, it is thought that the reason is that the active esterifying agent before heating can be more easily dissolved in the developing solution during development by blending with the polyimide precursor. Suppresses residue. In addition, although the reason for showing the effect of suppressing the pores of Cu has not been determined, it is believed that the active esterification agent generates polar functional groups (such as hydroxyl groups) during heating. This hydroxyl group strongly interacts with Cu ions, inhibits the diffusion of Cu, and consequently suppresses the pores of Cu. .

負型感光性樹脂組合物中之上述活性酯化劑相對於上述(A)聚醯亞胺前驅物100質量份，較佳為0.1～30質量份，更佳為1質量份以上且15質量份以下。藉由相對於(A)聚醯亞胺前驅物100質量份，於0.1質量份以上且30質量份以下之範圍內進行調配，可獲得Cu孔隙抑制效果、解像性提高及耐化學品性提高之效果尤其優異之負型感光性樹脂組合物。The active esterifying agent in the negative photosensitive resin composition is preferably 0.1 to 30 parts by mass, more preferably 1 part by mass or more and 15 parts by mass, with respect to 100 parts by mass of the (A) polyimide precursor. the following. By blending 100 mass parts of (A) polyfluorene imide precursor in a range of 0.1 mass parts or more and 30 mass parts or less, the effect of suppressing Cu pores, improving resolution, and improving chemical resistance can be obtained. The negative photosensitive resin composition is particularly excellent in effect.

(C)光聚合起始劑
對本實施形態中使用之(C)光聚合起始劑進行說明。作為光聚合起始劑，較佳為光自由基聚合起始劑，可較佳地列舉：二苯甲酮、鄰苯甲醯基苯甲酸甲酯、4-苯甲醯基-4'-甲基二苯基酮、二苄基酮、茀酮等二苯甲酮衍生物、2,2'-二乙氧基苯乙酮、2-羥基-2-甲基苯丙酮、1-羥基環己基苯基酮等苯乙酮衍生物、9-氧硫、2-甲基-9-氧硫、2-異丙基-9-氧硫、二乙基-9-氧硫等9-氧硫衍生物、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-(O-甲氧基羰基)肟、1-苯基-1,2-丙二酮-2-(O-甲氧基羰基)肟、1-苯基-1,2-丙二酮-2-(O-乙氧基羰基)肟、1-苯基-1,2-丙二酮-2-(O-苯甲醯基)肟、1,3-二苯基丙三酮-2-(O-乙氧基羰基)肟、1-苯基-3-乙氧基丙三酮-2-(O-苯甲醯基)肟等肟類、N-苯基甘胺酸等N-芳基甘胺酸類、全氯苯甲醯等過氧化物類、芳香族聯咪唑類、二茂鈦類、α-(正辛烷磺醯氧基亞胺基)-4-甲氧基苄基氰化物等光酸產生劑類等，但並不限定於該等。上述光聚合起始劑之中，尤其就光感度之觀點而言，更佳為肟類。(C) Photopolymerization initiator The (C) photopolymerization initiator used in this embodiment will be described. As the photopolymerization initiator, a photoradical polymerization initiator is preferable, and benzophenone, methyl o-benzoyl benzoate, 4-benzyl-4'-methyl Benzophenone derivatives such as diphenyl ketone, dibenzyl ketone, fluorenone, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylphenylacetone, 1-hydroxycyclohexyl Acetophenone derivatives such as phenylketone, 9-oxysulfur 2-methyl-9-oxysulfur , 2-isopropyl-9-oxysulfur Diethyl-9-oxysulfur 9-oxysulfur Derivatives, Benzophenone, Benzophenone dimethyl ketal, Benzophenone derivatives such as Benzophenone-β-methoxyethyl acetal, Benzoin derivatives such as benzoin, 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-benzylidene) oxime, 1,3- Diphenylglycerone-2- (O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxyglycerone-2- (O-benzylidene) oxime, N- N-arylglycines such as phenylglycine, peroxides such as perchlorobenzidine, aromatic biimidazoles, titanocene, α- (n-octanesulfonyloxyimino) Photoacid generators such as 4-methoxybenzyl cyanide and the like are not limited thereto. Among the above-mentioned photopolymerization initiators, especially from the viewpoint of photosensitivity, oximes are more preferable.

負型感光性樹脂組合物中之(C)光聚合起始劑之調配量相對於(A)聚醯亞胺前驅物100質量份，較佳為0.1質量份以上且20質量份以下，更佳為1質量份以上且8質量份以下。就光感度或圖案化性之觀點而言，上述調配量為0.1質量份以上，就負型感光性樹脂組合物之硬化後之感光性樹脂層之物性之觀點而言，上述調配量為20質量份以下。The blending amount of the (C) photopolymerization initiator in the negative photosensitive resin composition is more preferably 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polyimide precursor (A). It is 1 part by mass or more and 8 parts by mass or less. From the viewpoint of light sensitivity or patternability, the above-mentioned blending amount is 0.1 parts by mass or more, and from the viewpoint of physical properties of the photosensitive resin layer after curing of the negative photosensitive resin composition, the above-mentioned blending amount is 20 masses. The following.

本實施形態之負型感光性樹脂組合物可進而含有上述(A)～(C)成分以外之成分。作為(A)～(C)成分以外之成分，並無限定，可列舉：溶劑、含氮雜環化合物、受阻酚化合物、有機鈦化合物、接著助劑、增感劑、光聚合性不飽和單體、熱聚合抑制劑等。
其中，作為任意成分之含氮雜環化合物為下述第五態樣中說明之「含氮化合物」以外之化合物。The negative-type photosensitive resin composition according to this embodiment may further contain components other than the components (A) to (C). The components other than the components (A) to (C) are not limited, and examples thereof include solvents, nitrogen-containing heterocyclic compounds, hindered phenol compounds, organic titanium compounds, adhesion promoters, sensitizers, and photopolymerizable unsaturated monomers. And thermal polymerization inhibitors.
The nitrogen-containing heterocyclic compound as an optional component is a compound other than the "nitrogen-containing compound" described in the fifth aspect below.

溶劑
作為溶劑，可列舉：醯胺類、亞碸類、脲類、酮類、酯類、內酯類、醚類、鹵化烴類、烴類、醇類等，例如可使用N-甲基-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、二甲基亞碸、四甲基脲、丙酮、甲基乙基酮、甲基異丁基酮、環戊酮、環己酮、乙酸甲酯、乙酸乙酯、乙酸丁酯、草酸二乙酯、乳酸乙酯、乳酸甲酯、乳酸丁酯、γ-丁內酯、丙二醇單甲醚乙酸酯、丙二醇單甲醚、苄醇、苯乙二醇、四氫糠醇、乙二醇二甲醚、二乙二醇二甲醚、四氫呋喃、啉、二氯甲烷、1,2-二氯乙烷、1,4-二氯丁烷、氯苯、鄰二氯苯、苯甲醚、己烷、庚烷、苯、甲苯、二甲苯、均三甲苯等。其中，就樹脂之溶解性、樹脂組合物之穩定性、及對基板之接著性之觀點而言，較佳為N-甲基-2-吡咯啶酮、二甲基亞碸、四甲基脲、乙酸丁酯、乳酸乙酯、γ-丁內酯、丙二醇單甲醚乙酸酯、丙二醇單甲醚、二乙二醇二甲醚、苄醇、苯乙二醇、及四氫糠醇。Examples of the solvent include amines, fluorenes, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and alcohols. For example, N-methyl- 2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfine, tetramethylurea, acetone, methyl ethyl ketone, methyl isopropyl Butyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl Ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 1,2-di Ethyl chloride, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene and the like. Among these, from the viewpoints of the solubility of the resin, the stability of the resin composition, and the adhesiveness to the substrate, N-methyl-2-pyrrolidone, dimethylsulfinium, and tetramethylurea are preferred. , Butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, benzyl alcohol, phenyl ethylene glycol, and tetrahydrofurfuryl alcohol.

於此種溶劑之中，尤佳為完全溶解生成聚合物者，例如可列舉：N-甲基-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、二甲基亞碸、四甲基脲、γ-丁內酯等。Among such solvents, those which are completely dissolved to form a polymer are particularly preferred. Examples include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and N, N-dimethyl. Formamidine, dimethylmethylene, tetramethylurea, γ-butyrolactone, and the like.

於本實施形態之感光性樹脂組合物中，溶劑之使用量相對於(A)聚醯亞胺前驅物100質量份，較佳為100～1000質量份，更佳為120～700質量份，進而較佳為125～500質量份之範圍。In the photosensitive resin composition of this embodiment, the amount of the solvent to be used is preferably 100 to 1,000 parts by mass, more preferably 120 to 700 parts by mass, with respect to 100 parts by mass of the polyimide precursor (A). The range of 125 to 500 parts by mass is preferred.

含氮雜環化合物
於使用本實施形態之感光性樹脂組合物於包含銅或銅合金之基板上形成硬化膜之情形時，為了抑制銅上之變色，負型感光性樹脂組合物可任意包含含氮雜環化合物。作為含氮雜環化合物，可列舉唑化合物、及嘌呤衍生物等。In the case where the nitrogen-containing heterocyclic compound is used to form a cured film on a substrate containing copper or a copper alloy using the photosensitive resin composition of this embodiment, in order to suppress discoloration on copper, the negative photosensitive resin composition may optionally contain Nitrogen heterocyclic compounds. Examples of the nitrogen-containing heterocyclic compound include an azole compound and a purine derivative.

作為唑化合物，可列舉：1H-三唑、5-甲基-1H-三唑、5-乙基-1H-三唑、4,5-二甲基-1H-三唑、5-苯基-1H-三唑、4-第三丁基-5-苯基-1H-三唑、5-羥基苯基-1H-三唑、苯基三唑、對乙氧基苯基三唑、5-苯基-1-(2-二甲胺基乙基)三唑、5-苄基-1H-三唑、羥基苯基三唑、1,5-二甲基三唑、4,5-二乙基-1H-三唑、1H-苯并三唑、2-(5-甲基-2-羥基苯基)苯并三唑、2-[2-羥基-3,5-雙(α,α-二甲基苄基)苯基]-苯并三唑、2-(3,5-二-第三丁基-2-羥基苯基)苯并三唑、2-(3-第三丁基-5-甲基-2-羥基苯基)-苯并三唑、2-(3,5-二-第三戊基-2-羥基苯基)苯并三唑、2-(2'-羥基-5'-第三辛基苯基)苯并三唑、羥基苯基苯并三唑、甲苯并三唑、5-甲基-1H-苯并三唑、4-甲基-1H-苯并三唑、4-羧基-1H-苯并三唑、5-羧基-1H-苯并三唑、1H-四唑、5-甲基-1H-四唑、5-苯基-1H-四唑、5-胺基-1H-四唑、1-甲基-1H-四唑等。Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, and 5-phenyl- 1H-triazole, 4-tert-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-benzene -1- (2-dimethylaminoethyl) triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl -1H-triazole, 1H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-di Methylbenzyl) phenyl] -benzotriazole, 2- (3,5-di-third-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-thirdbutyl-5 -Methyl-2-hydroxyphenyl) -benzotriazole, 2- (3,5-di-tertiarypentyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '-Third octylphenyl) benzotriazole, hydroxyphenylbenzotriazole, tolutriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole , 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 and the like.

尤佳為可列舉甲苯并三唑、5-甲基-1H-苯并三唑、及4-甲基-1H-苯并三唑。又，該等唑化合物可使用1種，亦可使用2種以上之混合物。Particularly preferred examples include toluenetriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or as a mixture of two or more.

作為嘌呤衍生物之具體例，可列舉：嘌呤、腺嘌呤、鳥嘌呤、次黃嘌呤、黃嘌呤、可可鹼、咖啡因、尿酸、異鳥嘌呤、2,6-二胺基嘌呤、9-甲基腺嘌呤、2-羥基腺嘌呤、2-甲基腺嘌呤、1-甲基腺嘌呤、N-甲基腺嘌呤、N,N-二甲基腺嘌呤、2-氟腺嘌呤、9-(2-羥基乙基)腺嘌呤、鳥嘌呤肟、N-(2-羥基乙基)腺嘌呤、8-胺基腺嘌呤、6-胺基-8-苯基-9H-嘌呤、1-乙基腺嘌呤、6-乙基胺基嘌呤、1-苄基腺嘌呤、N-甲基鳥嘌呤、7-(2-羥基乙基)鳥嘌呤、N-(3-氯苯基)鳥嘌呤、N-(3-乙基苯基)鳥嘌呤、2-氮雜腺嘌呤、5-氮雜腺嘌呤、8-氮雜腺嘌呤、8-氮雜鳥嘌呤、8-氮雜嘌呤、8-氮雜黃嘌呤、8-氮雜次黃嘌呤等及其衍生物。Specific examples of the purine derivative include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-formyl Base adenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N, N-dimethyladenine, 2-fluoroadenine, 9- ( 2-hydroxyethyl) adenine, guanine oxime, N- (2-hydroxyethyl) adenine, 8-amino adenine, 6-amino-8-phenyl-9H-purine, 1-ethyl Adenine, 6-ethylaminopurine, 1-benzyl adenine, N-methylguanine, 7- (2-hydroxyethyl) guanine, N- (3-chlorophenyl) guanine, N -(3-ethylphenyl) guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-aza Xanthine, 8-azahypoxanthine and its derivatives.

感光性樹脂組合物含有上述唑化合物或嘌呤衍生物之情形時之調配量較佳為相對於(A)聚醯亞胺前驅物100質量份為0.1～20質量份，就光感度特性之觀點而言，更佳為0.5～5質量份。於唑化合物之相對於(A)聚醯亞胺前驅物100質量份之調配量為0.1質量份以上之情形時，於銅或銅合金上形成本實施形態之感光性樹脂組合物之情形時銅或銅合金表面之變色得到抑制，另一方面，於為20質量份以下之情形時，光感度優異。When the photosensitive resin composition contains the above-mentioned azole compound or purine derivative, the blending amount is preferably 0.1 to 20 parts by mass based on 100 parts by mass of the polyimide precursor (A). From the viewpoint of light sensitivity characteristics, In other words, it is more preferably 0.5 to 5 parts by mass. When the compounding amount of the azole compound relative to 100 parts by mass of the (A) polyfluorene imide precursor is 0.1 parts by mass or more, when the photosensitive resin composition of this embodiment is formed on copper or a copper alloy, copper Or the discoloration of the surface of a copper alloy is suppressed, and when it is 20 parts by mass or less, the light sensitivity is excellent.

受阻酚化合物
又，為了抑制銅表面上之變色，負型感光性樹脂組合物可任意包含受阻酚化合物。作為受阻酚化合物，可列舉：2,6-二-第三丁基-4-甲基苯酚、2,5-二-第三丁基-對苯二酚、3-(3,5-二-第三丁基-4-羥基苯基)丙酸十八烷基酯、3-(3,5-二-第三丁基-4-羥基苯基)丙酸異辛酯、4,4'-亞甲基雙(2,6-二-第三丁基苯酚)、4,4'-硫代-雙(3-甲基-6-第三丁基苯酚)、4,4'-亞丁基-雙(3-甲基-6-第三丁基苯酚)、三乙二醇-雙[3-(3-第三丁基-5-甲基-4-羥基苯基)丙酸酯]、1,6-己二醇-雙[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、2,2-硫代-二伸乙基雙[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、N,N'-六亞甲基雙(3,5-二-第三丁基-4-羥基-苯丙醯胺)、2,2'-亞甲基-雙(4-甲基-6-第三丁基苯酚)、2,2'-亞甲基-雙(4-乙基-6-第三丁基苯酚)、季戊四醇-四[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、異氰尿酸三-(3,5-二-第三丁基-4-羥基苄基)酯、1,3,5-三甲基-2,4,6-三(3,5-二-第三丁基-4-羥基苄基)苯、1,3,5-三(3-羥基-2,6-二甲基-4-異丙基苄基)-1,3,5-三-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-3-羥基-2,6-二甲基苄基)-1,3,5-三-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第二丁基-3-羥基-2,6-二甲基苄基)-1,3,5-三-2,4,6-(1H,3H,5H)-三酮、1,3,5-三[4-(1-乙基丙基)-3-羥基-2,6-二甲基苄基]-1,3,5-三-2,4,6-(1H,3H,5H)-三酮、1,3,5-三[4-三乙基甲基-3-羥基-2,6-二甲基苄基]-1,3,5-三-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(3-羥基-2,6-二甲基-4-苯基苄基)-1,3,5-三-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-3-羥基-2,5,6-三甲基苄基)-1,3,5-三-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-5-乙基-3-羥基-2,6-二甲基苄基)-1,3,5-三-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-6-乙基-3-羥基-2-甲基苄基)-1,3,5-三-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-6-乙基-3-羥基-2,5-二甲基苄基)-1,3,5-三-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-5,6-二乙基-3-羥基-2-甲基苄基)-1,3,5-三-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-3-羥基-2-甲基苄基)-1,3,5-三-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-3-羥基-2,5-二甲基苄基)-1,3,5-三-2,4,6-(1H,3H,5H)-三酮、1,3,5-三(4-第三丁基-5-乙基-3-羥基-2-甲基苄基)-1,3,5-三-2,4,6-(1H,3H,5H)-三酮等，但並不限定於其。該等之中，尤佳為1,3,5-三(4-第三丁基-3-羥基-2,6-二甲基苄基)-1,3,5-三-2,4,6-(1H,3H,5H)-三酮等。Hindered phenol compound In order to suppress discoloration on the copper surface, the negative photosensitive resin composition may optionally include a hindered phenol compound. Examples of the hindered phenol compound include 2,6-di-third-butyl-4-methylphenol, 2,5-di-third-butyl-hydroquinone, and 3- (3,5-di- Tert-butyl-4-hydroxyphenyl) octadecyl propionate, 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanoate isooctyl, 4,4'- Methylenebis (2,6-di-third-butylphenol), 4,4'-thio-bis (3-methyl-6-third-butylphenol), 4,4'-butylene- Bis (3-methyl-6-third butylphenol), triethylene glycol-bis [3- (3-third butyl-5-methyl-4-hydroxyphenyl) propionate], 1 , 6-hexanediol-bis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylidenebis [3- ( 3,5-di-third-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-third-butyl-4-hydroxy-phenylpropyl) Hydrazine), 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 2,2'-methylene-bis (4-ethyl-6-tert-butyl) Phenol), pentaerythritol-tetrakis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate], isocyanuric acid tri- (3,5-di-third-butyl- 4-hydroxybenzyl) ester, 1,3,5-trimethyl-2,4,6-tri (3,5-di-third-butyl-4-hydroxybenzyl) benzene, 1,3,5 -Tris (3-hydroxy-2,6-dimethyl -4-isopropylbenzyl) -1,3,5-tri-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tri (4-thirdbutyl- 3-hydroxy-2,6-dimethylbenzyl) -1,3,5-tri-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tri (4- Second butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-tri-2,4,6- (1H, 3H, 5H) -trione, 1,3,5 -Tris [4- (1-ethylpropyl) -3-hydroxy-2,6-dimethylbenzyl] -1,3,5-tri-2,4,6- (1H, 3H, 5H) -Trione, 1,3,5-tris [4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl] -1,3,5-tri-2,4,6- ( 1H, 3H, 5H) -trione, 1,3,5-tri (3-hydroxy-2,6-dimethyl-4-phenylbenzyl) -1,3,5-tri-2,4, 6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-third butyl-3-hydroxy-2,5,6-trimethylbenzyl) -1,3,5 -Tri-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-thirdbutyl-5-ethyl-3-hydroxy-2,6-dimethyl) Benzyl) -1,3,5-tri-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tri (4-thirdbutyl-6-ethyl- 3-hydroxy-2-methylbenzyl) -1,3,5-tri-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tri (4-tert-butyl) -6-ethyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-tri-2,4,6- (1H, 3H, 5H) -trione, 1,3 , 5-tris (4-third butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl) -1,3,5-tri-2,4,6- (1H, 3H , 5H) -trione 1,3,5-tris (4-third-butyl-3-hydroxy-2-methylbenzyl) -1,3,5-tris-2,4,6- (1H, 3H, 5H) -tris Ketone, 1,3,5-tris (4-third butyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-tri-2,4,6- (1H, 3H , 5H) -trione, 1,3,5-tris (4-third butyl-5-ethyl-3-hydroxy-2-methylbenzyl) -1,3,5-tri-2,4 , 6- (1H, 3H, 5H) -trione and the like, but are not limited thereto. Of these, 1,3,5-tris (4-thirdbutyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-tri-2,4, is particularly preferred. 6- (1H, 3H, 5H) -trione and the like.

受阻酚化合物之調配量較佳為相對於(A)聚醯亞胺前驅物100質量份為0.1～20質量份，就光感度特性之觀點而言，更佳為0.5～10質量份。於受阻酚化合物之相對於(A)聚醯亞胺前驅物100質量份之調配量為0.1質量份以上之情形時，例如於銅或銅合金上形成本發明之感光性樹脂組合物之情形時，可防止銅或銅合金之變色・腐蝕，另一方面，於為20質量份以下之情形時，光感度優異。The compounding amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass based on 100 parts by mass of the polyamidoimide precursor (A), and more preferably 0.5 to 10 parts by mass from the viewpoint of light sensitivity characteristics. When the compounded amount of the hindered phenol compound with respect to 100 parts by mass of the (A) polyfluorene imide precursor is 0.1 parts by mass or more, for example, when the photosensitive resin composition of the present invention is formed on copper or a copper alloy It can prevent discoloration and corrosion of copper or copper alloys. On the other hand, when it is 20 parts by mass or less, it has excellent light sensitivity.

有機鈦化合物
本實施形態之負型感光性樹脂組合物可含有有機鈦化合物。藉由含有有機鈦化合物，即便於在低溫下硬化之情形時，亦可形成耐化學品性優異之感光性樹脂層。Organic Titanium Compound The negative photosensitive resin composition of this embodiment may contain an organic titanium compound. By containing an organic titanium compound, a photosensitive resin layer excellent in chemical resistance can be formed even when it is cured at a low temperature.

作為能夠使用之有機鈦化合物，可列舉經由共價鍵或離子鍵於鈦原子上鍵結有有機化學物質者。
將有機鈦化合物之具體例示於以下之I)～VII)：
I)鈦螯合化合物：其中，就可獲得負型感光性樹脂組合物之保存穩定性及良好之圖案之方面而言，更佳為具有2個以上之烷氧基之鈦螯合物。具體例為雙(三乙醇胺)二異丙醇鈦、雙(2,4-戊二酸)二(正丁醇)鈦、雙(2,4-戊二酸)二異丙醇鈦、雙(四甲基庚二酸)二異丙醇鈦、雙(乙醯乙酸乙酯)二異丙醇鈦等。
II)四烷氧基鈦化合物：例如為四(正丁醇)鈦、四乙醇鈦、四(2-乙基己醇)鈦、四異丁醇鈦、四異丙醇鈦、四甲醇鈦、四甲氧基丙醇鈦、四甲基苯酚鈦、四(正壬醇)鈦、四(正丙醇)鈦、四硬脂醇鈦、四[雙{2,2-(烯丙氧基甲基)丁醇}]鈦等。
III)二茂鈦化合物：例如為(五甲基環戊二烯基)三甲醇鈦、雙(η5-2,4-環戊二烯-1-基)雙(2,6-二氟苯基)鈦、雙(η5-2,4-環戊二烯-1-基)雙(2,6-二氟-3-(1H-吡咯-1-基)苯基)鈦等。
IV)單烷氧基鈦化合物：例如為三(二辛基磷酸)異丙醇鈦、三(十二烷基苯磺酸)異丙醇鈦等。
V)氧鈦化合物：例如為雙(戊二酸)氧鈦、雙(四甲基庚二酸)氧鈦、酞菁氧鈦等。
VI)四乙醯丙酮鈦化合物：例如為四乙醯丙酮鈦等。
VII)鈦酸酯偶合劑：例如為異丙基三(十二烷基苯磺醯基)鈦酸酯等。Examples of usable organic titanium compounds include those in which an organic chemical substance is bonded to a titanium atom via a covalent bond or an ionic bond.
Specific examples of the organic titanium compound 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 terms of obtaining the storage stability and good pattern of the negative photosensitive resin composition. Specific examples are titanium bis (triethanolamine) diisopropoxide, titanium bis (2,4-glutaric acid) di (n-butanol), titanium bis (2,4-glutaric acid) diisopropoxide, and bis ( Tetramethylpimelate) titanium diisopropoxide, titanium bis (ethyl acetate) diisopropoxide, and the like.
II) Tetraalkoxy titanium compounds: For example, titanium (n-butanol), titanium tetraethoxide, titanium (2-ethylhexanol), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, Titanium tetramethoxypropoxide, titanium tetramethylphenol, titanium tetra-n-nonanol, titanium tetra-n-propanol, titanium stearate, tetra [bis {2,2- (allyloxymethyl) Group) butanol}] titanium and the like.
III) Titanocene compounds: for example, (pentamethylcyclopentadienyl) titanium methoxide, 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-pyrrole-1-yl) phenyl) titanium, and the like.
IV) Titanium monoalkoxide compounds: For example, titanium tris (dioctyl phosphate) isopropoxide, titanium tris (dodecylbenzenesulfonic acid) isopropoxide, and the like.
V) Titanium oxide compounds: For example, bis (glutarate) oxytitanium, bis (tetramethylpimelate) oxytitanium, phthalocyanine oxytitanium, and the like.
VI) Tetraacetamidine titanium acetone compound: For example, tetraacetamidine titanium acetone and the like.
VII) Titanate coupling agent: for example, isopropyltris (dodecylbenzenesulfonyl) titanate and the like.

其中，就發揮更良好之耐化學品性之觀點而言，有機鈦化合物較佳為選自由上述I)鈦螯合化合物、II)四烷氧基鈦化合物、及III)二茂鈦化合物所組成之群中之至少1種化合物，尤佳為雙(乙醯乙酸乙酯)二異丙醇鈦、四(正丁醇)鈦、及雙(η5-2,4-環戊二烯-1-基)雙(2,6-二氟-3-(1H-吡咯-1-基)苯基)鈦。Among these, from the viewpoint of exhibiting better chemical resistance, the organic titanium compound is preferably selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxy titanium compound, and III) titanocene compound. At least one compound in the group, particularly preferably bis (ethyl acetate) titanium diisopropoxide, titanium (n-butanol), and bis (η5-2,4-cyclopentadiene-1- Group) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium.

調配有機鈦化合物之情形時之調配量較佳為相對於(A)聚醯亞胺前驅物100質量份為0.05～10質量份，更佳為0.1～2質量份。於該調配量為0.05質量份以上之情形時，表現良好之耐熱性及耐化學品性，另一方面，於為10質量份以下之情形時，保存穩定性優異。When the organic titanium compound is prepared, the blending amount is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the polyamidoimide precursor (A). When the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited. On the other hand, when it is 10 parts by mass or less, storage stability is excellent.

接著助劑
為了提高使用本實施形態之負型感光性樹脂組合物所形成之膜與基材之接著性，負型感光性樹脂組合物可任意包含接著助劑。作為接著助劑，可列舉：γ-胺基丙基二甲氧基矽烷、N-(β-胺基乙基)-γ-胺基丙基甲基二甲氧基矽烷、γ-縮水甘油氧基丙基甲基二甲氧基矽烷、γ-巰基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基二甲氧基甲基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、二甲氧基甲基-3-哌啶基丙基矽烷、二乙氧基-3-縮水甘油氧基丙基甲基矽烷、N-(3-二乙氧基甲基矽烷基丙基)丁二醯亞胺、N-[3-(三乙氧基矽烷基)丙基]鄰苯二甲醯胺酸、二苯甲酮-3,3'-雙(N-[3-三乙氧基矽烷基]丙基醯胺)-4,4'-二羧酸、苯-1,4-雙(N-[3-三乙氧基矽烷基]丙基醯胺)-2,5-二羧酸、3-(三乙氧基矽烷基)丙基丁二酸酐、N-苯基胺基丙基三甲氧基矽烷、3-脲基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、3-(三烷氧基矽烷基)丙基丁二酸酐等矽烷偶合劑、及三(乙醯乙酸乙酯)鋁、三(乙醯丙酮)鋁、乙醯乙酸乙酯二異丙醇鋁等鋁系接著助劑等。Adhesion adjuvant In order to improve the adhesion between a film and a substrate formed using the negative photosensitive resin composition of this embodiment, the negative photosensitive resin composition may optionally include an adhesion adjuvant. Examples of the adhesion promoter include γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, and γ-glycidyloxy Propylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxysilane Propyltrimethoxysilane, dimethoxymethyl-3-piperidylpropylsilane, diethoxy-3-glycidyloxypropylmethylsilane, N- (3-diethoxymethyl Silylpropyl) succinimide, N- [3- (triethoxysilyl) propyl] phthalic acid, benzophenone-3,3'-bis (N- [3-Triethoxysilyl] propylamidoamine) -4,4'-dicarboxylic acid, benzene-1,4-bis (N- [3-triethoxysilyl] propylamidoamine) -2,5-dicarboxylic acid, 3- (triethoxysilyl) propylsuccinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3 -Silane coupling agents such as ureidopropyltriethoxysilane, 3- (trialkoxysilyl) propylsuccinic anhydride, and tris (ethylacetate) aluminum, tris (acetamidoacetone) aluminum, Ethyl ethyl acetate diisopropyl Aluminum-based adhesives such as aluminum alkoxide and the like.

該等接著助劑之中，就接著力之觀點而言，更佳為使用矽烷偶合劑。於感光性樹脂組合物含有接著助劑之情形時，接著助劑之調配量較佳為相對於(A)聚醯亞胺前驅物100質量份為0.5～25質量份之範圍內。Among these adhesion promoters, a silane coupling agent is more preferably used from the viewpoint of adhesion. When the photosensitive resin composition contains a bonding aid, the blending amount of the bonding aid is preferably within a range of 0.5 to 25 parts by mass relative to 100 parts by mass of the polyamidoimide precursor (A).

作為矽烷偶合劑，可列舉：3-巰基丙基三甲氧基矽烷(信越化學工業股份有限公司製造：商品名KBM803、Chisso股份有限公司製造：商品名Sila-Ace S810)、3-巰基丙基三乙氧基矽烷(Azmax股份有限公司製造：商品名SIM6475.0)、3-巰基丙基甲基二甲氧基矽烷(信越化學工業股份有限公司製造：商品名LS1375、Azmax股份有限公司製造：商品名SIM6474.0)、巰基甲基三甲氧基矽烷(Azmax股份有限公司製造：商品名SIM6473.5C)、巰基甲基甲基二甲氧基矽烷(Azmax股份有限公司製造：商品名SIM6473.0)、3-巰基丙基二乙氧基甲氧基矽烷、3-巰基丙基乙氧基二甲氧基矽烷、3-巰基丙基三丙氧基矽烷、3-巰基丙基二乙氧基丙氧基矽烷、3-巰基丙基乙氧基二丙氧基矽烷、3-巰基丙基二甲氧基丙氧基矽烷、3-巰基丙基甲氧基二丙氧基矽烷、2-巰基乙基三甲氧基矽烷、2-巰基乙基二乙氧基甲氧基矽烷、2-巰基乙基乙氧基二甲氧基矽烷、2-巰基乙基三丙氧基矽烷、2-巰基乙基三丙氧基矽烷、2-巰基乙基乙氧基二丙氧基矽烷、2-巰基乙基二甲氧基丙氧基矽烷、2-巰基乙基甲氧基二丙氧基矽烷、4-巰基丁基三甲氧基矽烷、4-巰基丁基三乙氧基矽烷、4-巰基丁基三丙氧基矽烷、N-(3-三乙氧基矽烷基丙基)脲(信越化學工業股份有限公司製造：商品名LS3610、Azmax股份有限公司製造：商品名SIU9055.0)、N-(3-三甲氧基矽烷基丙基)脲(Azmax股份有限公司製造：商品名SIU9058.0)、N-(3-二乙氧基甲氧基矽烷基丙基)脲、N-(3-乙氧基二甲氧基矽烷基丙基)脲、N-(3-三丙氧基矽烷基丙基)脲、N-(3-二乙氧基丙氧基矽烷基丙基)脲、N-(3-乙氧基二丙氧基矽烷基丙基)脲、N-(3-二甲氧基丙氧基矽烷基丙基)脲、N-(3-甲氧基二丙氧基矽烷基丙基)脲、N-(3-三甲氧基矽烷基乙基)脲、N-(3-乙氧基二甲氧基矽烷基乙基)脲、N-(3-三丙氧基矽烷基乙基)脲、N-(3-三丙氧基矽烷基乙基)脲、N-(3-乙氧基二丙氧基矽烷基乙基)脲、N-(3-二甲氧基丙氧基矽烷基乙基)脲、N-(3-甲氧基二丙氧基矽烷基乙基)脲、N-(3-三甲氧基矽烷基丁基)脲、N-(3-三乙氧基矽烷基丁基)脲、N-(3-三丙氧基矽烷基丁基)脲、3-(間胺基苯氧基)丙基三甲氧基矽烷(Azmax股份有限公司製造：商品名SLA0598.0)、間胺基苯基三甲氧基矽烷(Azmax股份有限公司製造：商品名SLA0599.0)、對胺基苯基三甲氧基矽烷(Azmax股份有限公司製造：商品名SLA0599.1)、胺基苯基三甲氧基矽烷(Azmax股份有限公司製造：商品名SLA0599.2)、2-(三甲氧基矽烷基乙基)吡啶(Azmax股份有限公司製造：商品名SIT8396.0)、2-(三乙氧基矽烷基乙基)吡啶、2-(二甲氧基矽烷基甲基乙基)吡啶、2-(二乙氧基矽烷基甲基乙基)吡啶、(3-三乙氧基矽烷基丙基)-第三丁基胺基甲酸酯、(3-縮水甘油氧基丙基)三乙氧基矽烷、四甲氧基矽烷、四乙氧基矽烷、四-正丙氧基矽烷、四-異丙氧基矽烷、四-正丁氧基矽烷、四-異丁氧基矽烷、四-第三丁氧基矽烷、四(甲氧基乙氧基矽烷)、四(甲氧基-正丙氧基矽烷)、四(乙氧基乙氧基矽烷)、四(甲氧基乙氧基乙氧基矽烷)、雙(三甲氧基矽烷基)乙烷、雙(三甲氧基矽烷基)己烷、雙(三乙氧基矽烷基)甲烷、雙(三乙氧基矽烷基)乙烷、雙(三乙氧基矽烷基)乙烯、雙(三乙氧基矽烷基)辛烷、雙(三乙氧基矽烷基)辛二烯、雙[3-(三乙氧基矽烷基)丙基]二硫醚、雙[3-(三乙氧基矽烷基)丙基]四硫醚、二-第三丁氧基二乙醯氧基矽烷、二-異丁氧基鋁氧基三乙氧基矽烷、苯基矽烷三醇、甲基苯基矽烷二醇、乙基苯基矽烷二醇、正丙基苯基矽烷二醇、異丙基苯基矽烷二醇、正丁基苯基矽烷二醇、異丁基苯基矽烷二醇、第三丁基苯基矽烷二醇、二苯基矽烷二醇、二甲氧基二苯基矽烷、二乙氧基二苯基矽烷、二甲氧基二-對甲苯基矽烷、乙基甲基苯基矽烷醇、正丙基甲基苯基矽烷醇、異丙基甲基苯基矽烷醇、正丁基甲基苯基矽烷醇、異丁基甲基苯基矽烷醇、第三丁基甲基苯基矽烷醇、乙基正丙基苯基矽烷醇、乙基異丙基苯基矽烷醇、正丁基乙基苯基矽烷醇、異丁基乙基苯基矽烷醇、第三丁基乙基苯基矽烷醇、甲基二苯基矽烷醇、乙基二苯基矽烷醇、正丙基二苯基矽烷醇、異丙基二苯基矽烷醇、正丁基二苯基矽烷醇、異丁基二苯基矽烷醇、第三丁基二苯基矽烷醇、三苯基矽烷醇等，但並不限定於該等。該等可單獨使用，亦可組合複數種使用。Examples of the silane coupling agent include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name KBM803, manufactured by Chisso Co., Ltd .: trade name Sila-Ace S810), and 3-mercaptopropyltrimethoxysilane. Ethoxysilane (manufactured by Azmax Co., Ltd .: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name LS1375, manufactured by Azmax Co., Ltd .: merchandise Name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SIM6473.0) , 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropyl Oxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyl Trimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethyl Ethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyl Dimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyl Tripropoxysilane, N- (3-triethoxysilylpropyl) urea (manufactured by Shin-Etsu Chemical Industry Co., Ltd .: trade name LS3610, Azmax Co., Ltd .: trade name SIU9055.0), N- ( 3-trimethoxysilylpropyl) urea (manufactured by Azmax Co., Ltd .: trade name SIU9058.0), N- (3-diethoxymethoxysilylpropyl) urea, N- (3-ethyl Oxydimethoxysilylpropyl) urea, N- (3-tripropoxysilylpropyl) urea, N- (3-diethoxypropoxysilylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N- (3-dimethoxypropoxysilylpropyl) urea, N- (3-methoxydipropoxysilyl) Propyl) urea, N- (3-trimethoxysilylethyl) urea, N- (3-ethoxydimethoxysilylethyl) urea, N -(3-tripropoxysilylethyl) urea, N- (3-tripropoxysilylethyl) urea, N- (3-ethoxydipropoxysilylethyl) urea, N- (3-dimethoxypropoxysilylethyl) urea, N- (3-methoxydipropoxysilylethyl) urea, N- (3-trimethoxysilylbutyl) ) Urea, N- (3-triethoxysilylbutyl) urea, N- (3-tripropoxysilylbutyl) urea, 3- (m-aminophenoxy) propyltrimethoxy Silane (manufactured by Azmax Corporation: trade name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.0), p-aminophenyltrimethoxysilane (Azmax Corporation) Co., Ltd .: trade name SLA0599.1), aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.2), 2- (trimethoxysilylethyl) pyridine (Azmax Corporation) Manufacturing: trade name SIT8396.0), 2- (triethoxysilylethyl) pyridine, 2- (dimethoxysilylmethylethyl) pyridine, 2- (diethoxysilylmethyl) Ethyl) pyridine, (3-triethoxysilylpropyl) -tert-butylcarbamate, (3-glycidyl (Oxypropyl) triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-isopropoxysilane, tetra-n-butoxysilane, tetra-iso Butoxysilane, tetra-third butoxysilane, tetra (methoxyethoxysilane), tetra (methoxy-n-propoxysilane), tetra (ethoxyethoxysilane), tetra (Methoxyethoxyethoxysilane), bis (trimethoxysilyl) ethane, bis (trimethoxysilyl) hexane, bis (triethoxysilyl) methane, bis (triethyl Oxysilyl) ethane, bis (triethoxysilyl) ethylene, bis (triethoxysilyl) octane, bis (triethoxysilyl) octadiene, bis [3- (tri Ethoxysilyl) propyl] disulfide, bis [3- (triethoxysilyl) propyl] tetrasulfide, di-third-butoxydiethoxysilane, di-isobutyl Oxyaluminum triethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol , N-butylphenylsilanediol, isobutylphenylsilanediol, third butylphenylsilane Alcohol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propyl Methylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilane Alcohol, ethyl isopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, third butylethylphenylsilanol, methyldiphenylsilanol , Ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, third butyldiphenylsilanol Phenylsilanol, triphenylsilanol, and the like are not limited thereto. These can be used alone or in combination.

作為矽烷偶合劑，於上述矽烷偶合劑之中，就保存穩定性之觀點而言，較佳為苯基矽烷三醇、三甲氧基苯基矽烷、三甲氧基(對甲苯基)矽烷、二苯基矽烷二醇、二甲氧基二苯基矽烷、二乙氧基二苯基矽烷、二甲氧基二-對甲苯基矽烷、三苯基矽烷醇、及具有下述式：
[化62]

所表示之結構之矽烷偶合劑。As the silane coupling agent, among the above-mentioned silane coupling agents, from the viewpoint of storage stability, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy (p-tolyl) silane, and diphenyl are preferred. Silanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and have the following formula:
[Chem 62]

Silane coupling agent of the indicated structure.

作為使用矽烷偶合劑之情形時之感光性樹脂組合物中之調配量，較佳為相對於(A)聚醯亞胺前驅物100質量份為0.01～20質量份。The blending amount in the photosensitive resin composition when a silane coupling agent is used is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the polyamidoimide precursor (A).

增感劑
為了提高光感度，本實施形態之負型感光性樹脂組合物可任意包含增感劑。作為該增感劑，例如可列舉：米其勒酮、4,4'-雙(二乙胺基)二苯甲酮、2,5-雙(4'-二乙胺基亞苄基)環戊烷、2,6-雙(4'-二乙胺基亞苄基)環己酮、2,6-雙(4'-二乙胺基亞苄基)-4-甲基環己酮、4,4'-雙(二甲胺基)查耳酮、4,4'-雙(二乙胺基)查耳酮、對二甲胺基亞桂皮基茚酮、對二甲胺基亞苄基茚酮、2-(對二甲胺基苯基聯伸苯基)-苯并噻唑、2-(對二甲胺基苯基伸乙烯基)苯并噻唑、2-(對二甲胺基苯基伸乙烯基)異萘并噻唑、1,3-雙(4'-二甲胺基亞苄基)丙酮、1,3-雙(4'-二乙胺基亞苄基)丙酮、3,3'-羰基-雙(7-二乙胺基香豆素)、3-乙醯基-7-二甲胺基香豆素、3-乙氧基羰基-7-二甲胺基香豆素、3-苄氧基羰基-7-二甲胺基香豆素、3-甲氧基羰基-7-二乙胺基香豆素、3-乙氧基羰基-7-二乙胺基香豆素、N-苯基-N'-乙基乙醇胺、N-苯基二乙醇胺、N-對甲苯基二乙醇胺、N-苯基乙醇胺、4-啉基二苯甲酮、二甲胺基苯甲酸異戊酯、二乙胺基苯甲酸異戊酯、2-巰基苯并咪唑、1-苯基-5-巰基四唑、2-巰基苯并噻唑、2-(對二甲胺基苯乙烯基)苯并㗁唑、2-(對二甲胺基苯乙烯基)苯并噻唑、2-(對二甲胺基苯乙烯基)萘并(1,2-d)噻唑、2-(對二甲胺基苯甲醯基)苯乙烯等。該等可單獨使用或以例如2～5種之組合使用。Sensitizer In order to improve the light sensitivity, the negative-type photosensitive resin composition of the present embodiment may optionally include a sensitizer. Examples of the sensitizer include Michelin, 4,4'-bis (diethylamino) benzophenone, and 2,5-bis (4'-diethylaminobenzylidene) ring. Pentane, 2,6-bis (4'-diethylaminobenzylidene) cyclohexanone, 2,6-bis (4'-diethylaminobenzylidene) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminocinidinylindene, p-dimethylaminobenzylidene Indanone, 2- (p-dimethylaminophenylphenylphenyl) -benzothiazole, 2- (p-dimethylaminophenylphenyl) benzothiazole, 2- (p-dimethylaminophenylbenzene) Vinylidene) isonaphthothiazole, 1,3-bis (4'-dimethylaminobenzylidene) acetone, 1,3-bis (4'-diethylaminobenzylidene) acetone, 3,3 '-Carbonyl-bis (7-diethylaminocoumarin), 3-ethylamido-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin , N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-phosphinobenzophenone, Isoamyl methylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylene Aminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2- (p-dimethylaminostyryl) naphtho (1,2-d) thiazole, 2- (p-dimethylaminobenzyl) styrene and the like. These can be used individually or in combination of 2 to 5 types, for example.

感光性樹脂組合物含有用以提高光感度之增感劑之情形時之調配量較佳為相對於(A)聚醯亞胺前驅物100質量份為0.1～25質量份。In the case where the photosensitive resin composition contains a sensitizer for improving the light sensitivity, the blending amount is preferably 0.1 to 25 parts by mass based on 100 parts by mass of the polyamidoimide precursor (A).

光聚合性不飽和單體
為了提高凹凸圖案之解像性，負型感光性樹脂組合物可任意包含具有光聚合性之不飽和鍵之單體。作為此種單體，較佳為藉由光聚合起始劑進行自由基聚合反應之(甲基)丙烯酸系化合物，可列舉：二乙二醇二甲基丙烯酸酯、四乙二醇二甲基丙烯酸酯等乙二醇或聚乙二醇之單或二丙烯酸酯及甲基丙烯酸酯、丙二醇或聚丙二醇之單或二丙烯酸酯及甲基丙烯酸酯、甘油之單、二或三丙烯酸酯及甲基丙烯酸酯、環己烷二丙烯酸酯及二甲基丙烯酸酯、1,4-丁二醇之二丙烯酸酯及二甲基丙烯酸酯、1,6-己二醇之二丙烯酸酯及二甲基丙烯酸酯、新戊二醇之二丙烯酸酯及二甲基丙烯酸酯、雙酚A之單或二丙烯酸酯及甲基丙烯酸酯、苯三甲基丙烯酸酯、丙烯酸異酯及甲基丙烯酸異酯、丙烯醯胺及其衍生物、甲基丙烯醯胺及其衍生物、三羥甲基丙烷三丙烯酸酯及甲基丙烯酸酯、甘油之二或三丙烯酸酯及甲基丙烯酸酯、季戊四醇之二、三、或四丙烯酸酯及甲基丙烯酸酯、以及該等化合物之環氧乙烷或環氧丙烷加成物等化合物，但並不特別限定於以上。Photopolymerizable unsaturated monomer In order to improve the resolution of the uneven pattern, the negative photosensitive resin composition may optionally include a monomer having a photopolymerizable unsaturated bond. 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 and tetraethylene glycol dimethyl Mono- or di-acrylates and methacrylates of ethylene glycol or polyethylene glycol, such as acrylates, mono- or di-acrylates and methacrylates of propylene glycol or polypropylene glycol, mono-, di-, or tri-acrylates of glycerol and formazan Acrylate, cyclohexane diacrylate and dimethacrylate, 1,4-butanediol diacrylate and dimethacrylate, 1,6-hexanediol diacrylate and dimethacrylate Acrylates, diacrylates and dimethacrylates of neopentyl glycol, mono- or diacrylates and methacrylates of bisphenol A, benzenetrimethacrylates, isoacrylates and isomethacrylates, Acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, two or three glycerol and methacrylate, two and three pentaerythritol , Or tetraacrylate and methacrylate, And the compound of ethylene oxide or propylene oxide adducts of such compounds and the like, but is not particularly limited to the above.

於感光性樹脂組合物含有用以提高凹凸圖案之解像性之上述具有光聚合性之不飽和鍵之單體之情形時，具有光聚合性之不飽和鍵之單體之調配量較佳為相對於(A)聚醯亞胺前驅物100質量份為1～50質量份。When the photosensitive resin composition contains the above-mentioned monomer having a photopolymerizable unsaturated bond to improve the resolution of the uneven pattern, the blending amount of the monomer having a photopolymerizable unsaturated bond is preferably 1-50 mass parts with respect to 100 mass parts of (A) polyfluorene imide precursors.

熱聚合抑制劑
又，關於本實施形態之負型感光性樹脂組合物，尤其是為了提高於包含溶劑之溶液之狀態下保存時之負型感光性樹脂組合物之黏度及光感度之穩定性，而亦可任意包含熱聚合抑制劑。作為熱聚合抑制劑，例如可使用：對苯二酚、N-亞硝基二苯基胺、對第三丁基鄰苯二酚、啡噻、N-苯基萘基胺、乙二胺四乙酸、1,2-環己烷二胺四乙酸、二醇醚二胺四乙酸、2,6-二-第三丁基-對甲基苯酚、5-亞硝基-8-羥基喹啉、1-亞硝基-2-萘酚、2-亞硝基-1-萘酚、2-亞硝基-5-(N-乙基-N-磺丙基胺基)苯酚、N-亞硝基-N-苯基羥基胺銨鹽、N-亞硝基-N-(1-萘基)羥基胺銨鹽等。The thermal polymerization inhibitor is related to the negative photosensitive resin composition of this embodiment, in particular, to improve the stability of the viscosity and light sensitivity of the negative photosensitive resin composition when stored in a solution containing a solvent, Alternatively, a thermal polymerization inhibitor may be optionally included. As the thermal polymerization inhibitor, for example, hydroquinone, N-nitrosodiphenylamine, p-third butylcatechol, phenanthrene, N-phenylnaphthylamine, and ethylenediaminetetramethylene Acetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-third-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso -N-phenylhydroxyamine ammonium salt, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, and the like.

＜硬化凹凸圖案之製造方法及半導體裝置＞
又，本發明提供一種硬化凹凸圖案之製造方法，其包括：(1)將上述本實施形態之負型感光性樹脂組合物塗佈於基板上而於上述基板上形成感光性樹脂層之步驟、(2)對上述感光性樹脂層進行曝光之步驟、(3)對曝光後之上述感光性樹脂層進行顯影而形成凹凸圖案之步驟、及(4)對上述凹凸圖案進行加熱處理而形成硬化凹凸圖案之步驟。<Manufacturing method of hardened uneven pattern and semiconductor device>
In addition, the present invention provides a method for producing a hardened uneven pattern, comprising: (1) a step of applying the negative photosensitive resin composition of the present embodiment on a substrate to form a photosensitive resin layer on the substrate; (2) a step of exposing the photosensitive resin layer, (3) a step of developing the photosensitive resin layer after exposure to form a concave-convex pattern, and (4) a heat treatment of the concave-convex pattern to form a hardened unevenness Steps of pattern.

(1)感光性樹脂層形成步驟
於本步驟中，將本發明之負型感光性樹脂組合物塗佈於基材上，視需要於其後進行乾燥，形成感光性樹脂層。作為塗佈方法，可使用先前以來用於感光性樹脂組合物之塗佈之方法、例如利用旋轉塗佈機、棒式塗佈機、刮刀塗佈機、簾幕式塗佈機、網版印刷機等進行塗佈之方法、利用噴塗機進行噴霧塗佈之方法等。(1) Photosensitive resin layer formation step In this step, the negative-type photosensitive resin composition of the present invention is applied to a substrate, and thereafter, if necessary, dried to form a photosensitive resin layer. As a coating method, a conventional method for coating a photosensitive resin composition can be used, for example, a spin coater, a bar coater, a blade coater, a curtain coater, and screen printing can be used. A method of coating by a machine, a method of spray coating by a sprayer, and the like.

視需要可對包含感光性樹脂組合物之塗膜進行乾燥。作為乾燥方法，可使用風乾、利用烘箱或加熱板之加熱乾燥、真空乾燥等方法。具體而言，於進行風乾或加熱乾燥之情形時，可於20℃～140℃、1分鐘～1小時之條件下進行乾燥。如以上所示，可於基板上形成感光性樹脂層。If necessary, the coating film containing the photosensitive resin composition may be dried. As the drying method, methods such as air drying, heating drying using 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 performed under the conditions of 20 ° C to 140 ° C for 1 minute to 1 hour. As described above, a photosensitive resin layer can be formed on a substrate.

(2)曝光步驟
於本步驟中，使用接觸式對準機、鏡面投影曝光機、步進機等曝光裝置，經由具有圖案之光罩或光柵、或者直接藉由紫外線光源等對上述所形成之感光性樹脂層進行曝光。(2) Exposure step In this step, an exposure device such as a contact-type alignment machine, a mirror projection exposure machine, a stepper, etc. is used to pass through the mask or grating with a pattern, or directly through an ultraviolet light source, etc. The photosensitive resin layer is exposed.

其後，亦可出於光感度之提高等目的，視需要實施任意之溫度及時間之組合下之曝光後烘烤(PEB)及/或顯影前烘烤。關於烘烤條件之範圍，較佳為溫度為40℃～120℃，並且時間為10秒～240秒，但只要不阻礙本發明之感光性樹脂組合物之各特性，則不限於該範圍。Thereafter, for the purpose of improving the light sensitivity, etc., a post-exposure baking (PEB) and / or a pre-development baking at any combination of temperature and time may be implemented as needed. The range of the baking conditions is preferably a temperature of 40 ° C. to 120 ° C. and a time of 10 seconds to 240 seconds. However, the range is not limited as long as the characteristics of the photosensitive resin composition of the present invention are not hindered.

(3)凹凸圖案形成步驟
於本步驟中，對曝光後之感光性樹脂層中之未曝光部進行顯影去除。作為對曝光(照射)後之感光性樹脂層進行顯影之顯影方法，可自先前已知之光阻之顯影方法、例如旋轉噴霧法、浸置法、伴有超音波處理之浸漬法等之中選擇任意之方法來使用。又，顯影之後，亦可出於調整凹凸圖案之形狀等目的，視需要實施任意之溫度及時間之組合下之顯影後烘烤。(3) Concave-convex pattern forming step In this step, unexposed portions in the photosensitive resin layer after exposure are developed and removed. As a developing method for developing the photosensitive resin layer after exposure (irradiation), it can be selected from previously known developing methods of photoresist, such as a rotary spray method, an immersion method, an immersion method with ultrasonic treatment, and the like. Use any method. In addition, after development, it is also possible to perform post-development baking at any combination of temperature and time for the purpose of adjusting the shape of the uneven pattern, etc., as necessary.

作為用於顯影之顯影液，例如較佳為對於負型感光性樹脂組合物之良溶劑、或該良溶劑與不良溶劑之組合。作為良溶劑，例如較佳為N-甲基-2-吡咯啶酮、N-環己基-2-吡咯啶酮、N,N-二甲基乙醯胺、環戊酮、環己酮、γ-丁內酯、α-乙醯基-γ-丁內酯等。作為不良溶劑，例如較佳為甲苯、二甲苯、甲醇、乙醇、異丙醇、乳酸乙酯、丙二醇甲醚乙酸酯及水等。於混合使用良溶劑與不良溶劑之情形時，較佳為根據負型感光性樹脂組合物中之聚合物之溶解性來調整不良溶劑相對於良溶劑之比率。又，亦可將各溶劑組合2種以上、例如組合數種而使用。As a developing solution for development, for example, a good solvent for a negative photosensitive resin composition or a combination of the good solvent and a poor solvent is preferred. Examples of good solvents include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, and γ. -Butyrolactone, α-ethenyl-γ-butyrolactone, and the like. Examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate, and water. 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 according to the solubility of the polymer in the negative photosensitive resin composition. Moreover, you may use each solvent combining two or more types, for example, combining several types.

(4)硬化凹凸圖案形成步驟
於本步驟中，對藉由上述顯影所得之凹凸圖案進行加熱而使感光成分稀散，並且使(A)聚醯亞胺前驅物進行醯亞胺化，藉此轉換為包含聚醯亞胺之硬化凹凸圖案。作為加熱硬化之方法，例如可選擇利用加熱板者、使用烘箱者、使用可設定溫控程式之升溫式烘箱者等各種方法。加熱例如可於170℃～400℃、30分鐘～5小時之條件下進行。作為加熱硬化時之環境氣體，可使用空氣，亦可使用氮氣、氬氣等惰性氣體。(4) Step of forming a hardened concave-convex pattern In this step, the concave-convex pattern obtained by the above development is heated to diffuse the photosensitive component, and (A) a polyimide precursor is subjected to fluorimidization, thereby converting It is a hardened uneven pattern containing polyimide. As a method of heating and hardening, various methods such as those using a hot plate, those using an oven, and those using a heating type oven that can set a temperature control program can be selected. Heating can be performed, for example, under conditions of 170 ° C. to 400 ° C. for 30 minutes to 5 hours. As the ambient gas during heating and hardening, air can be used, and inert gases such as nitrogen and argon can also be used.

＜聚醯亞胺＞
由上述聚醯亞胺前驅物組合物形成之硬化凹凸圖案中所含之聚醯亞胺之結構係由下述通式(8)所表示。
[化63]

{式中，X¹ 及Y¹ 與通式(2)中之X₁ 及Y₁ 相同，m為正之整數}
通式(2)中之較佳之X₁ 與Y₁ 根據相同之理由，於通式(8)之聚醯亞胺中亦較佳。通式(8)之重複單元數m只要為正之整數，則並無特別限定，可為2～150之整數、或3～140之整數。
又，上述所說明之包含將負型感光性樹脂組合物轉換為聚醯亞胺之步驟之聚醯亞胺之製造方法亦為本發明之一態樣。＜ Polyimide ＞
The structure of the polyimide contained in the hardened uneven | corrugated pattern formed from the said polyimide precursor composition is represented by following General formula (8).
[Chem 63]

{In the formula, X ¹ and Y ¹ in the general formula (2) in the same as X ₁ and Y _1, m is a positive integer} of
X ₁ and Y _{1 which are} preferable in the general formula (2) are also preferable in the polyfluorene imine of the general formula (8) for the same reason. The number of repeating units m in 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.
In addition, the method for producing polyimide including the step of converting the negative photosensitive resin composition to polyimide as described above is also one aspect of the present invention.

＜半導體裝置＞
於本實施形態中，亦提供具有藉由上述硬化凹凸圖案之製造方法所得之硬化凹凸圖案之半導體裝置。因此，可提供具有作為半導體元件之基材與藉由上述硬化凹凸圖案製造方法而形成於該基材上之聚醯亞胺之硬化凹凸圖案之半導體裝置。又，本發明亦適用於使用半導體元件作為基材，包含上述硬化凹凸圖案之製造方法作為步驟之一部分之半導體裝置之製造方法。本發明之半導體裝置可藉由形成利用上述硬化凹凸圖案製造方法所形成之硬化凹凸圖案作為表面保護膜、層間絕緣膜、再配線用絕緣膜、覆晶裝置用保護膜、或具有凸塊結構之半導體裝置之保護膜等，且與既知之半導體裝置之製造方法組合而製造。＜ Semiconductor device ＞
In this embodiment, a semiconductor device having a hardened uneven pattern obtained by the method for producing a hardened uneven pattern is also provided. Therefore, a semiconductor device having a base material as a semiconductor element and a hardened bump pattern of polyimide formed on the base material by the above-mentioned hardened bump pattern manufacturing method can be provided. In addition, the present invention is also applicable to a method for manufacturing a semiconductor device using a semiconductor element as a base material and including the above-mentioned method for manufacturing a hardened uneven pattern as part of a step. The semiconductor device of the present invention can be formed as a surface protection film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip-chip device, or a bump structure by forming a hardened uneven pattern formed using the hardened uneven pattern manufacturing method described above. A protective film or the like of a semiconductor device is manufactured in combination with a known method for manufacturing a semiconductor device.

＜顯示體裝置＞
於本實施形態中，提供一種具備顯示體元件與設置於該顯示體元件之上部之硬化膜，且該硬化膜為上述硬化凹凸圖案之顯示體裝置。此處，該硬化凹凸圖案可直接與該顯示體元件相接而積層，亦可於其間夾持其他層而積層。例如作為該硬化膜，可列舉：薄膜電晶體(TFT)液晶顯示元件及彩色濾光片元件之表面保護膜、絕緣膜、及平坦化膜、多域垂直配向(MVA)型液晶顯示裝置用之突起、以及有機電致發光(EL)元件陰極用之間隔壁。＜ Display body device ＞
In this embodiment, there is provided a display device including a display element and a cured film provided on an upper portion of the display element, and the cured film is the above-mentioned cured uneven pattern. Here, the hardened concave-convex pattern may be directly connected to the display element and laminated, or may be laminated with other layers sandwiched therebetween. Examples of the hardened film include surface protection films, insulating films, and planarization films for thin film transistor (TFT) liquid crystal display elements and color filter elements, and multi-domain vertical alignment (MVA) type liquid crystal display devices. A projection and a partition wall for a cathode of an organic electroluminescence (EL) element.

本發明之負型感光性樹脂組合物除了如上所述之半導體裝置中之應用以外，亦可用於多層電路之層間絕緣、可撓性銅箔板之覆蓋塗層、阻焊膜、及液晶配向膜等用途。The negative-type photosensitive resin composition of the present invention can be used for interlayer insulation of multilayer circuits, cover coatings of flexible copper foils, solder resist films, and liquid crystal alignment films in addition to applications in semiconductor devices as described above. And other uses.

[第二態樣]
對本實施形態之第二態樣進行說明。
＜負型感光性樹脂組合物＞
本實施形態之負型感光性樹脂組合物包含：
(A)聚醯亞胺前驅物；
(B2)熱硬化劑；及
光聚合起始劑。[Second aspect]
A second aspect of this embodiment will be described.
<Negative photosensitive resin composition>
The negative photosensitive resin composition of this embodiment includes:
(A) a polyimide precursor;
(B2) a thermosetting agent; and a photopolymerization initiator.

就獲得較高之解像度之觀點而言，負型感光性樹脂組合物較佳為包含100質量份之(A)聚醯亞胺前驅物、以(A)聚醯亞胺前驅物100質量份為基準之0.1～30質量份之(B2)熱硬化劑、及以(A)聚醯亞胺前驅物100質量份為基準之0.1～20質量份之(C)光聚合起始劑。From the viewpoint of obtaining a 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. 0.1 to 30 parts by mass of (B2) a thermosetting agent and 0.1 to 20 parts by mass of (C) a photopolymerization initiator based on (A) 100 parts by mass of a polyimide precursor.

(A)聚醯亞胺前驅物
於本實施形態中，(A)聚醯亞胺前驅物可使用第一態樣中所示者。(A) Polyfluorene imide precursor In this embodiment, the (A) polyfluorene imide precursor may be the one shown in the first aspect.

(B2)熱硬化劑
本實施形態中之(B2)熱硬化劑只要為可藉由加熱而進行硬化之化合物則並無限定。其中，就與密封材之密接性之觀點而言，較佳為苯并㗁、環氧樹脂、氧雜環丁烷樹脂，更佳為苯并㗁。
作為苯并㗁，可列舉下述通式(10)或(11)所表示之結構。
[化64]

[化65]

作為環氧樹脂，可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、萘環氧樹脂等芳香族環氧樹脂、3,4-環氧環己烷羧酸3',4'-環氧環己基甲酯、ε-己內酯改性3,4-環氧環己烷羧酸3',4'-環氧環己基甲酯等脂環式環氧樹脂等。作為脂環式環氧樹脂，亦可列舉下述通式(12)：
[化66]

等。
作為氧雜環丁烷樹脂，例如可列舉3-烯丙氧基氧雜環丁烷、對甲苯磺酸3-氧雜環丁酯等。(B2) Thermosetting agent The (B2) thermosetting agent in this embodiment is not limited as long as it is a compound that can be cured by heating. Among these, benzofluorene, an epoxy resin, and an oxetane resin are preferable from a viewpoint of the adhesiveness with a sealing material, and benzofluorene is more preferable.
Examples of the benzofluorene include a structure represented by the following general formula (10) or (11).
[Chemical 64]

[Chem 65]

Examples of the epoxy resin include aromatic epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and naphthalene epoxy resin, and 3,4-epoxy cyclohexanecarboxylic acid 3 ', 4. Alicyclic epoxy resins such as '-epoxycyclohexylmethyl ester and ε-caprolactone-modified 3,4-epoxycyclohexanecarboxylic acid 3', 4'-epoxycyclohexylmethyl ester. As the alicyclic epoxy resin, the following general formula (12) can also be cited:
[Chemical 66]

Wait.
Examples of the oxetane resin include 3-allyloxyoxetane and 3-oxetane p-toluenesulfonic acid.

若使用上述熱硬化劑，則可獲得良好之耐化學品性與解像性、及Cu孔隙抑制效果。雖受理論約束，但關於可獲得良好之耐化學品性之理由，認為藉由在熱交聯後形成高次網狀結構而抑制藥液之滲入，提高耐化學品性。
又，可獲得良好之解像性之理由雖不明確，但認為其原因在於：加熱硬化前之熱硬化劑藉由與聚醯亞胺前驅物進行調配，更容易溶解於顯影時之顯影液而抑制殘渣。此外，顯示Cu孔隙抑制效果之理由雖未確定，但認為熱硬化劑藉由加熱而產生羥基等，該羥基與Cu離子強烈相互作用，抑制Cu之擴散，結果抑制Cu孔隙。When the above-mentioned thermosetting agent is used, good chemical resistance and resolving power, and Cu pore suppression effect can be obtained. Although bound by theory, the reason for obtaining good chemical resistance is considered to be to improve the chemical resistance by suppressing the penetration of the medicinal solution by forming a higher-order network structure after thermal crosslinking.
Although the reason for obtaining good resolution is not clear, it is thought that the reason is that the heat curing agent before heat curing is more easily dissolved in the developing solution during development by blending with the polyimide precursor. Suppresses residue. In addition, although the reason for showing the effect of suppressing the pores of Cu is not determined, it is considered that the thermosetting agent generates a hydroxyl group or the like by heating, and this hydroxyl group strongly interacts with Cu ions to suppress the diffusion of Cu and consequently suppress the pores of Cu.

負型感光性樹脂組合物中之上述熱硬化劑相對於上述(A)聚醯亞胺前驅物100質量份，較佳為0.1～30質量份，更佳為1質量份以上且15質量份以下。藉由相對於(A)聚醯亞胺前驅物100質量份，於0.1質量份以上且30質量份以下之範圍內進行調配，可獲得Cu孔隙抑制效果、解像性提高及耐化學品性提高之效果尤其優異之負型感光性樹脂組合物。The thermosetting agent in the negative photosensitive resin composition is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 15 parts by mass, based on 100 parts by mass of the (A) polyimide precursor. . By blending 100 mass parts of (A) polyfluorene imide precursor in a range of 0.1 mass parts or more and 30 mass parts or less, the effect of suppressing Cu pores, improving resolution, and improving chemical resistance can be obtained. The negative photosensitive resin composition is particularly excellent in effect.

(C)光聚合起始劑
於本實施形態中，(C)光聚合起始劑可使用第一態樣中所示者。(C) Photopolymerization initiator In this embodiment, as the (C) photopolymerization initiator, those shown in the first aspect can be used.

其他成分
於本實施形態中，關於作為其他成分之溶劑、含氮雜環化合物、受阻酚化合物、有機鈦化合物、接著助劑、增感劑、光聚合性不飽和單體、熱聚合抑制劑，可使用第一態樣中所示者。Other components In this embodiment, as a solvent for other components, a nitrogen-containing heterocyclic compound, a hindered phenol compound, an organic titanium compound, an adhesion promoter, a sensitizer, a photopolymerizable unsaturated monomer, and a thermal polymerization inhibitor, The one shown in the first aspect may be used.

＜硬化凹凸圖案之製造方法及半導體裝置＞
於本實施形態中，硬化凹凸圖案之製造方法及半導體裝置可應用與第一態樣中所示者相同者。<Manufacturing method of hardened uneven pattern and semiconductor device>
In this embodiment, the manufacturing method of the hardened uneven pattern and the semiconductor device may be the same as those shown in the first aspect.

＜聚醯亞胺＞
於本實施形態中，聚醯亞胺可應用與第一態樣中所示者相同者。＜ Polyimide ＞
In the present embodiment, the polyimide may be the same as that shown in the first aspect.

＜半導體裝置＞
於本實施形態中，半導體裝置可應用與第一態樣中所示者相同者。＜ Semiconductor device ＞
In this embodiment, the semiconductor device can be the same as that shown in the first aspect.

＜顯示裝置＞
於本實施形態中，顯示裝置可應用與第一態樣中所示者相同者。＜ Display device ＞
In this embodiment, the display device can be the same as that shown in the first aspect.

本實施形態之負型感光性樹脂組合物與第一態樣中所示之負型感光性樹脂組合物同樣地，除了如上所述之半導體裝置中之應用以外，亦可用於多層電路之層間絕緣、可撓性銅箔板之覆蓋塗層、阻焊膜、及液晶配向膜等用途。第一態樣中所示之較佳之構成、數值範圍或步驟等於本實施形態中亦同樣地作為較佳之構成、數值範圍或步驟等處理。The negative photosensitive resin composition of this embodiment is the same as the negative photosensitive resin composition shown in the first aspect, and can be used for interlayer insulation of a multilayer circuit in addition to the application in the semiconductor device as described above. Covering coatings for flexible copper foils, solder masks, and liquid crystal alignment films. The preferred configuration, numerical range, or step shown in the first aspect is equal to that in this embodiment, and is also treated as the preferred configuration, numerical range, or step.

[第三態樣]
對本實施形態之第三態樣進行說明。
＜負型感光性樹脂組合物＞
本實施形態之負型感光性樹脂組合物包含：
(A)聚醯亞胺前驅物；
(B3)下述通式(B-1)：
[化67]

{式中，Ra及Rb分別獨立為可包含雜原子之碳數1～10之1價之有機基，Rc分別獨立為可包含雜原子之1價之有機基，且m表示0～5之整數}
所表示之三級胺化合物及/或胍化合物；以及
(C)光聚合起始劑。[Third aspect]
A third aspect of this embodiment will be described.
<Negative photosensitive resin composition>
The negative photosensitive resin composition of this embodiment includes:
(A) a polyimide precursor;
(B3) The following general formula (B-1):
[Chemical 67]

{In the formula, Ra and Rb are each independently a monovalent organic group having 1 to 10 carbon atoms that may contain a hetero atom, Rc is each independently a monovalent organic group that may include a hetero atom, and m represents an integer of 0 to 5 }
The tertiary amine compound and / or guanidine compound represented; and
(C) Photopolymerization initiator.

就獲得較高之解像度之觀點而言，負型感光性樹脂組合物較佳為包含100質量份之(A)聚醯亞胺前驅物、以(A)聚醯亞胺前驅物100質量份為基準之0.1～30質量份之(B3)上述三級胺化合物及/或胍化合物、及以(A)聚醯亞胺前驅物100質量份為基準之0.1～20質量份之(C)光聚合起始劑。From the viewpoint of obtaining a 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. 0.1 to 30 parts by mass of reference (B3) the tertiary amine compound and / or guanidine compound, and 0.1 to 20 parts by mass of (C) photopolymerization based on 100 parts by mass of (A) a polyimide precursor Initiator.

(B3)三級胺化合物及/或胍化合物
本實施形態中之(B3)三級胺化合物係下述通式(B-1)：
[化68]

{式中，Ra及Rb分別獨立為可包含雜原子之碳數1～10之1價之有機基，Rc分別獨立為可包含雜原子之1價之有機基，且m表示0～5之整數}
所表示之三級胺化合物。
於通式(B-1)中，Ra及Rb只要為可包含雜原子之碳數1～10之有機基則並無限定，就耐熱性之觀點而言，較佳為選自由甲基、乙基、正丙基、及異丙基所組成之群中之至少1種，就解像性之觀點而言，更佳為甲基及/或乙基。
Rc只要為可包含雜原子之1價之有機基則並無限定。其中，就耐熱性之觀點而言，較佳為碳數1～10之1價之有機基。
作為此種通式(B-1)所表示之三級胺化合物，例如可列舉：4-羥基甲基-N,N-二甲基苯胺、雙[4-(二甲胺基)苯基]甲烷等。(B3) Tertiary amine compound and / or guanidine compound (B3) The tertiary amine compound in this embodiment is the following general formula (B-1):
[Chemical 68]

{In the formula, Ra and Rb are each independently a monovalent organic group having 1 to 10 carbon atoms that may contain a hetero atom, Rc is each independently a monovalent organic group that may include a hetero atom, and m represents an integer of 0 to 5 }
The tertiary amine compound represented.
In the general formula (B-1), Ra and Rb are not limited as long as they are an organic group having 1 to 10 carbon atoms that can contain a hetero atom. From the viewpoint of heat resistance, it is preferably selected from methyl and ethyl. From the viewpoint of resolvability, at least one of the group consisting of a methyl group, an n-propyl group, and an isopropyl group is more preferably a methyl group and / or an ethyl group.
Rc is not limited as long as it is a monovalent organic group which may contain a hetero atom. Among these, a monovalent organic group having 1 to 10 carbon atoms is preferred from the viewpoint of heat resistance.
Examples of the tertiary amine compound represented by such a general formula (B-1) include 4-hydroxymethyl-N, N-dimethylaniline and bis [4- (dimethylamino) phenyl] Methane, etc.

本實施形態中之胍化合物只要具有胍結構則並無限定。其中，就樹脂組合物之保存穩定性之觀點而言，較佳為下述通式(B-2)：
[化69]

{式中，Rd表示氫原子、或可包含雜原子之碳數1～10之1價之有機基}
所表示之結構。
於通式(B-2)中，Rd只要為氫原子、或可包含雜原子之碳數1～10之有機基則並無限定。其中，作為Rd，就解像性之觀點而言，較佳為碳數1～5之有機基。
作為此種胍化合物，例如可列舉：硫酸胍基丁胺、雙氰胺、精胺酸(例如，D-(-)-精胺酸)、1-(第三丁氧基羰基)胍等。The guanidine compound in this embodiment is not limited as long as it has a guanidine structure. Among these, from the viewpoint of storage stability of the resin composition, the following general formula (B-2) is preferred:
[Chemical 69]

{In the formula, Rd represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms which may include a hetero atom}
The structure represented.
In the general formula (B-2), Rd is not limited as long as it is a hydrogen atom or an organic group having 1 to 10 carbon atoms which may contain a hetero atom. Among these, Rd is preferably an organic group having 1 to 5 carbon atoms in terms of resolvability.
Examples of such guanidine compounds include guanidinium sulfate, dicyandiamide, arginine (for example, D-(-)-spermine), 1- (third butoxycarbonyl) guanidine, and the like.

若使用上述三級胺化合物及/或胍化合物，則可獲得良好之耐化學品性與解像性、及Cu孔隙抑制效果。雖受理論約束，但關於可獲得良好之耐化學品性之理由，認為於加熱硬化後氮原子與聚醯亞胺樹脂形成高次網狀結構，藉此抑制藥液之滲入，提高耐化學品性。
又，可獲得良好之解像性之理由雖不明確，但認為其原因在於：加熱硬化前之上述三級胺化合物及/或胍化合物藉由與聚醯亞胺前驅物進行調配，更容易溶解於顯影時之顯影液而抑制殘渣。此外，顯示Cu孔隙抑制效果之理由雖未確定，但認為上述化合物之氮原子與Cu離子強烈相互作用，抑制Cu之擴散，結果抑制Cu孔隙。When the above-mentioned tertiary amine compound and / or guanidine compound is used, good chemical resistance and resolution, and Cu pore suppression effect can be obtained. Although it is bound by theory, it is considered that the reason for obtaining good chemical resistance is that nitrogen atoms and polyimide resins form a higher-order network structure after heat curing, thereby suppressing the penetration of chemical liquid and improving chemical resistance. Sex.
Although the reason for obtaining good resolution is not clear, it is thought that the reason is that the above-mentioned tertiary amine compound and / or guanidine compound before heating and hardening can be more easily dissolved by blending with a polyimide precursor. The developing solution during development suppresses residues. In addition, although the reason for showing the effect of suppressing Cu pores has not been determined, it is considered that the nitrogen atom of the above-mentioned compound strongly interacts with Cu ions to suppress the diffusion of Cu, and as a result, the pores of Cu are suppressed.

負型感光性樹脂組合物中之上述三級胺化合物或胍化合物相對於上述(A)聚醯亞胺前驅物100質量份，較佳為0.1～30質量份，更佳為1質量份以上且15質量份以下。藉由相對於(A)聚醯亞胺前驅物100質量份，於0.1質量份以上且30質量份以下之範圍內進行調配，可獲得Cu孔隙抑制效果、解像性提高及耐化學品性提高之效果尤其優異之負型感光性樹脂組合物。The tertiary amine compound or guanidine compound in the negative-type photosensitive resin composition is preferably 0.1 to 30 parts by mass, more preferably 1 part by mass or more, based on 100 parts by mass of the polyamidoimide precursor (A). 15 parts by mass or less. By blending 100 mass parts of (A) polyfluorene imide precursor in a range of 0.1 mass parts or more and 30 mass parts or less, the effect of suppressing Cu pores, improving resolution, and improving chemical resistance can be obtained. The negative photosensitive resin composition is particularly excellent in effect.

本實施形態之負型感光性樹脂組合物與第一態樣中所示之負型感光性樹脂組合物同樣地，除了應用於如上所述之半導體裝置以外，亦可用於多層電路之層間絕緣、可撓性銅箔板之覆蓋塗層、阻焊膜、及液晶配向膜等用途。第一態樣中所示之較佳之構成、數值範圍或步驟等於本實施形態中亦同樣地作為較佳之構成、數值範圍或步驟等處理。The negative-type photosensitive resin composition of this embodiment is the same as the negative-type photosensitive resin composition shown in the first aspect. In addition to being applied to the semiconductor device described above, it can also be used for interlayer insulation of multilayer circuits, Cover coatings for flexible copper foils, solder masks, and liquid crystal alignment films. The preferred configuration, numerical range, or step shown in the first aspect is equal to that in this embodiment, and is also treated as the preferred configuration, numerical range, or step.

[第四態樣]
對本實施形態之第四態樣進行說明。
＜負型感光性樹脂組合物＞
本實施形態之負型感光性樹脂組合物包含：
(A)聚醯亞胺前驅物；
(B4)酸性化合物；及
(C)光聚合起始劑。
作為(B4)酸性化合物，可列舉：(B-3)於結構中具有2個以上之酚性羥基或羧基之酸性化合物、或(B-4)於結構中具有1個選自酚性羥基或羧基中之基且具有1個以上之選自-NH-CO-A₁ 、或-CO-NH₂ 中之基之酸性化合物(A₁ 為碳數1～4之有機基)。[Fourth aspect]
A fourth aspect of this embodiment will be described.
<Negative photosensitive resin composition>
The negative photosensitive resin composition of this embodiment includes:
(A) a polyimide precursor;
(B4) an acidic compound; and
(C) Photopolymerization initiator.
Examples of the (B4) acidic compound include (B-3) an acidic compound having two or more phenolic hydroxyl groups or carboxyl groups in the structure, or (B-4) one of the phenolic hydroxyl groups or (B-4) in the structure. An acidic compound having a group in a carboxyl group and having one or more groups selected from -NH-CO-A ₁ or -CO-NH ₂ (A ₁ is an organic group having 1 to 4 carbon atoms).

就獲得較高之解像度之觀點而言，負型感光性樹脂組合物較佳為包含100質量份之(A)聚醯亞胺前驅物、以(A)聚醯亞胺前驅物100質量份為基準之0.1～30質量份之(B4)酸性化合物、及以(A)聚醯亞胺前驅物100質量份為基準之0.1～20質量份之(C)光聚合起始劑。From the viewpoint of obtaining a 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. 0.1 to 30 parts by mass of a reference (B4) acidic compound and (C) 0.1 to 20 parts by mass of a (C) photopolymerization initiator based on 100 parts by mass of a polyimide precursor.

(B4)酸性化合物
(B-3)
本實施形態中之(B-3)酸性化合物係於結構中具有2個以上之酚性羥基或羧基之酸性化合物。本實施形態之酸性化合物於結構中可具有2個以上之羧基，亦可具有2個以上之酚性羥基，亦可同時具有羧基與酚性羥基。該等之中，就顯影性與Cu孔隙抑制之觀點而言，較佳為同時具有羧基與酚性羥基之化合物。(B4) acidic compounds
(B-3)
The (B-3) acidic compound in this embodiment is an acidic compound having two or more phenolic hydroxyl or carboxyl groups in the structure. The acidic compound of this embodiment may have two or more carboxyl groups in the structure, may have two or more phenolic hydroxyl groups, and may have both a carboxyl group and a phenolic hydroxyl group. Among these, a compound having a carboxyl group and a phenolic hydroxyl group is preferred from the viewpoint of developability and Cu porosity suppression.

作為本實施形態之具有2個以上之羧基之化合物，可列舉：鄰苯二甲酸、均苯四甲酸、2,3-萘二羧酸、偏苯三甲酸、苯五羧酸、4-甲基鄰苯二甲酸、4-三氟甲基鄰苯二甲酸、4-甲氧基鄰苯二甲酸、1,3,5-三苯羧酸、間苯二甲酸、5-甲基間苯二甲酸、對苯二甲酸、1,4-萘對苯二甲酸、2,5-二甲基對苯二甲酸、3,4-吡啶二羧酸等。該等化合物之中，就耐化學品性之觀點而言，較佳為鄰苯二甲酸、間苯二甲酸、對苯二甲酸。Examples of the compound having two or more carboxyl groups in this embodiment include phthalic acid, pyromellitic acid, 2,3-naphthalenedicarboxylic acid, trimellitic acid, benzenepentacarboxylic acid, and 4-methyl Phthalic acid, 4-trifluoromethylphthalic acid, 4-methoxyphthalic acid, 1,3,5-triphenylcarboxylic acid, isophthalic acid, 5-methylisophthalic acid Terephthalic acid, 1,4-naphthalene terephthalic acid, 2,5-dimethyl terephthalic acid, 3,4-pyridine dicarboxylic acid, and the like. Among these compounds, phthalic acid, isophthalic acid, and terephthalic acid are preferred from the viewpoint of chemical resistance.

作為本實施形態之具有2個以上之酚性羥基之化合物，可列舉：鄰苯二酚、鄰苯三酚、2,3-二羥基萘、1,2-二羥基萘、1,2,4-三羥基苯、六羥基苯、4-甲基鄰苯二酚、3-甲氧基鄰苯二酚、沒食子酸甲酯、5-甲基鄰苯三酚、2,3,4-三羥基苯甲醛、間苯二酚、1,3-二羥基萘、5-甲氧基間苯二酚、2,4-二羥基苯甲醯胺、3,5-二羥基苯甲醯胺等。該等化合物之中，就耐化學品性之觀點而言，較佳為沒食子酸甲酯、1,2,4-三羥基苯、2,4-二羥基苯甲醯胺、3,5-二羥基苯甲醯胺。Examples of the compound having two or more phenolic hydroxyl groups according to this embodiment include catechol, catechol, 2,3-dihydroxynaphthalene, 1,2-dihydroxynaphthalene, and 1,1,2 -Trihydroxybenzene, hexahydroxybenzene, 4-methylcatechol, 3-methoxycatechol, methyl gallate, 5-methylcatechol, 2,3,4- Trihydroxybenzaldehyde, resorcinol, 1,3-dihydroxynaphthalene, 5-methoxyresorcinol, 2,4-dihydroxybenzamide, 3,5-dihydroxybenzamide, etc. . Among these compounds, from the viewpoint of chemical resistance, methyl gallate, 1,2,4-trihydroxybenzene, 2,4-dihydroxybenzamide, and 3,5 are preferred. -Dihydroxybenzamide.

作為本實施形態之同時具有酚性羥基與羧基之化合物，可列舉：亞甲基二水楊酸、鄰香豆酸、2-羥基苯甲酸、4-甲基水楊酸、4-羥基間苯二甲酸、4-羥基鄰苯二甲酸、5-羥基間苯二甲酸等。該等之中，就耐化學品性之觀點而言，較佳為亞甲基二水楊酸、鄰香豆酸。Examples of the compound having a phenolic hydroxyl group and a carboxyl group in this embodiment include methylene disalicylic acid, o-coumaric acid, 2-hydroxybenzoic acid, 4-methylsalicylic acid, and 4-hydroxym-benzene Dicarboxylic acid, 4-hydroxyphthalic acid, 5-hydroxyisophthalic acid, etc. Among these, from the viewpoint of chemical resistance, methylene disalicylic acid and o-coumaric acid are preferred.

(B-4)
作為另一實施形態，(B-4)酸性化合物係於結構中具有1個選自酚性羥基或羧基中之基，且具有1個以上之選自-NH-CO-A₁ 、或-CO-NH₂ 中之基之酸性化合物(A₁ 為碳數1～4之有機基)。(B-4)
As another embodiment, the (B-4) acidic compound has one group selected from the group consisting of a phenolic hydroxyl group or a carboxyl group in the structure, and has one or more groups selected from the group consisting of -NH-CO-A ₁ or -CO. -NH ₂ is an acidic compound (A ₁ is an organic group having 1 to 4 carbon atoms).

就耐化學品性之觀點而言，(B-4)酸性化合物較佳為具有下述通式(1)：
[化70]

{式(1)中，A₂ 為羥基、或羧基，A₃ 為選自-NH-CO-A₁ 、或-CO-NH₂ 中之基，A₁ 為碳數1～4之有機基，A₄ 為1價之基，m₂ 為1或2，m₃ 為0～4之整數}
所表示之結構之化合物。From the viewpoint of chemical resistance, the (B-4) acidic compound preferably has the following general formula (1):
[Chem 70]

{In formula (1), A ₂ is a hydroxyl group or a carboxyl group, A ₃ is a group selected from -NH-CO-A ₁ or -CO-NH ₂ , and A ₁ is an organic group having 1 to 4 carbon atoms. A ₄ is a monovalent base, m ₂ is 1 or 2, m ₃ is an integer from 0 to 4}
Compounds of the indicated structure.

A₁ 為碳數1～4之有機基，就耐化學品性之觀點而言，較佳為碳數1～4之烷基，更佳為甲基。
A₂ 為羥基、或羧基，就感度之觀點而言，較佳為羧基。
A₃ 為選自-NH-CO-A₁ 、或-CO-NH₂ 中之基，就耐化學品性之觀點而言，更佳為-NH-CO-A₁ 。
A₄ 為1價之基，更佳為1價之有機基，進而較佳為碳數1～4之烷基。
m₂ 為1或2，更佳為1。
m₃ 為0～4之整數，更佳為0或1。A ₁ is an organic group having 1 to 4 carbon atoms, and from the viewpoint of chemical resistance, an alkyl group having 1 to 4 carbon atoms is preferred, and a methyl group is more preferred.
A ₂ is a hydroxyl group or a carboxyl group, and from the viewpoint of sensitivity, a carboxyl group is preferred.
A ₃ is a group selected from -NH-CO-A ₁ or -CO-NH ₂ , and from the viewpoint of chemical resistance, more preferably -NH-CO-A ₁ .
A ₄ is a monovalent group, more preferably a monovalent organic group, and even more preferably an alkyl group having 1 to 4 carbon atoms.
m ₂ is 1 or 2, and more preferably 1.
m ₃ is an integer of 0 to 4, and more preferably 0 or 1.

作為本實施形態之於結構中具有1個選自酚性羥基或羧基中之基，且具有1個以上之-NH-CO-A₁ 之酸性化合物，可列舉：2-乙醯胺苯甲酸、3-乙醯胺苯甲酸、4-乙醯胺苯甲酸、5-乙醯胺-2-胺基苯甲酸、2-乙醯胺-5-溴苯甲酸、2-(乙醯乙醯胺)苯甲酸、2-乙醯胺-6-硝基苯甲酸、2-乙醯胺苯酚、3-乙醯胺苯酚、4-乙醯胺苯酚、2-乙醯胺-4-甲基苯酚。該等化合物之中，就耐化學品性之觀點而言，較佳為2-乙醯胺苯甲酸、3-乙醯胺苯甲酸、4-乙醯胺苯甲酸、2-乙醯胺苯酚、3-乙醯胺苯酚、4-乙醯胺苯酚，就感度之觀點而言，更佳為2-乙醯胺苯甲酸、3-乙醯胺苯甲酸、4-乙醯胺苯甲酸。Examples of the acidic compound having one group selected from a phenolic hydroxyl group or a carboxyl group and one or more -NH-CO-A ₁ in the structure in this embodiment include 2-acetamidobenzoic acid, 3-acetamidobenzoic acid, 4-acetamidobenzoic acid, 5-acetamido-2-aminobenzoic acid, 2-acetamido-5-bromobenzoic acid, 2- (acetamidoacetamido) Benzoic acid, 2-acetamido-6-nitrobenzoic acid, 2-acetamidophenol, 3-acetamidophenol, 4-acetamidophenol, 2-acetamido-4-methylphenol. Among these compounds, from the viewpoint of chemical resistance, 2-acetamidobenzoic acid, 3-acetamidobenzoic acid, 4-acetamidobenzoic acid, 2-acetamidophenol, From the viewpoint of sensitivity, 3-acetamidophenol and 4-acetamidophenol are more preferably 2-acetamidobenzoic acid, 3-acetamidobenzoic acid, and 4-acetamidobenzoic acid.

作為本實施形態之於結構中具有1個選自酚性羥基或羧基中之基，且具有1個以上之-CO-NH₂ 之酸性化合物，可列舉：鄰苯二甲醯胺酸、對苯二甲醯胺酸、2-羥基苯甲醯胺、2-羥基-4-甲氧基苯甲醯胺、4-羥基苯甲醯胺、5-乙醯基-2-羥基苯甲醯胺、5-氯-2-羥基苯甲醯胺、3-羥基苯甲醯胺。該等化合物之中，就耐化學品性之觀點而言，較佳為鄰苯二甲醯胺酸、對苯二甲醯胺酸、2-羥基苯甲醯胺、3-羥基苯甲醯胺、4-羥基苯甲醯胺。Examples of the acidic compound having one group selected from a phenolic hydroxyl group or a carboxyl group and one or more -CO-NH ₂ in the structure in this embodiment include phthalic acid, p-benzene Dimethylformamide, 2-hydroxybenzamide, 2-hydroxy-4-methoxybenzamide, 4-hydroxybenzamide, 5-ethylbenzyl-2-hydroxybenzamide, 5-chloro-2-hydroxybenzamide, 3-hydroxybenzamide. Among these compounds, from the viewpoint of chemical resistance, phthalic acid, p-xylylenediamine, 2-hydroxybenzidine, and 3-hydroxybenzidine are preferred. , 4-hydroxybenzidine.

若使用上述(B4)酸性化合物，則可獲得良好之耐化學品性與解像性、及Cu孔隙抑制效果。雖受理論約束，但關於可獲得良好之耐化學品性之理由，認為於熱硬化後，聚醯亞胺部分與氫鍵等相互作用，形成高次網狀結構，藉此抑制藥液之滲入而提高耐化學品性。又，可獲得良好之解像性之理由雖不明確，但認為其原因在於：加熱硬化前之酸性化合物藉由與聚醯亞胺前驅物進行調配，更容易溶解於顯影時之顯影液而抑制殘渣。此外，顯示Cu孔隙抑制效果之理由雖未確定，但認為酸性化合物中之羧基、酚性羥基、及/或醯胺基與Cu離子強烈相互作用，抑制Cu之擴散，結果抑制Cu孔隙。When the above-mentioned (B4) acidic compound is used, good chemical resistance and resolving power, and Cu pore suppression effect can be obtained. Although bound by theory, the reason for obtaining good chemical resistance is that after heat curing, the polyimide part interacts with hydrogen bonds to form a higher-order network structure, thereby suppressing the penetration of the medicinal solution. And improve chemical resistance. Although the reason for obtaining good resolution is not clear, it is thought that the reason is that the acidic compound before heating and curing can be more easily dissolved and inhibited in the developing solution during development by blending with the polyimide precursor. Residue. In addition, although the reason for showing the effect of suppressing Cu pores has not been determined, it is considered that the carboxyl group, phenolic hydroxyl group, and / or amido group in the acidic compound strongly interact with Cu ions to suppress the diffusion of Cu, and as a result, the pores of Cu are suppressed.

負型感光性樹脂組合物中之上述酸性化合物相對於上述(A)聚醯亞胺前驅物100質量份，較佳為0.1～30質量份，更佳為1質量份以上且15質量份以下。藉由相對於(A)聚醯亞胺前驅物100質量份，於0.1質量份以上且30質量份以下之範圍內進行調配，可獲得Cu孔隙抑制效果、解像性提高及耐化學品性提高之效果尤其優異之負型感光性樹脂組合物。The acidic compound in the negative-type photosensitive resin composition is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 15 parts by mass, based on 100 parts by mass of the polyimide precursor (A). By blending 100 mass parts of (A) polyfluorene imide precursor in a range of 0.1 mass parts or more and 30 mass parts or less, the effect of suppressing Cu pores, improving resolution, and improving chemical resistance can be obtained. The negative photosensitive resin composition is particularly excellent in effect.

其他成分
於本實施形態中，關於作為其他成分之溶劑、含氮雜環化合物、受阻酚化合物、有機鈦化合物、接著助劑、增感劑、光聚合性不飽和單體、熱聚合抑制劑，可使用第一態樣中所示者。Other components In this embodiment, the solvents, nitrogen-containing heterocyclic compounds, hindered phenol compounds, organic titanium compounds, adhesion promoters, sensitizers, photopolymerizable unsaturated monomers, and thermal polymerization inhibitors as other components The one shown in the first aspect may be used.

[第五態樣]
對本實施形態之第五形態進行說明。
＜負型感光性樹脂組合物＞
本實施形態之負型感光性樹脂組合物包含：
(A)聚醯亞胺前驅物；
(B5)選自由縮二脲、咔唑、吲哚、乙內醯脲、尿嘧啶衍生物及巴比妥酸所組成之群中之至少1種含氮化合物；及
(C)光聚合起始劑。[Fifth aspect]
A fifth aspect of this embodiment will be described.
<Negative photosensitive resin composition>
The negative photosensitive resin composition of this embodiment includes:
(A) a polyimide precursor;
(B5) at least one nitrogen-containing compound selected from the group consisting of biuret, carbazole, indole, hydantoin, a uracil derivative, and barbituric acid; and
(C) Photopolymerization initiator.

就獲得較高之解像度之觀點而言，負型感光性樹脂組合物包含100質量份之(A)聚醯亞胺前驅物、以(A)聚醯亞胺前驅物100質量份為基準之0.1～30質量份之(B5)選自由縮二脲、咔唑、吲哚、乙內醯脲、尿嘧啶衍生物及巴比妥酸所組成之群中之至少1種含氮化合物、及以(A)聚醯亞胺前驅物100質量份為基準之0.1～20質量份之(C)光聚合起始劑。From the viewpoint of obtaining a higher resolution, the negative photosensitive resin composition contains 100 parts by mass of (A) a polyimide precursor, and 0.1 based on 100 parts by mass of a (A) polyimide precursor. -30 parts by mass of (B5) at least one nitrogen-containing compound selected from the group consisting of biuret, carbazole, indole, hydantoin, uracil derivative, and barbituric acid, and ( A) 0.1 to 20 parts by mass of (C) a photopolymerization initiator based on 100 parts by mass of a polyimide precursor.

(B5)含氮化合物
本實施形態中之(B5)含氮化合物選自縮二脲化合物、咔唑化合物、吲哚化合物、乙內醯脲化合物、尿嘧啶衍生物、及巴比妥酸化合物。
本實施形態之縮二脲化合物只要具有縮二脲結構(R-NH-CO-NR'-CO-NH-R'')則並無限定。R、R'、及R''分別獨立為氫原子、或碳數1～20之1價之有機基。
其中，較佳為R、R'、及R''之全部為氫原子之下述結構(縮二脲)。
[化71]
(B5) Nitrogen-containing compound (B5) The nitrogen-containing compound in this embodiment is selected from the group consisting of a biuret compound, a carbazole compound, an indole compound, a hydantoin compound, a uracil derivative, and a barbituric acid compound.
The biuret compound of this embodiment is not limited as long as it has a biuret structure (R-NH-CO-NR'-CO-NH-R ''). R, R ', and R''are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
Among them, the following structure (biuret) in which all of R, R ′, and R ″ are hydrogen atoms is preferred.
[Chemical 71]

本實施形態之咔唑化合物只要具有咔唑結構則並無限定。作為此種化合物，例如可列舉：咔唑、3,6-二胺基咔唑、3,6-二甲基咔唑、3-甲基-9H-咔唑、3-苯基-9H-咔唑、3-第三丁基-9H-咔唑、3,6-二乙炔基咔唑、2-甲氧基咔唑等。該等之中，就耐化學品性之觀點而言，較佳為咔唑、及3,6-二胺基咔唑。The carbazole compound of this embodiment is not limited as long as it has a carbazole structure. Examples of such a compound include carbazole, 3,6-diaminocarbazole, 3,6-dimethylcarbazole, 3-methyl-9H-carbazole, and 3-phenyl-9H-carbazole. Azole, 3-tert-butyl-9H-carbazole, 3,6-diethynylcarbazole, 2-methoxycarbazole, and the like. Among these, carbazole and 3,6-diaminocarbazole are preferred from the viewpoint of chemical resistance.

本實施形態之吲哚化合物只要具有吲哚結構則並無限定。作為此種化合物，例如可列舉：吲哚、6-胺基吲哚、5-胺基吲哚、4-胺基吲哚、5-甲基吲哚、7-甲基吲哚、吲哚-5-羧基醛、5-羥基吲哚、5-硝基吲哚、甲基吲哚-5-羧酸酯、6-甲氧基吲哚、3-乙醯基吲哚等。該等之中，就耐化學品性之觀點而言，較佳為吲哚、6-胺基吲哚、5-胺基吲哚、及4-胺基吲哚。The indole compound of this embodiment is not limited as long as it has an indole structure. Examples of such compounds include indole, 6-aminoindole, 5-aminoindole, 4-aminoindole, 5-methylindole, 7-methylindole, and indole- 5-carboxyaldehyde, 5-hydroxyindole, 5-nitroindole, methylindole-5-carboxylic acid ester, 6-methoxyindole, 3-acetamidoindole, and the like. Among these, from the viewpoint of chemical resistance, indole, 6-aminoindole, 5-aminoindole, and 4-aminoindole are preferred.

本實施形態之乙內醯脲化合物只要具有乙內醯脲結構則並無限定。作為此種化合物，例如可列舉：乙內醯脲、5,5-二甲基乙內醯脲、5-甲基乙內醯脲、5-乙基乙內醯脲、5-苯基乙內醯脲、5-(4-羥基苯基)乙內醯脲等。該等之中，就耐化學品性之觀點而言，較佳為乙內醯脲、5-甲基乙內醯脲、及5-(4-羥基苯基)乙內醯脲。The hydantoin compound of this embodiment is not limited as long as it has a hydantoin structure. Examples of such compounds include hydantoin, 5,5-dimethylhydantoin, 5-methylhydantoin, 5-ethylhydantoin, and 5-phenylhydantoin Carbamide, 5- (4-hydroxyphenyl) hydantoin and the like. Among these, from the viewpoint of chemical resistance, hydantoin, 5-methylhydantoin, and 5- (4-hydroxyphenyl) hydantoin are preferred.

本實施形態之尿嘧啶衍生物只要為尿嘧啶、其互變異構物、或其衍生物則並無限定。作為此種化合物，例如可列舉：尿嘧啶(別名：嘧啶-2,4(1H,3H)-二酮)、羥基嘧啶酮、2,4-二羥基嘧啶、由尿嘧啶衍生之核苷(例如尿苷等)、5位之甲基置換體(胸腺嘧啶)、氟尿嘧啶、尿苷酸等。該等之中，就耐化學品性之觀點而言，較佳為尿嘧啶。The uracil derivative according to this embodiment is not limited as long as it is uracil, a tautomer thereof, or a derivative thereof. Examples of such compounds include uracil (alias: pyrimidine-2,4 (1H, 3H) -dione), hydroxypyrimidone, 2,4-dihydroxypyrimidine, and nucleosides derived from uracil (for example, Uridine, etc.), methyl substitution (thymine) at position 5, fluorouracil, uridine, and the like. Among these, uracil is preferable from the viewpoint of chemical resistance.

所謂本實施形態之巴比妥酸化合物，只要具有巴比妥酸結構則並無限定。作為此種化合物，例如可列舉：紫尿酸、巴比妥酸、5-胺基巴比妥酸、阿洛巴比妥、環己巴比妥等。該等之中，就耐化學品性之觀點而言，較佳為紫尿酸、及巴比妥酸。The barbituric acid compound of this embodiment is not limited as long as it has a barbituric acid structure. Examples of such compounds include violuric acid, barbituric acid, 5-aminobarbituric acid, alobarbitur, and cyclohexyl barbiturate. Among these, from the viewpoint of chemical resistance, violuric acid and barbituric acid are preferred.

若使用上述含氮化合物，則可獲得良好之耐化學品性與解像性、及Cu孔隙抑制效果。雖受理論約束，但關於可獲得良好之耐化學品性之理由，認為於熱硬化後與聚醯亞胺部分相互作用，形成高次網狀結構，藉此抑制藥液之滲入而提高耐化學品性。
又，可獲得良好之解像性之理由雖不明確，但認為其原因在於：加熱硬化前之含氮化合物藉由與聚醯亞胺前驅物進行調配，更容易溶解於顯影時之顯影液而抑制殘渣。此外，顯示Cu孔隙抑制效果之理由雖未確定，但認為含氮化合物藉由加熱而產生脲衍生物等，該官能基與Cu離子強烈相互作用，抑制Cu之擴散，結果抑制Cu孔隙。
就上述所說明之觀點而言，作為(B5)含氮化合物，更佳為縮二脲化合物、咔唑化合物、及吲哚化合物，進而較佳為縮二脲化合物。When the nitrogen-containing compound is used, good chemical resistance and resolution, and Cu pore suppression effect can be obtained. Although it is bound by theory, it is considered that the reason for obtaining good chemical resistance is that after thermal curing, it partially interacts with polyimide to form a higher-order network structure, thereby suppressing the penetration of chemical liquid and improving chemical resistance. Character.
Although the reason for obtaining good resolution is not clear, it is thought that the reason is that the nitrogen-containing compound before the heat curing is more easily dissolved in the developing solution during development by blending with the polyimide precursor. Suppresses residue. In addition, although the reason for showing the effect of suppressing Cu pores has not been determined, it is thought that a nitrogen-containing compound generates a urea derivative or the like by heating, and this functional group strongly interacts with Cu ions to suppress Cu diffusion and consequently suppress Cu pores.
From the viewpoints described above, the (B5) nitrogen-containing compound is more preferably a biuret compound, a carbazole compound, and an indole compound, and even more preferably a biuret compound.

負型感光性樹脂組合物中之上述含氮化合物之調配量相對於上述(A)聚醯亞胺前驅物100質量份，較佳為0.1～30質量份，更佳為1質量份以上且15質量份以下。藉由相對於(A)聚醯亞胺前驅物100質量份，於0.1質量份以上且30質量份以下之範圍內調配含氮化合物，可獲得Cu孔隙抑制效果、解像性提高及耐化學品性提高之效果尤其優異之負型感光性樹脂組合物。The blending amount of the nitrogen-containing compound in the negative photosensitive resin composition is preferably 0.1 to 30 parts by mass, more preferably 1 part by mass or more and 15 parts by mass relative to 100 parts by mass of the polyamidoimide precursor (A) described above. Mass parts or less. By blending a nitrogen-containing compound in a range of 0.1 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the polyamidoimide precursor (A), the pore suppression effect of Cu, improvement in resolution, and chemical resistance can be obtained A negative-type photosensitive resin composition having particularly excellent effect of improving properties.

其他成分
於本實施形態中，關於作為其他成分之溶劑、含氮雜環化合物、受阻酚化合物、有機鈦化合物、接著助劑、增感劑、光聚合性不飽和單體、熱聚合抑制劑，可使用第一態樣中所示者。
其中，如上所述，作為其他成分之上述含氮雜環化合物係本實施形態中之(B5)含氮化合物以外之化合物。Other components In this embodiment, the solvents, nitrogen-containing heterocyclic compounds, hindered phenol compounds, organic titanium compounds, adhesion promoters, sensitizers, photopolymerizable unsaturated monomers, and thermal polymerization inhibitors as other components, The one shown in the first aspect may be used.
However, as described above, the nitrogen-containing heterocyclic compound as another component is a compound other than the nitrogen-containing compound (B5) in the present embodiment.

[各態樣之組合]
根據上述各態樣，均可提供一種可獲得較高之耐化學品性與解像度，且於高溫保存(high temperature storage)試驗後抑制Cu層之與樹脂層相接之界面產生孔隙之負型感光性樹脂組合物，又，可提供使用該負型感光性樹脂組合物之硬化凹凸圖案之形成方法。
並且，上述各態樣可互相組合。即，(B1)活性酯化劑、(B2)熱硬化劑、(B3)三級胺化合物及/或胍化合物、(B4)酸性化合物、(B5)含氮化合物可互相組合而使用。
於將上述各態樣互相組合之情形時，負型感光性樹脂組合物中之(B1)活性酯化劑、(B2)熱硬化劑、(B3)三級胺化合物及/或胍化合物、(B4)酸性化合物、及(B5)含氮化合物之合計質量相對於(A)聚醯亞胺前驅物100質量份，較佳為0.1～30質量份，更佳為1質量份以上且15質量份以下。藉由相對於(A)聚醯亞胺前驅物100質量份，於0.1質量份以上且30質量份以下之範圍內進行調配，可獲得Cu孔隙抑制效果、解像性提高及耐化學品性提高之效果尤其優異之負型感光性樹脂組合物。
[實施例][Combination of various aspects]
According to the above aspects, it is possible to provide a negative-type photosensitivity that can obtain higher chemical resistance and resolution, and can inhibit the generation of voids at the interface between the Cu layer and the resin layer after a high temperature storage test. A negative resin composition can also provide a method for forming a hardened uneven pattern using the negative photosensitive resin composition.
Moreover, the above aspects can be combined with each other. That is, (B1) an active esterifying agent, (B2) a thermosetting agent, (B3) a tertiary amine compound and / or a guanidine compound, (B4) an acidic compound, and (B5) a nitrogen-containing compound can be used in combination with each other.
When the above-mentioned aspects are combined with each other, (B1) an active esterifying agent, (B2) a thermosetting agent, (B3) a tertiary amine compound and / or a guanidine compound, ( B4) The total mass of the acidic compound and (B5) the nitrogen-containing compound is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 15 parts by mass, relative to 100 parts by mass of the (A) polyfluorene imide precursor. the following. By blending 100 mass parts of (A) polyfluorene imide precursor in a range of 0.1 mass parts or more and 30 mass parts or less, the effect of suppressing Cu pores, improving resolution, and improving chemical resistance can be obtained. The negative photosensitive resin composition is particularly excellent in effect.
[Example]

以下，藉由實施例對本實施形態進行具體說明，但本發明並不限定於其。於實施例、比較例、及製造例中，依據以下之方法對聚合物或負型感光性樹脂組合物之物性進行測定及評價。
以下，對第一態樣進行說明。Hereinafter, this 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.
The first aspect will be described below.

＜測定及評價方法＞
(1)重量平均分子量
使用凝膠滲透層析法(標準聚苯乙烯換算)，於以下之條件下測定各樹脂之重量平均分子量(Mw)。
泵：JASCO PU-980
檢測器：JASCO RI-930
管柱烘箱：JASCO CO-965 40℃
管柱：昭和電工(股)製造之Shodex KD-806M 串聯2根、或
昭和電工(股)製造之Shodex 805M/806M串聯
標準單分散聚苯乙烯：昭和電工(股)製造之Shodex STANDARD SM-105
流動相：0.1 mol/L LiBr/N-甲基-2-吡咯啶酮(NMP)
流速：1 mL/min.＜ Measurement and evaluation method ＞
(1) Weight average molecular weight Using gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) of each resin was measured under the following conditions.
Pump: JASCO PU-980
Detector: JASCO RI-930
Column oven: JASCO CO-965 40 ℃
Column: 2 Shodex KD-806M series manufactured by Showa Denko, or Shodex 805M / 806M series standard monodisperse polystyrene manufactured by Showa Denko: Shodex STANDARD SM-105 manufactured by Showa Denko
Mobile phase: 0.1 mol / L LiBr / N-methyl-2-pyrrolidone (NMP)
Flow rate: 1 mL / min.

(2)Cu上之硬化凹凸圖案之製作
使用濺鍍裝置(L-440S-FHL型，Canon-Anelva公司製造)，於6英吋矽晶圓(富士見電子工業股份有限公司製造，厚度625±25 μm)上依序濺鍍200 nm厚之Ti、400 nm厚之Cu。繼而，使用塗佈顯影機(D-Spin60A型，SOKUDO公司製造)，於該晶圓上旋轉塗佈藉由下述方法製備之感光性樹脂組合物，利用加熱板於110℃下預烘烤180秒，形成約7 μm厚之塗膜。使用附測試圖案之遮罩，藉由Prisma GHI(Ultratech公司製造)，對該塗膜照射500 mJ/cm² 之能量。繼而，使用環戊酮作為顯影液，以塗佈顯影機(D-Spin60A型，SOKUDO公司製造)對該塗膜進行噴霧顯影，利用丙二醇甲醚乙酸酯進行沖洗，藉此獲得Cu上之凹凸圖案。
使用升溫程式固化爐(VF-2000型，Koyo Lindberg公司製造)，將於Cu上形成有該凹凸圖案之晶圓於氮氣環境下以表1中記載之固化溫度加熱處理2小時，藉此獲得於Cu上包含約4～5 μm厚之樹脂之硬化凹凸圖案。(2) Sputtering device (L-440S-FHL type, manufactured by Canon-Anelva) is used for the production of hardened concave and convex pattern on Cu. μm) were sequentially sputtered with 200 nm thick Ti and 400 nm thick Cu. Next, using a coating and developing machine (D-Spin60A type, manufactured by SOKUDO), the photosensitive resin composition prepared by the following method was spin-coated on the wafer, and pre-baked at 110 ° C for 180 hours using a hot plate. In seconds, a coating film having a thickness of about 7 μm was formed. Using a mask with a test pattern, the coating film was irradiated with energy of 500 mJ / cm ² by Prisma GHI (manufactured by Ultratech). Then, using cyclopentanone as a developing solution, this coating film was spray-developed with a coating and developing machine (D-Spin60A type, manufactured by SOKUDO), and washed with propylene glycol methyl ether acetate to obtain unevenness on Cu pattern.
Using a temperature-programming curing furnace (VF-2000 type, manufactured by Koyo Lindberg), the wafer having the uneven pattern formed on Cu was heat-treated at a curing temperature described in Table 1 for 2 hours under a nitrogen atmosphere, thereby obtaining Cu contains a hardened uneven pattern of about 4 to 5 μm thick resin.

(3)Cu上之硬化凹凸圖案之解像性評價
於光學顯微鏡下觀察利用上述方法所得之硬化凹凸圖案，求出最小開口圖案之尺寸。此時，若所得之圖案之開口部之面積為對應之圖案遮罩開口面積之1/2以上則視為經解像者，將經解像之開口部中具有最小面積者所對應之遮罩開口邊之長度設為解像度。將解像度未達10 μm者設為「優」、將10 μm以上且未達14 μm者設為「良」、將14 μm以上且未達18 μm者設為「可」、將18 μm以上者設為「不可」。(3) Evaluation of the resolution of the hardened concave-convex pattern on Cu The hardened concave-convex pattern obtained by the above method was observed under an optical microscope, and the size of the smallest opening pattern was determined. At this time, if the area of the opening of the obtained pattern is 1/2 or more of the opening area of the corresponding pattern mask, it is regarded as a resolved person, and the mask corresponding to the smallest area in the resolved opening portion The length of the open side is set to the resolution. Those with a resolution of less than 10 μm are rated as “excellent”, those with a resolution of 10 μm or more and less than 14 μm are set as “good”, those with a resolution of 14 μm and less than 18 μm are set as “good”, and those with a resolution of 18 μm or more Set to "impossible".

(4)Cu上之硬化凹凸圖案之高溫保存(high temperature storage)試驗與其後之孔隙面積評價
使用升溫程式固化爐(VF-2000型，Koyo Lindberg公司製造)，將於Cu上形成有該硬化凹凸圖案之晶圓於空氣中以150℃加熱168小時。繼而，使用電漿表面處理裝置(EXAM型，神港精機公司製造)，藉由電漿蝕刻將Cu上之樹脂層全部去除。電漿蝕刻條件如下所述。
輸出：133 W
氣體種・流量：O₂ ：40 mL/min＋CF₄ ：1 mL/min
氣體壓力：50 Pa
模式：困難模式
蝕刻時間：1800秒(4) High temperature storage test of hardened uneven pattern on Cu and evaluation of pore area thereafter Using a temperature-programmed curing furnace (VF-2000 type, manufactured by Koyo Lindberg), the hardened unevenness is formed on Cu The patterned wafer was heated in air at 150 ° C for 168 hours. Next, a plasma surface treatment apparatus (EXAM type, manufactured by Shinko Seiki Co., Ltd.) was used to remove all the resin layers on Cu by plasma etching. The plasma etching conditions are as follows.
Output: 133 W
Gas type and flow rate: O ₂ : 40 mL / min + CF ₄ : 1 mL / min
Gas pressure: 50 Pa
Mode: Hard Mode Etching Time: 1800 seconds

藉由FE-SEM(Field-emission Scanning Electron Microscope，場效掃描式電子顯微鏡)(S-4800型，Hitachi High-Technologies公司製造)觀察將樹脂層全部去除之Cu表面，使用圖像解析軟體(A像君，旭化成公司製造)，算出Cu層之表面所占之孔隙之面積。將評價比較例1中記載之感光性樹脂組合物時之孔隙之總面積設為100%時，將孔隙之總面積比率未達50%者判定為「優」、將50%以上且未達75%者判定為「良」、將75%以上且未達100%者判定為「可」、將100%以上者判定為「不可」。The Cu surface from which the resin layer was completely removed was observed with a FE-SEM (Field-emission Scanning Electron Microscope) (S-4800, manufactured by Hitachi High-Technologies), and image analysis software (A (Like Jun, manufactured by Asahi Kasei Corporation), calculate the area of the pores occupied by the surface of the Cu layer. When the total area of pores when the photosensitive resin composition described in Comparative Example 1 was evaluated was set to 100%, those with a total area ratio of pores of less than 50% were judged to be "excellent", 50% or more and less than 75 % Is judged as "good", 75% or more and less than 100% is judged as "good", and 100% or more is judged as "impossible".

(5)硬化凹凸圖案(聚醯亞胺塗膜)之耐化學品性評價
於將抗蝕劑剝離液{ATMI公司製造，製品名ST-44，主成分：2-(2-胺基乙氧基)乙醇、及1-環己基-2-吡咯啶酮}加熱至50℃而成者中將形成於Cu上之該硬化凹凸圖案浸漬5分鐘，利用流水洗淨1分鐘並進行風乾。其後，利用光學顯微鏡目視觀察膜表面，基於龜裂等由藥液引起之損傷之有無、及/或藥液處理後之膜厚之變化率評價耐化學品性。作為評價基準，將未產生龜裂等損傷且膜厚變化率以藥品浸漬前之膜厚為基準時為10%以內者設為「優」、將超過10%且15%以內者設為「良」、將超過15%且20%以內者設為「可」、將產生龜裂或膜厚變化率超過20%者設為「不可」。(5) Evaluation of the chemical resistance of the hardened uneven pattern (polyimide coating film) The resist stripping solution (manufactured by ATMI, product name ST-44, main component: 2- (2-aminoethoxy) Group) ethanol and 1-cyclohexyl-2-pyrrolidone} were heated to 50 ° C., the hardened uneven pattern formed on Cu was immersed for 5 minutes, washed with running water for 1 minute, and air-dried. Thereafter, the film surface was visually observed with an optical microscope, and chemical resistance was evaluated based on the presence or absence of damage caused by the chemical solution such as cracks and / or the rate of change in film thickness after the chemical solution treatment. As an evaluation criterion, a case where no damage such as cracks occurs and the film thickness change rate is based on a film thickness before drug immersion of less than 10% is regarded as "excellent", and those exceeding 10% and less than 15% are regarded as "good"", If it is more than 15% and less than 20%, it is" allowable ", and if it is cracked or the film thickness change rate is more than 20%, it is" impossible ".

製造例1：作為(A)聚醯亞胺前驅物之聚合物A-1之合成
將4,4'-氧二鄰苯二甲酸二酐(ODPA)155.1 g添加至容量2 L之可分離式燒瓶中，並添加甲基丙烯酸2-羥基乙酯(HEMA)131.2 g與γ-丁內酯400 mL，於室溫下進行攪拌，一面攪拌一面添加吡啶81.5 g，獲得反應混合物。於由反應引起之放熱結束後，將反應混合物放冷至室溫並放置16小時。
繼而，於冰浴冷卻下，一面攪拌一面歷時40分鐘將二環己基碳二醯亞胺(DCC)206.3 g溶解於γ-丁內酯180 mL而成之溶液添加至反應混合物中，繼而一面攪拌一面歷時60分鐘添加使4,4'-氧二苯胺(ODA)93.0 g懸浮於γ-丁內酯350 mL而成者。進而於室溫下攪拌2小時後，添加乙醇30 mL攪拌1小時，繼而添加γ-丁內酯400 mL。將反應混合物中產生之沈澱物藉由過濾去除，獲得反應液。
將所得之反應液添加至3 L之乙醇中而生成包含粗聚合物之沈澱物。將所生成之粗聚合物過濾分離，溶解於四氫呋喃1.5 L，獲得粗聚合物溶液。將所得之粗聚合物溶液滴加至28 L之水中使聚合物沈澱，將所得之沈澱物過濾分離後，進行真空乾燥獲得粉末狀之聚合物(聚合物A-1)。利用凝膠滲透層析法(標準聚苯乙烯換算)測定聚合物(A-1)之分子量，結果重量平均分子量(Mw)為20,000。Production Example 1: Synthesis of polymer A-1 as (A) polyfluorene imine precursor A separable formula in which 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was added to a capacity of 2 L In the flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone were added, and the mixture was stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the exotherm caused by the reaction was completed, the reaction mixture was allowed to cool to room temperature and left for 16 hours.
Next, while cooling in an ice bath, a solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 mL of γ-butyrolactone was added to the reaction mixture while stirring for 40 minutes, followed by stirring. One side was prepared by adding 93.0 g of 4,4'-oxydiphenylamine (ODA) in 350 mL of γ-butyrolactone over 60 minutes. After further stirring at room temperature for 2 hours, 30 mL of ethanol was added and stirred for 1 hour, and then 400 mL of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.
The obtained reaction solution was added to 3 L of ethanol to produce a precipitate containing a crude polymer. The produced crude polymer was separated by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 L of water to precipitate a polymer. The obtained precipitate was separated by filtration, and then vacuum-dried to obtain a powdery polymer (Polymer A-1). When the molecular weight of the polymer (A-1) was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000.

製造例2：作為(A)聚醯亞胺前驅物之聚合物A-2之合成
使用3,3',4,4'-聯苯四羧酸二酐(BPDA)147.1 g代替製造例1之4,4'-氧二鄰苯二甲酸二酐(ODPA)155.1 g，除此以外，以與上述製造例1中記載之方法同樣之方式進行反應，獲得聚合物(A-2)。利用凝膠滲透層析法(標準聚苯乙烯換算)測定聚合物(A-2)之分子量，結果重量平均分子量(Mw)為22,000。Production Example 2: Synthesis of Polymer A-2 as (A) Polyfluorene Imide Precursor 147.1 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of Production Example 1 A polymer (A-2) was obtained by reacting in the same manner as in the method described in Production Example 1 above except that 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) was obtained. When the molecular weight of the polymer (A-2) was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 22,000.

製造例3：作為(A)聚醯亞胺前驅物之聚合物A-3之合成
使用對苯二胺50.2 g代替製造例1之4,4'-氧二苯胺(ODA)93.0 g，除此以外，以與上述製造例1中記載之方法同樣之方式進行反應，獲得聚合物(A-3)。利用凝膠滲透層析法(標準聚苯乙烯換算)測定聚合物(A-3)之分子量，結果重量平均分子量(Mw)為19,000。Production Example 3: Synthesis of Polymer A-3 as (A) Polyfluorene Imide Precursor 50.2 g of p-phenylenediamine was used in place of 93.0 g of 4,4'-oxydiphenylamine (ODA) in Production Example 1 Other than that, it reacted by the method similar to the method described in said manufacturing example 1, and obtained the polymer (A-3). When the molecular weight of the polymer (A-3) was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 19,000.

＜實施例1-1＞
使用聚合物A-1，藉由以下之方法製備負型感光性樹脂組合物，進行所製備之組合物之評價。將作為(A)聚醯亞胺前驅物之聚合物A-1：100 g、作為(B1)活性酯化劑之化合物B-11：5 g、及作為(C)光聚合起始劑之1-苯基-1,2-丙二酮-2-(O-乙氧基羰基)-肟(相當於感光劑C-1)：3 g溶解於γ-丁內酯(以下記載為GBL)：150 g中。藉由進而添加少量之GBL，將所得之溶液之黏度調整至約30泊，製成負型感光性樹脂組合物。依據上述方法評價該組合物。將結果示於表1。<Example 1-1>
Using the polymer A-1, a negative-type photosensitive resin composition was prepared by the following method, and evaluation of the prepared composition was performed. (A) Polymer A-1 as a precursor of polyfluorene imine: 100 g, Compound B-11 as a (B1) active esterifying agent: 5 g, and 1 as a (C) photopolymerization initiator -Phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime (equivalent to photosensitizer C-1): 3 g dissolved in γ-butyrolactone (hereinafter referred to as GBL): 150 g. By further adding a small amount of GBL, the viscosity of the obtained solution was adjusted to about 30 poise to prepare a negative photosensitive resin composition. The composition was evaluated according to the method described above. The results are shown in Table 1.

＜實施例1-2～1-10、比較例1＞
以如表1所示之成分與調配比進行製備，除此以外，製備與實施例1-1同樣之負型感光性樹脂組合物，進行與實施例1-1同樣之評價。將其結果示於表1。表1中記載之化合物(B-11～B-15)與感光劑(C-1)分別如下所述。<Examples 1-2 to 1-10, Comparative Example 1>
A negative-type photosensitive resin composition similar to that of Example 1-1 was prepared with the exception of preparing the components and blending ratios shown in Table 1, and the same evaluation as that of Example 1-1 was performed. The results are shown in Table 1. The compounds (B-11 to B-15) and the photosensitizer (C-1) described in Table 1 are as follows.

B-11：1-羥基-7-氮雜苯并三唑
B-12：五氟苯酚
B-13：碳酸雙(五氟苯基)酯
B-14：碳酸雙(4-硝基苯基)酯
B-15：三氟乙酸4-硝基苯酯
C-1：1-苯基-1,2-丙二酮-2-(O-乙氧基羰基)-肟B-11: 1-hydroxy-7-azabenzotriazole
B-12: Pentafluorophenol
B-13: Bis (pentafluorophenyl) carbonate
B-14: bis (4-nitrophenyl) carbonate
B-15: 4-nitrophenyl trifluoroacetate
C-1: 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime

[表1]
[Table 1]

以下，對第二態樣進行說明。
其中，＜測定及評價方法＞及製造例1～3係與上述同樣。The second aspect will be described below.
Among them, the <Measurement and Evaluation Method> and Production Examples 1 to 3 are the same as described above.

＜實施例2-1＞
使用聚合物A-1，藉由以下之方法製備負型感光性樹脂組合物，進行所製備之組合物之評價。將作為(A)聚醯亞胺前驅物之聚合物A-1：100 g、作為(B2)熱硬化劑之化合物B-21：8 g、及作為(C)光聚合起始劑之1-苯基-1,2-丙二酮-2-(O-乙氧基羰基)-肟(相當於感光劑C-1)：3 g溶解於γ-丁內酯(以下記載為GBL)：150 g中。藉由進而添加少量之GBL，將所得之溶液之黏度調整至約30泊，製成負型感光性樹脂組合物。依據上述方法評價該組合物。將結果示於表2。<Example 2-1>
Using the polymer A-1, a negative-type photosensitive resin composition was prepared by the following method, and evaluation of the prepared composition was performed. Polymer (A) as a precursor of (A) polyimide, 100 g, compound B-21 as a (B2) thermosetting agent, 8 g, and 1- (1) as a photopolymerization initiator Phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime (equivalent to photosensitizer C-1): 3 g dissolved in γ-butyrolactone (hereinafter referred to as GBL): 150 g. By further adding a small amount of GBL, the viscosity of the obtained solution was adjusted to about 30 poise to prepare a negative photosensitive resin composition. The composition was evaluated according to the method described above. The results are shown in Table 2.

＜實施例2-2～2-11、比較例1＞
以如表2所示之成分與調配比進行製備，除此以外，製備與實施例2-1同樣之負型感光性樹脂組合物，進行與上述同樣之評價。將其結果示於表2。表2中記載之化合物(B-21～B-26)與感光劑(C-1)分別如下所述。<Examples 2-2 to 2-11, Comparative Example 1>
A negative-type photosensitive resin composition similar to that of Example 2-1 was prepared with the exception of preparing the components and blending ratios shown in Table 2 and evaluated in the same manner as described above. The results are shown in Table 2. The compounds (B-21 to B-26) and the photosensitizer (C-1) described in Table 2 are as follows.

B-21：下述通式(10)所表示之苯并㗁
[化72]

B-22：下述通式(11)所表示之苯并㗁
[化73]

B-23：雙酚A型環氧樹脂(LX-01，Daiso公司製造)
B-24：雙酚F型環氧樹脂(YL983U，Japan Epoxy Resins公司製造)
B-25：下述通式(12)所表示之化合物
[化74]

B-26：3-烯丙氧基氧雜環丁烷
C-1：1-苯基-1,2-丙二酮-2-(O-乙氧基羰基)-肟B-21: benzopyrene represented by the following general formula (10)
[Chemical 72]

B-22: benzopyrene represented by the following general formula (11)
[Chemical 73]

B-23: Bisphenol A epoxy resin (LX-01, manufactured by Daiso)
B-24: Bisphenol F-type epoxy resin (YL983U, manufactured by Japan Epoxy Resins)
B-25: Compound represented by the following general formula (12)
[Chemical 74]

B-26: 3-allyloxyoxetane
C-1: 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime

[表2]
[Table 2]

以下，對第三態樣進行說明。
其中，＜測定及評價方法＞及製造例1～3係與上述同樣。The third aspect will be described below.
Among them, the <Measurement and Evaluation Method> and Production Examples 1 to 3 are the same as described above.

＜實施例3-1＞
使用聚合物A-1，藉由以下之方法製備負型感光性樹脂組合物，進行所製備之組合物之評價。將作為(A)聚醯亞胺前驅物之聚合物A-1：100 g、作為(B3)三級胺化合物及/或胍化合物之化合物B-31：8 g、及作為(C)光聚合起始劑之1-苯基-1,2-丙二酮-2-(O-乙氧基羰基)-肟(相當於感光劑C-1)：3 g溶解於γ-丁內酯(以下記載為GBL)：150 g中。藉由進而添加少量之GBL，將所得之溶液之黏度調整至約30泊，製成負型感光性樹脂組合物。依據上述方法評價該組合物。將結果示於表3。<Example 3-1>
Using the polymer A-1, a negative-type photosensitive resin composition was prepared by the following method, and evaluation of the prepared composition was performed. (A) Polymer A-1 as a polyfluorene imine precursor: 100 g, (B3) a tertiary amine compound and / or a guanidine compound B-31: 8 g, and (C) photopolymerization 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime (equivalent to photosensitizer C-1): 3 g dissolved in γ-butyrolactone (hereinafter Recorded as GBL): 150 g. By further adding a small amount of GBL, the viscosity of the obtained solution was adjusted to about 30 poise to prepare a negative photosensitive resin composition. The composition was evaluated according to the method described above. The results are shown in Table 3.

＜實施例3-2～3-8、比較例1＞
以如表3所示之成分與調配比進行製備，除此以外，製備與實施例3-1同樣之負型感光性樹脂組合物，進行與上述同樣之評價。將其結果示於表3。表3中記載之化合物(B-31～B-34)與感光劑(C-1)分別如下所述。<Examples 3-2 to 3-8, Comparative Example 1>
A negative-type photosensitive resin composition similar to that of Example 3-1 was prepared except that components and blending ratios shown in Table 3 were used for preparation, and the same evaluations as described above were performed. The results are shown in Table 3. The compounds (B-31 to B-34) and the photosensitizer (C-1) described in Table 3 are as follows.

B-31：4-羥基甲基-N,N-二甲基苯胺
B-32：雙[4-(二甲胺基)苯基]甲烷
B-33：雙氰胺
B-34：D-(-)-精胺酸
C-1：1-苯基-1,2-丙二酮-2-(O-乙氧基羰基)-肟B-31: 4-hydroxymethyl-N, N-dimethylaniline
B-32: bis [4- (dimethylamino) phenyl] methane
B-33: Dicyandiamide
B-34: D-(-)-Spermine
C-1: 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime

[表3]
[table 3]

以下，對第四態樣進行說明。
其中，＜測定及評價方法＞及製造例1～3係與上述同樣。The fourth aspect will be described below.
Among them, the <Measurement and Evaluation Method> and Production Examples 1 to 3 are the same as described above.

＜實施例4-1＞
使用聚合物A-1，藉由以下之方法製備負型感光性樹脂組合物，進行所製備之組合物之評價。將作為(A)聚醯亞胺前驅物之聚合物A-1：100 g、作為(B4)酸性化合物之化合物B-41：8 g、及作為(C)光聚合起始劑之1-苯基-1,2-丙二酮-2-(O-乙氧基羰基)-肟(相當於感光劑C-1)：3 g溶解於γ-丁內酯(以下記載為GBL)：150 g中。藉由進而添加少量之GBL，將所得之溶液之黏度調整至約30泊，製成負型感光性樹脂組合物。依據上述方法評價該組合物。將結果示於表4。<Example 4-1>
Using the polymer A-1, a negative-type photosensitive resin composition was prepared by the following method, and evaluation of the prepared composition was performed. (A) Polymer A-1 as a precursor of polyfluorene imine: 100 g, Compound B-41 as an acidic compound (B4): 8 g, and 1-benzene as a photopolymerization initiator -1,2-propanedione-2- (O-ethoxycarbonyl) -oxime (equivalent to photosensitizer C-1): 3 g dissolved in γ-butyrolactone (hereinafter referred to as GBL): 150 g in. By further adding a small amount of GBL, the viscosity of the obtained solution was adjusted to about 30 poise to prepare a negative photosensitive resin composition. The composition was evaluated according to the method described above. The results are shown in Table 4.

＜實施例4-2～4-10、比較例1＞
以如表4所示之成分與調配比進行製備，除此以外，製備與實施例4-1同樣之負型感光性樹脂組合物，進行與上述同樣之評價。將其結果示於表4。表4中記載之化合物(B-41～B-46)與感光劑(C-1)分別如下所述。<Examples 4-2 to 4-10, Comparative Example 1>
A negative-type photosensitive resin composition similar to that of Example 4-1 was prepared with the exception of preparing the components and blending ratios shown in Table 4 and evaluated in the same manner as described above. The results are shown in Table 4. The compounds (B-41 to B-46) and the photosensitizer (C-1) described in Table 4 are as follows.

B-41：沒食子酸甲酯
B-42：亞甲基二水楊酸
B-43：鄰香豆酸
B-44：鄰苯二甲酸
B-45：4-乙醯胺苯甲酸
B-46：3-羥基苯甲醯胺
C-1：1-苯基-1,2-丙二酮-2-(O-乙氧基羰基)-肟B-41: methyl gallate
B-42: methylene disalicylic acid
B-43: o-coumaric acid
B-44: Phthalic acid
B-45: 4-acetamidobenzoic acid
B-46: 3-hydroxybenzidine
C-1: 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime

[表4]
[Table 4]

以下，對第五態樣進行說明。
其中，＜測定及評價方法＞及製造例1～3係與上述同樣。The fifth aspect will be described below.
Among them, the <Measurement and Evaluation Method> and Production Examples 1 to 3 are the same as described above.

＜實施例5-1＞
使用聚合物A-1，藉由以下之方法製備負型感光性樹脂組合物，進行所製備之組合物之評價。將作為(A)聚醯亞胺前驅物之聚合物A-1：100 g、作為(B5)含氮化合物之化合物B-51：8 g、及作為(C)光聚合起始劑之1-苯基-1,2-丙二酮-2-(O-乙氧基羰基)-肟(相當於感光劑C-1)：3 g溶解於γ-丁內酯(以下記載為GBL)：150 g中。藉由進而添加少量之GBL，將所得之溶液之黏度調整至約30泊，製成負型感光性樹脂組合物。依據上述方法評價該組合物。將結果示於表5。<Example 5-1>
Using the polymer A-1, a negative-type photosensitive resin composition was prepared by the following method, and evaluation of the prepared composition was performed. (A) Polymer A-1 as a precursor of polyfluorene imine: 100 g, Compound B-51 as (B5) nitrogen-containing compound: 8 g, and 1- (1) as a photopolymerization initiator Phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime (equivalent to photosensitizer C-1): 3 g dissolved in γ-butyrolactone (hereinafter referred to as GBL): 150 g. By further adding a small amount of GBL, the viscosity of the obtained solution was adjusted to about 30 poise to prepare a negative photosensitive resin composition. The composition was evaluated according to the method described above. The results are shown in Table 5.

＜實施例5-2～5-12、比較例1＞
以如表5所示之成分與調配比進行製備，除此以外，製備與實施例5-1同樣之負型感光性樹脂組合物，進行與上述同樣之評價。將其結果示於表5。表5中記載之化合物(B-51～B-57)與感光劑(C-1)分別如下所述。<Examples 5-2 to 5-12, Comparative Example 1>
A negative-type photosensitive resin composition similar to that of Example 5-1 was prepared with the exception of preparing the components and blending ratios shown in Table 5 and evaluated in the same manner as described above. The results are shown in Table 5. The compounds (B-51 to B-57) and the photosensitizer (C-1) described in Table 5 are as follows.

B-51：縮二脲
B-52：3,6-二胺基咔唑
B-53：5-胺基吲哚
B-54：乙內醯脲
B-55：巴比妥酸
B-56：紫尿酸
B-57：尿嘧啶
C-1：1-苯基-1,2-丙二酮-2-(O-乙氧基羰基)-肟B-51: Biuret
B-52: 3,6-diaminocarbazole
B-53: 5-aminoindole
B-54: Hydantoin
B-55: Barbituric acid
B-56: Purpuric acid
B-57: uracil
C-1: 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime

[表5]

[產業上之可利用性][table 5]

[Industrial availability]

藉由使用本發明之感光性樹脂組合物，可獲得具有較高之耐化學品性與解像性之硬化凹凸圖案，且可抑制Cu表面之孔隙產生。本發明例如可於對半導體裝置、多層配線基板等電氣・電子材料之製造有用之感光性材料之領域中較佳地使用。By using the photosensitive resin composition of the present invention, a hardened concave-convex pattern having high chemical resistance and resolution can be obtained, and generation of pores on the Cu surface can be suppressed. The present invention can be preferably used, for example, in the field of photosensitive materials useful for the manufacture of electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

A negative photosensitive resin composition comprising: (A) a polyimide precursor; (B) an active esterifying agent; and (C) Photopolymerization initiator.

The negative photosensitive resin composition according to claim 1, wherein the (B) active esterifying agent is selected from the group consisting of bis (pentafluorophenyl) carbonate, bis (4-nitrophenyl) carbonate, and bis (N -Succinimide) carbonate, pentafluorophenol, 1-hydroxy-7-azabenzotriazole and 4-nitrophenyl trifluoroacetate.

The negative-type photosensitive resin composition according to claim 1 or 2, wherein the (A) polyimide precursor comprises a polyimide precursor having a structural unit represented by the following general formula (2): [化1] {Wherein 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, R At least one of ₁ and R ₂ is a monovalent organic group}.

The negative-type photosensitive resin composition according to claim 3, wherein in the general formula (2), at least one of R ₁ and R ₂ is a monovalent organic group represented by the following general formula (3): [化 2] {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 according to claim 3 or 4, wherein in the general formula (2), X ₁ includes a structure represented by the following general formula (20a): [化 3] .

The negative photosensitive resin composition according to claim 3 or 4, wherein in the general formula (2), X ₁ includes a structure represented by the following general formula (20b): [化 4] .

The negative-type photosensitive resin composition according to any one of claims 3 to 6, wherein in the general formula (2), Y ₁ includes a structure represented by the following general formula (21b): [化 5] .

The negative photosensitive resin composition according to claim 3 or 4, wherein the (A) polyimide precursor comprises a polyimide precursor having a structural unit represented by the following general formula (4): 6] {Wherein R ₁ , R ₂ , and n ₁ are as defined above}.

The negative photosensitive resin composition according to claim 3 or 4, wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (5): [化7] {Wherein R ₁ , R ₂ , and n ₁ are as defined above}.

The negative-type photosensitive resin composition according to any one of claims 3 to 9, wherein the (A) polyimide precursor includes structural units represented by the following general formulae (4) and (5):化 8] {Wherein, R _1, R _2, and n ₁ are those defined above, _1, R _2, and the same as _a general formula R (5) are of n, or different} [Formula 9] {In the formula, R ₁ , R ₂ , and n ₁ are respectively defined above, and are the same as R ₁ , R ₂ , and n ₁ in the general formula (4), or may be different}.

The negative-type photosensitive resin composition according to claim 10, wherein the (A) polyimide precursor is a copolymer of a structural unit represented by the general formulae (4) and (5).

The negative photosensitive resin composition according to any one of claims 1 to 11, comprising: 100 parts by mass of the aforementioned (A) polyimide precursor, 0.1 to 30 parts by mass of the above (B) active esterifying agent based on 100 parts by mass of the aforementioned (A) polyfluorene imide precursor, and 0.1 to 20 parts by mass of the aforementioned (C) photopolymerization initiator based on 100 parts by mass of the aforementioned (A) polyfluorene imide precursor.

A method for producing polyimide, comprising the step of converting the negative photosensitive resin composition according to any one of claims 1 to 12 to polyimide.

A method for manufacturing a hardened uneven pattern includes: (1) a step of applying the negative photosensitive resin composition according to any one of claims 1 to 12 on a substrate to form a photosensitive resin layer on the substrate; (2) a step of exposing the photosensitive resin layer, (3) a step of developing the photosensitive resin layer after exposure to form a concave-convex pattern, and (4) A step of heating the aforementioned uneven pattern to form a hardened uneven pattern.

A negative photosensitive resin composition comprising: (A) a polyimide precursor; (B) a thermosetting agent; and (C) Photopolymerization initiator.

The negative-type photosensitive resin composition according to claim 15, wherein the (B) thermosetting agent is at least one selected from the group consisting of benzofluorene, epoxy resin, and oxetane resin.

The negative-type photosensitive resin composition according to claim 15 or 16, wherein the (B) thermosetting agent is benzofluorene.

The negative photosensitive resin composition according to any one of claims 15 to 17, wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (2) Thing: [化 10] {Wherein 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, R At least one of ₁ and R ₂ is a monovalent organic group}.

The negative photosensitive resin composition according to claim 18, wherein in the general formula (2), at least one of R ₁ and R ₂ is a monovalent organic group represented by the following general formula (3): [化 11] {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 according to claim 18 or 19, wherein in the general formula (2), X ₁ includes a structure represented by the following general formula (20a): [化 12] .

The negative photosensitive resin composition according to claim 18 or 19, wherein in the general formula (2), X ₁ includes a structure represented by the following general formula (20b): [化 13] .

The negative-type photosensitive resin composition according to any one of claims 18 to 21, wherein in the general formula (2), Y ₁ includes a structure represented by the following general formula (21b): [化 14] .

The negative-type photosensitive resin composition according to claim 18 or 19, wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (4): 15] {Wherein R ₁ , R ₂ , and n ₁ are as defined above}.

The negative photosensitive resin composition according to claim 18 or 19, wherein the (A) polyimide precursor comprises a polyimide precursor having a structural unit represented by the following general formula (5): [化16] {Wherein R ₁ , R ₂ , and n ₁ are as defined above}.

The negative photosensitive resin composition according to any one of claims 18 to 24, wherein the (A) polyimide precursor includes structural units represented by the following general formulae (4) and (5):化 17] {Wherein, R _1, R _2, and n ₁ are those defined above, _1, R _2, and the same as _a general formula R (5) are of n, or different} [Formula 18] {In the formula, R ₁ , R ₂ , and n ₁ are respectively defined above, and are the same as R ₁ , R ₂ , and n ₁ in the general formula (4), or may be different}.

The negative photosensitive resin composition according to claim 25, wherein the (A) polyimide precursor is a copolymer of a structural unit represented by the general formulae (4) and (5).

The negative photosensitive resin composition according to any one of claims 15 to 26, comprising: 100 parts by mass of the aforementioned (A) polyimide precursor, 0.1 to 30 parts by mass of the above (B) thermosetting agent based on 100 parts by mass of the aforementioned (A) polyfluorene imide precursor, and 0.1 to 20 parts by mass of the aforementioned (C) photopolymerization initiator based on 100 parts by mass of the aforementioned (A) polyfluorene imide precursor.

A method for producing polyimide, comprising the step of converting the negative photosensitive resin composition according to any one of claims 15 to 27 to polyimide.

A method for manufacturing a hardened uneven pattern includes: (1) a step of applying the negative photosensitive resin composition according to any one of claims 15 to 27 on a substrate to form a photosensitive resin layer on the substrate; (2) a step of exposing the photosensitive resin layer, (3) a step of developing the photosensitive resin layer after exposure to form a concave-convex pattern, and (4) A step of heating the aforementioned uneven pattern to form a hardened uneven pattern.

A negative photosensitive resin composition, comprising: (A) a polyimide precursor; (B) selected from the following general formula (B-1): [化 19] {In the formula, Ra and Rb are each independently a monovalent organic group having 1 to 10 carbon atoms that may contain a hetero atom, Rc is each independently a monovalent organic group that may include a hetero atom, and m represents an integer of 0 to 5 } At least one selected from the group consisting of a tertiary amine compound and a guanidine compound; and (C) a photopolymerization initiator.

The negative photosensitive resin composition according to claim 30, wherein in the general formula (B-1), Ra and Rb are selected from the group consisting of methyl, ethyl, n-propyl, and isopropyl At least one of them.

The negative-type photosensitive resin composition according to claim 30, wherein the guanidine compound is a compound represented by the following general formula (B-2): [化 20] {In the formula, Rd represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms which may include a hetero atom}.

The negative photosensitive resin composition according to any one of claims 30 to 32, wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (2) Object: [化 21] {Wherein 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, R At least one of ₁ and R ₂ is a monovalent organic group}.

The negative photosensitive resin composition according to claim 33, wherein in the general formula (2), at least one of R ₁ and R ₂ is a monovalent organic group represented by the following general formula (3): [ 22] {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-type photosensitive resin composition according to claim 33 or 34, wherein in the general formula (2), X ₁ includes a structure represented by the following general formula (20a): [化 23] .

The negative photosensitive resin composition according to claim 33 or 34, wherein in the general formula (2), X ₁ includes a structure represented by the following general formula (20b): [化 24] .

The negative photosensitive resin composition according to any one of claims 33 to 36, wherein in the general formula (2), Y ₁ includes a structure represented by the following general formula (21b): [化 25] .

The negative photosensitive resin composition according to claim 33 or 34, wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (4): 26] {Wherein R ₁ , R ₂ , and n ₁ are as defined above}.

The negative photosensitive resin composition according to claim 33 or 34, wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (5): [化27] {Wherein R ₁ , R ₂ , and n ₁ are as defined above}.

The negative photosensitive resin composition according to any one of claims 33 to 39, wherein the (A) polyimide precursor includes structural units represented by the following general formulae (4) and (5): Hua 28] {In the formula, R ₁ , R ₂ , and n ₁ are respectively defined above, and are the same as R ₁ , R ₂ , and n ₁ in the general formula (5), or may be different} [化 29] {In the formula, R ₁ , R ₂ , and n ₁ are respectively defined above, and are the same as R ₁ , R ₂ , and n ₁ in the general formula (4), or may be different}.

The negative-type photosensitive resin composition according to claim 40, wherein the (A) polyimide precursor is a copolymer of a structural unit represented by the general formulae (4) and (5).

The negative photosensitive resin composition according to any one of claims 30 to 41, comprising: 100 parts by mass of the aforementioned (A) polyimide precursor, 0.1 to 30 parts by mass of the above (B) tertiary amine compound and / or guanidine compound based on 100 parts by mass of the aforementioned (A) polyfluorene imide precursor, and 0.1 to 20 parts by mass of the aforementioned (C) photopolymerization initiator based on 100 parts by mass of the aforementioned (A) polyfluorene imide precursor.

A method for producing polyimide, comprising the step of converting the negative photosensitive resin composition according to any one of claims 30 to 42 to polyimide.

A method for manufacturing a hardened uneven pattern includes: (1) a step of applying a negative photosensitive resin composition according to any one of claims 30 to 42 on a substrate to form a photosensitive resin layer on the substrate; (2) a step of exposing the photosensitive resin layer, (3) a step of developing the photosensitive resin layer after exposure to form a concave-convex pattern, and (4) A step of heating the aforementioned uneven pattern to form a hardened uneven pattern.

A negative photosensitive resin composition containing the following components: (A) a polyimide precursor; (B-1) an acidic compound having two or more phenolic hydroxyl or carboxyl groups in the structure; and (C) Photopolymerization initiator.

The negative photosensitive resin composition according to claim 45, wherein the (B-1) acidic compound is selected from the group consisting of methyl gallate, methylene disalicylic acid, o-coumaric acid, and phthalic acid. At least one acidic compound in the group.

The negative-type photosensitive resin composition according to claim 45 or 46, wherein the (B-1) acidic compound is methylene disalicylic acid or o-coumaric acid.

A negative photosensitive resin composition comprising the following components: (A) a polyimide precursor; (B-2) having 1 group selected from a phenolic hydroxyl group or a carboxyl group in the structure, and having 1 More than _one acidic compound selected from the group consisting of -NH-CO-A ₁ or -CO-NH ₂ (A ₁ is an organic group having 1 to 4 carbon atoms); and (C) a photopolymerization initiator.

The negative photosensitive resin composition according to claim 48, wherein the (B-2) acidic compound is represented by the following general formula (1): [化 30] {In formula (1), A ₂ is a hydroxyl group or a carboxyl group, A ₃ is a group selected from -NH-CO-A ₁ or -CO-NH ₂ , and A ₁ is an organic group having 1 to 4 carbon atoms. A ₄ is a monovalent base, m ₂ is 1 or 2, and m ₃ is an integer of 0 to 4}.

The negative photosensitive resin composition according to any one of claims 45 to 49, wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (2) Object: [化 31] {Wherein 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, R At least one of ₁ and R ₂ is a monovalent organic group}.

The negative photosensitive resin composition according to claim 50, wherein in the general formula (2), at least one of R ₁ and R ₂ is a monovalent organic group represented by the following general formula (3): [ 32] {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 according to claim 50 or 51, wherein in the general formula (2), X ₁ includes a structure represented by the following general formula (20a): [化 33] .

The negative photosensitive resin composition according to claim 50 or 51, wherein in the general formula (2), X ₁ includes a structure represented by the following general formula (20b): [化 34] .

The negative photosensitive resin composition according to any one of claims 50 to 53, wherein in the general formula (2) above, Y ₁ includes a structure represented by the following general formula (21b) or (7): [Chemical 35] [Chemical 36] (Wherein R ₉ to R ₁₂ are a hydrogen atom or a monovalent aliphatic group having 1 to 4 carbon atoms, and may be the same as or different from each other).

The negative photosensitive resin composition according to claim 50 or 51, wherein the (A) polyimide precursor comprises a polyimide precursor having a structural unit represented by the following general formula (4): [化37] {Wherein R ₁ , R ₂ , and n ₁ are as defined above}.

The negative photosensitive resin composition according to claim 50 or 51, wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (5): 38] {Wherein R ₁ , R ₂ , and n ₁ are as defined above}.

The negative photosensitive resin composition according to any one of claims 50 to 56, wherein the (A) polyimide precursor includes both of the following general formula (4) and the following general formula (5) Structural unit: [化 39] {Wherein, R _1, R _2, and n ₁ are those defined above, _1, R _2, and the same as _a general formula R (5) are of n, or different} [Formula 40] {In the formula, R ₁ , R ₂ , and n ₁ are respectively defined above, and are the same as R ₁ , R ₂ , and n ₁ in the general formula (4), or may be different}.

The negative photosensitive resin composition according to claim 57, wherein the (A) polyfluorene imide precursor is a copolymer of a structural unit represented by the general formulae (4) and (5).

The negative photosensitive resin composition according to any one of claims 45 to 47, comprising: 100 parts by mass of the aforementioned (A) polyimide precursor, 0.1 to 30 parts by mass of the above (B-1) acidic compound 2 based on 100 parts by mass of the aforementioned (A) polyfluorene imide precursor, and 0.1 to 20 parts by mass of the aforementioned (C) photopolymerization initiator based on 100 parts by mass of the aforementioned (A) polyfluorene imide precursor.

The negative photosensitive resin composition according to claim 48 or 49, comprising: 100 parts by mass of the aforementioned (A) polyimide precursor, 0.1 to 30 parts by mass of the above (B-2) acidic compound based on 100 parts by mass of the aforementioned (A) polyfluorene imide precursor, and 0.1 to 20 parts by mass of the aforementioned (C) photopolymerization initiator based on 100 parts by mass of the aforementioned (A) polyfluorene imide precursor.

A method for producing polyimide, comprising the step of converting the negative photosensitive resin composition according to any one of claims 45 to 60 to polyimide.

A method for manufacturing a hardened uneven pattern includes: (1) a step of applying the negative photosensitive resin composition according to any one of claims 45 to 60 on a substrate to form a photosensitive resin layer on the substrate; (2) a step of exposing the photosensitive resin layer, (3) a step of developing the photosensitive resin layer after exposure to form a concave-convex pattern, and (4) A step of heating the aforementioned uneven pattern to form a hardened uneven pattern.

A negative photosensitive resin composition comprising: (A) a polyimide precursor; (B) at least one nitrogen-containing compound selected from the group consisting of a biuret compound, a carbazole compound, an indole compound, a hydantoin compound, a uracil derivative, and a barbituric acid compound; and (C) Photopolymerization initiator.

The negative-type photosensitive resin composition according to claim 63, wherein the (B) nitrogen-containing compound is at least one selected from the group consisting of a biuret compound, a carbazole compound, and an indole compound.

The negative photosensitive resin composition according to claim 63 or 64, wherein the nitrogen-containing compound (B) is a biuret compound.

The negative photosensitive resin composition according to any one of claims 63 to 65, wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (2) Object: [化 41] {Wherein 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, R At least one of ₁ and R ₂ is a monovalent organic group}.

The negative photosensitive resin composition according to claim 66, wherein in the general formula (2), at least one of R ₁ and R ₂ is a monovalent organic group represented by the following general formula (3): [ 42] {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-type photosensitive resin composition according to claim 66 or 67, wherein in the general formula (2), X ₁ includes a structure represented by the following general formula (20a): [化 43] .

The negative-type photosensitive resin composition according to claim 66 or 67, wherein in the general formula (2), X ₁ contains a structure represented by the following general formula (20b): [化 44] .

The negative-type photosensitive resin composition according to any one of claims 66 to 69, wherein in the general formula (2), Y ₁ includes a structure represented by the following general formula (21b): [化 45] .

The negative photosensitive resin composition according to claim 66 or 67, wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (4): [化46] {Wherein R ₁ , R ₂ , and n ₁ are as defined above}.

The negative photosensitive resin composition according to claim 66 or 67, wherein the (A) polyimide precursor includes a polyimide precursor having a structural unit represented by the following general formula (5): 47] {Wherein R ₁ , R ₂ , and n ₁ are as defined above}.

The negative photosensitive resin composition according to any one of claims 66 to 72, wherein the (A) polyimide precursor includes structural units represented by the following general formulae (4) and (5): 48] {Wherein, R _1, R _2, and n ₁ are those defined above, _1, R _2, and the same as _a general formula R (5) are of n, or different} [Formula 49] {In the formula, R ₁ , R ₂ , and n ₁ are respectively defined above, and are the same as R ₁ , R ₂ , and n ₁ in the general formula (4), or may be different}.

The negative photosensitive resin composition according to claim 73, wherein the (A) polyfluorene imine precursor is a copolymer of a structural unit represented by the general formulae (4) and (5).

The negative photosensitive resin composition according to any one of claims 63 to 74, comprising: 100 parts by mass of the aforementioned (A) polyimide precursor, 0.1 to 30 parts by mass of the above-mentioned (B) nitrogen-containing compound based on 100 parts by mass of the aforementioned (A) polyimide precursor, and 0.1 to 20 parts by mass of the aforementioned (C) photopolymerization initiator based on 100 parts by mass of the aforementioned (A) polyfluorene imide precursor.

A method for producing polyimide, comprising the step of converting the negative photosensitive resin composition according to any one of claims 63 to 75 to polyimide.

A method for manufacturing a hardened uneven pattern includes: (1) a step of applying the negative photosensitive resin composition according to any one of claims 63 to 75 on a substrate to form a photosensitive resin layer on the substrate; (2) a step of exposing the photosensitive resin layer, (3) a step of developing the photosensitive resin layer after exposure to form a concave-convex pattern, and (4) A step of forming a hardened uneven pattern by heating the uneven pattern.